CN113755873B - Cathode for seawater electrolysis and preparation method thereof - Google Patents
Cathode for seawater electrolysis and preparation method thereof Download PDFInfo
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- CN113755873B CN113755873B CN202111072648.6A CN202111072648A CN113755873B CN 113755873 B CN113755873 B CN 113755873B CN 202111072648 A CN202111072648 A CN 202111072648A CN 113755873 B CN113755873 B CN 113755873B
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- 239000013535 sea water Substances 0.000 title claims abstract description 32
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 105
- 239000011248 coating agent Substances 0.000 claims abstract description 101
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000010936 titanium Substances 0.000 claims abstract description 69
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 230000004584 weight gain Effects 0.000 claims abstract description 6
- 235000019786 weight gain Nutrition 0.000 claims abstract description 6
- 150000002909 rare earth metal compounds Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 29
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 17
- 238000005498 polishing Methods 0.000 claims description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 9
- 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 8
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 8
- 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 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005238 degreasing Methods 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
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 230000008569 process Effects 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 230000001590 oxidative effect Effects 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 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
- 230000008901 benefit Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000002035 prolonged 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
- 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
- 239000008199 coating composition Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011159 matrix 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
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 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
Classifications
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- 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, the surface of a pretreated titanium plate is coated with a cathode coating liquid, and after stepwise thermal oxidation treatment, the weight gain of metal oxide reaching the titanium plate reaches 0.1-5g/m 2 The cathode is prepared; the cathode coating liquid is one or more of rare earth metal compound or valve metal compound solution. 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.
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 electrolytic preparation of chlorine from seawater is a widely used technical means for preventing marine biofouling at present. Generating ClO by direct current electrolysis of seawater - The microorganism in the seawater is killed, and the service lives of pipelines and operation equipment in the seawater can be effectively prolonged. In the process of preparing sodium hypochlorite by seawater electrolysis, a titanium coating anode is generally used as an anode and a titanium plate is generally used as a cathode. Since seawater contains Ca in addition to sodium chloride 2+ 、Mg 2+ Plasma metal ion impurities, which form scale that is deposited continuously on the cathode during electrolysis, affect the catalytic performance of the electrode.
In order to reduce the deposition of impurities, the cathode is generally polished to make the rough surface of the cathode in a smooth mirror surface state, thereby reducing the surface of the substrate and Ca-containing 2+ 、Mg 2+ The bonding force of the plasma metal ion scale is not easy to be firmly adsorbed on the surface of the cathode, and part of the scale can be washed away by flowing seawater. However, the treatment mode increases the reaction voltage between the cathode and the anode, and simultaneously, the use of the polished cathode only can 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 periodic pickling mode to maintain the normal operation of the electrolysis process.
The rare earth metal is the general name of 17 elements of scandium, yttrium and lanthanide series in the III B group of the periodic table, and in the heat treatment, the rare earth metal has the functions of purifying, activating and promoting the decomposition of the penetrating agent and the diffusion of atoms on the surface of the metal material and the medium around the surface of the metal material, so that the property of the surface of the metal can be changed, and the binding force between the matrix and the active layer can be increased.
Titanium and titanium alloys are conductive when used as a cathode in brine, and are immediately nonconductive when used as an anode, and because of their valve-like properties, such metals are often referred to as valve-type metals, which also include tantalum, tantalum alloys, zirconium alloys, niobium and niobium alloys, and their use in the preparation of cathode materials has some researches.
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 has certain significance by combining the related properties of rare earth metal and valve metal.
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 not only can delay the scaling condition on the surface of the cathode, but also can reduce the reaction voltage between the cathode and the anode, prolongs the pickling period of the electrode and reduces the energy consumption.
The technical scheme of the invention is as follows:
a cathode for seawater electrolysis, characterized in that: coating cathode coating liquid on the surface of the pretreated titanium plate, and carrying out stepwise thermal oxidation treatment until the weight gain of the metal oxide of the titanium plate reaches 0.1-5g/m 2 The cathode is obtained.
The cathode coating liquid is rare earth metal compound solution and/or valve 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) Pretreatment of a titanium plate;
2) Uniformly coating cathode coating liquid on the working surface of the titanium plate to be coated;
3) Step-by-step thermal oxidation treatment: drying the coated titanium plate at 90-180deg.C for 10-30 min, sintering at 200-700deg.C (preferably 400-590 deg.C) for 15-90 min, taking out, cooling to room temperature, and repeating the above coating, drying and sintering processes until the weight gain of the metal oxide of the titanium plate reaches 0.1-5g/m 2 The cathode is obtained.
As a preferable technical scheme:
in the step 1), the pretreatment of the titanium plate is as follows: polishing the titanium plate.
The polishing process comprises the following steps: polishing the two sides of the titanium plate to make the surface of the titanium plate show a smooth mirror surface, degreasing the titanium plate by alkali liquor and absolute ethyl alcohol in sequence after polishing, cleaning by distilled water, drying in a constant temperature drying oven at 100 ℃, and cooling for later use.
In the step 2), the cathode coating liquid 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, 0.3-5.0g/L niobium pentachloride. Wherein, organic solvent (such as n-butanol, absolute ethanol, etc.) is added into the cathode coating liquid containing tantalum pentachloride and/or niobium pentachloride.
The cathode 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, 0.5-3.0g/L niobium pentachloride.
The first coated cathode coating liquid is rare earth metal compound solution.
In step 3): the step-by-step thermal oxidation treatment adopts three-six steps of thermal oxidation treatment, the cathode coating liquid used in each step of thermal oxidation treatment is the same or different, and each step of thermal oxidation treatment is coated with 1-10 times of cathode coating liquid.
Drawings
FIG. 1 shows the variation of the sea water electrolyzer voltage with time.
Detailed Description
The preparation method of the cathode for seawater electrolysis comprises the following specific steps:
1) Pretreatment of a titanium plate:
2) Uniformly coating cathode coating liquid on the working surface of the titanium plate to be coated;
3) Step-by-step thermal oxidation treatment: drying the coated titanium plate at 90-180deg.C for 10-30 min, sintering at 200-700deg.C for 15-90 min, taking out, cooling to room temperature, and repeating the above coating, drying and sintering processes until the weight gain of the metal oxide of the titanium plate reaches 0.1-5g/m 2 The cathode is obtained.
Example 1
Pretreatment of a titanium plate:
firstly, polishing the two sides of a titanium plate by using a grinding wheel and a polishing wheel in sequence, then, degreasing the titanium plate by using alkali liquor and absolute ethyl alcohol in sequence, then, cleaning by using distilled water, drying in a constant-temperature drying oven at 100 ℃, and determining one surface to be a surface to be coated after cooling.
Preparing and coating cathode coating liquid:
coating a first coating solution of 0.3g/L cerium chloride solution on a pretreated titanium plate, drying at 150 ℃ for 10 minutes, taking out, and thermally oxidizing at 450 ℃ for 30 minutes;
the second coating liquid is 2g/L titanium trichloride solution, the coating liquid is coated on the titanium plate coated with the first coating liquid, then the titanium plate is dried for 10 minutes at 150 ℃, taken out and thermally oxidized for 30 minutes at 500 ℃, and the process is repeated for 5 times;
coating the third coating liquid on the titanium plate coated with the second coating liquid by using a mixed solution of 3g/L of titanium trichloride and 1g/L of n-butanol of tantalum pentachloride, 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 solution IV on the titanium plate coated with the coating solution III by using an absolute ethanol mixed solution of 5g/L of titanium trichloride, 1.5g/L of zirconium tetrachloride and 1g/L of niobium pentachloride, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 530 ℃ for 30 minutes, and repeating the process for 6 times before finishing;
the final treatment coating liquid is No. four coating liquid, the coating process is unchanged, the coating liquid is dried at 150 ℃ for 10 minutes, and the coating liquid is taken out and then is subjected to thermal oxidation at 550 ℃ for 90 minutes. The increment of the metal oxide on the final titanium plate reaches 0.4+/-0.01 g/m 2 Obtaining the required cathode.
Example 2
The pretreatment process of the titanium plate was the same as in example 1.
Preparing and coating cathode coating liquid:
the first coating liquid is a mixed solution containing 0.2g/L cerium chloride and 0.1g/L praseodymium chloride, the coating liquid is coated on a pretreated titanium plate, then dried at 150 ℃ for 10 minutes, taken out and thermally oxidized at 450 ℃ for 30 minutes;
coating the second coating solution with 3g/L titanium trichloride solution on the titanium plate coated with the first coating 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 third coating solution which is a mixed solution of 3.5g/L titanium trichloride and 1g/L zirconium tetrachloride on the titanium plate coated with the second coating solution, drying for 10 minutes at 150 ℃, taking out, thermally oxidizing for 30 minutes at 520 ℃, and repeating the process for 6 times;
coating the coating solution IV on the titanium plate coated with the coating solution III by using an absolute ethanol mixed solution of 4g/L of titanium trichloride, 1g/L of zirconium tetrachloride and 1.5g/L of niobium pentachloride, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 530 ℃ for 30 minutes, and repeating the process 7 times before finishing;
the final treatment coating liquid is No. four coating liquid, the coating process is unchanged, the coating liquid is dried at 150 ℃ for 10 minutes, and the coating liquid is taken out and then is subjected to thermal oxidation at 550 ℃ for 90 minutes. The increment of the metal oxide on the final titanium plate reaches 0.4+/-0.01 g/m 2 Obtaining the required cathode.
Example 3
The pretreatment process of the titanium plate was the same as in example 1.
Preparing and coating cathode coating liquid:
the first coating liquid is a mixed solution containing 0.25g/L cerium chloride and 0.5g/L lanthanum chloride, the coating liquid is coated on a pretreated titanium plate, then the titanium plate is dried at 150 ℃ for 10 minutes, and the titanium plate is taken out and then is thermally oxidized at 450 ℃ for 30 minutes;
the second coating liquid is 3g/L titanium trichloride solution, the coating liquid is coated on the titanium plate coated with the first coating liquid, then the titanium plate is dried for 10 minutes at 150 ℃, taken out and thermally oxidized for 30 minutes at 500 ℃, and the process is repeated for 5 times;
coating the coating solution III on the titanium plate coated with the coating solution II by using a mixed solution of 4g/L of titanium trichloride and 0.5g/L of zirconium tetrachloride, drying at 150 ℃ for 10 minutes, taking out, thermally oxidizing at 520 ℃ for 30 minutes, and repeating the process for 8 times;
coating the coating solution IV on the titanium plate coated with the coating solution III by using a mixed solution of 4.5g/L titanium trichloride and 1.5g/L zirconium tetrachloride, 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 treatment coating liquid is No. four coating liquid, the coating process is unchanged, the coating liquid is dried at 150 ℃ for 10 minutes, and the coating liquid is taken out and then is subjected to thermal oxidation at 550 ℃ for 90 minutes. The increment of the metal oxide on the final titanium plate reaches 0.6+/-0.02 g/m 2 Obtaining the required cathode.
Example 4
The pretreatment process of the titanium plate was the same as in example 1.
Preparing and coating cathode coating liquid:
coating a first coating solution of 0.25g/L cerium chloride solution on a pretreated titanium plate, drying at 150 ℃ for 10 minutes, taking out, and thermally oxidizing at 450 ℃ for 30 minutes;
coating the second coating solution on the titanium plate coated with the first coating solution by using a mixed solution of 2g/L of titanium trichloride and 1.5g/L of n-butanol of tantalum pentachloride, drying at 150 ℃ for 10 minutes, taking out, performing thermal oxidation at 500 ℃ for 30 minutes, and repeating the process for 5 times;
coating the third coating liquid with 2.5g/L titanium trichloride solution on the titanium plate coated with the second coating liquid, 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 solution on the titanium plate coated with the coating solution III by using an n-butanol mixed solution of 3g/L of titanium trichloride and 2.0g/L of tantalum pentachloride, drying at 150 ℃ for 10 minutes, taking out, performing thermal oxidation at 530 ℃ for 30 minutes, and repeating the process 6 times;
coating the coating solution No. five on the titanium plate coated with the coating solution No. four by using a titanium trichloride solution with the concentration of 4g/L, 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 treatment coating liquid is No. five coating liquid, the coating process is unchanged, the coating liquid is dried at 150 ℃ for 10 minutes, and the coating liquid is taken out and is subjected to thermal oxidation at 550 ℃ for 90 minutes. The increment of the metal oxide on the final titanium plate reaches 0.6+/-0.02 g/m 2 Obtaining the required cathode.
Comparative example 1
Sequentially polishing the two sides of the titanium plate by using a grinding wheel and a polishing wheel, sequentially degreasing the titanium plate by using alkali liquor and absolute ethyl alcohol, cleaning by using distilled water, drying in a constant-temperature drying oven at 100 ℃, and cooling to obtain the titanium plate.
Comparative example 2
Sequentially degreasing the titanium plate by using alkali liquor and absolute ethyl alcohol, cleaning by using distilled water, drying in a constant-temperature drying oven at 100 ℃, and cooling to obtain the finished product.
Parameters of seawater electrolysis:
the total salinity is about 3.5%, the natural seawater containing about 2.5% NaCl is about 1500A/m 2 Polar distance at 25±1 ℃): 2mm.
The assembly mode of the electrolytic cell is as follows:
six titanium anodes with the same preparation process and coating composition are prepared, wherein four anodes and cathodes prepared in examples 1-4 respectively form an electrolytic cell, the other two anodes and cathodes prepared in comparative examples 1 and 2 respectively form an electrolytic cell, and the six groups of electrolytic cells are powered in series for electrolysis, and the change condition of cell voltage is recorded.
The above prepared examples and comparative examples were tested according to the above test methods, with the following results:
as shown in FIG. 1, in the seawater electrolysis test, the cell voltages of examples 1-4 and comparative examples 1-2 increased substantially linearly, the rate of rise of comparative example 2 was maximum, examples 1-4 were much smaller than comparative example 2, and comparative example 1 was slightly larger than examples 1-4.
As is clear from a comparison of the rate of rise of the cell voltages of comparative example 1 and comparative example 2, the polishing treatment can reduce Ca 2+ 、Mg 2+ Binding force between plasma metal ion scale and the surface of the cathode, and delaying scaling of the cathode; by comparing the cell voltages of comparative example 1 and examples 1-4, it is known that preparing a cathode catalytic coating on the surface of the polished substrate can increase the catalytic activity of the cathode and reduce the reaction voltage.
The cathode reaction surface was observed visually, and in examples 1 to 4, ca was hardly deposited 2+ 、Mg 2+ Scale of plasma metal, a small amount of scale was found at some points of comparative example 1, and some areas of comparative example 2 had some amount of flaky scale.
As is clear from FIG. 1, the initial cell voltage of comparative example 2 was low, but Ca was contained therein 2+ 、Mg 2+ The cell voltage increase rate during electrolysis of plasma metal ions in seawater was significantly higher than in comparative example 1 and examples 1 to 4, since the surface of comparative example 2 had a certain roughness and contained Ca 2+ 、Mg 2+ Scale from plasma is more easily deposited on the surface of the cathode prepared in comparative example 2, and is tightly combined, so that the capability of the flowing seawater for removing the scale on the surface of the cathode is limited, the scale is continuously accumulated along with 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 is gradually not existed along with the long-term electrolysis.
In seawater electrolysis, the cell voltage of examples 1-4 was increased at a slow rate compared with comparative examples 1-2, and the advantages of anti-impurity deposition and catalytic performance had been significantly superior to those of comparative examples 1-2 as long-term electrolysis proceeded.
In seawater electrolysis, the substrate is subjected to polishing treatment, and although the cell voltage is higher, the formation of scale on the surface of the cathode can be delayed, the pickling period is prolonged, and the preparation of a catalytic coating on the polished titanium substrate as the cathode can reduce the cell voltage of the reaction and reduce the energy consumption. In comprehensive consideration, the preparation of a catalytic coating on a polished titanium substrate as a cathode is an effective means for delaying scaling and reducing energy consumption in the long-term process of preparing chlorine by seawater electrolysis.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Furthermore, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the present invention.
Claims (7)
1. A cathode for seawater electrolysis, characterized in that: coating cathode coating liquid on the surface of the pretreated titanium plate, and carrying out stepwise thermal oxidation treatment until the weight gain of the metal oxide of the titanium plate reaches 0.1-5g/m 2 The cathode is prepared;
the pretreatment of the titanium plate comprises the following steps: polishing the titanium plate;
the cathode coating liquid 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, 0.3-5.0g/L niobium pentachloride.
2. A method for preparing a cathode for seawater electrolysis according to claim 1, comprising the specific steps of:
1) Pretreatment of a titanium plate;
2) Uniformly coating cathode coating liquid on the working surface of the titanium plate to be coated;
3) Step-by-step thermal oxidation treatment: drying the coated titanium plate at 90-180deg.C for 10-30 min, sintering at 200-700deg.C for 15-90 min, taking out, cooling to room temperature, and repeating the above stepsCoating, drying and sintering until the weight gain of the metal oxide of the titanium plate reaches 0.1-5g/m 2 The cathode is obtained.
3. The method for preparing a cathode for seawater electrolysis according to claim 2, wherein the polishing process is as follows: polishing the two sides of the titanium plate to make the surface of the titanium plate show a smooth mirror surface, degreasing the titanium plate by alkali liquor and absolute ethyl alcohol in sequence after polishing, cleaning by distilled water, drying in a constant temperature drying oven at 100 ℃, and cooling for later use.
4. The method for preparing a cathode for seawater electrolysis according to claim 2, wherein in the steps 2) and 3), the cathode coating liquid used 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, 0.5-3.0g/L niobium pentachloride.
5. The method for producing a cathode for seawater electrolysis according to claim 2, wherein: the first coated cathode coating liquid is rare earth metal compound solution.
6. The method for producing a cathode for seawater electrolysis according to claim 2, wherein in step 3): the step-by-step thermal oxidation treatment adopts three-six steps of thermal oxidation treatment, the cathode coating liquid used in each step of thermal oxidation treatment is the same or different, and each step of thermal oxidation treatment is coated with 1-10 times of cathode coating liquid.
7. The method for producing a cathode for seawater electrolysis according to claim 2, 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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| 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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