CN113816471A - Preparation method and application of composite coating electrocatalytic electrode material - Google Patents
Preparation method and application of composite coating electrocatalytic electrode material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000007772 electrode material Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 3
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 3
- 238000004070 electrodeposition Methods 0.000 claims description 137
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 135
- 238000003756 stirring Methods 0.000 claims description 73
- 238000000151 deposition Methods 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 66
- 230000008021 deposition Effects 0.000 claims description 62
- 238000001035 drying Methods 0.000 claims description 50
- 238000005406 washing Methods 0.000 claims description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000012153 distilled water Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 230000032683 aging Effects 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 230000003064 anti-oxidating effect Effects 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- 238000010892 electric spark Methods 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000010411 cooking Methods 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910006529 α-PbO Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000012855 volatile organic compound Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 76
- 239000000463 material Substances 0.000 description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003211 malignant effect Effects 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
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- 238000005530 etching Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XGZGDYQRJKMWNM-UHFFFAOYSA-N tantalum tungsten Chemical compound [Ta][W][Ta] XGZGDYQRJKMWNM-UHFFFAOYSA-N 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- -1 titanium metal oxide Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a preparation method of a composite coating electrocatalysis electrode material, which comprises the steps of titanium substrate pretreatment, conductive underlayer preparation, antioxidant intermediate layer preparation, conductive compact intermediate layer preparation and catalyst layer preparation, wherein five steps are totally carried out to obtain the composite coating electrocatalysis electrode material with a rechecking coating. In addition, the process disclosed by the invention does not generate VOCs, and is environment-friendly and energy-saving.
Description
Technical Field
The invention relates to the field of preparation of electrode materials, in particular to a preparation method and application of a composite coating electrocatalysis electrode material.
Background
With the continuous progress of the electrochemical industry in China, electrochemical electrodes for various industrial applications are continuously appeared; from the initial development of inert graphite electrodes to various catalytically active alloy electrodes, the electrodes have gained a long, stable and enormous contribution in the electrochemical industry. The most typical meaning at present is titanium metal oxide coating electrode, which is also the most main material for supporting the industrial development, and the industrial market share is higher than 95 percent; it is widely applied to the fields of electrochemical chemical synthesis, chlor-alkali industry, chlorate production, electroplating and hydrometallurgy, sewage treatment and the like.
In order to improve the electrode performance, researchers make great efforts and researches, and find that the electrode performance, the service life, the energy efficiency and the like are related to the conductivity of an electrode material bonding layer, the bonding force between coatings, active substances on the surface of a catalyst layer and the depth of interlayer cracks; therefore, the study of characteristics from these aspects is becoming an important issue for electrode materials.
The core element of electrocatalysis is an electrocatalysis electrode material, so that a catalytic electrode material with good performance is a main reason for promoting the development of the technology.
Chinese patent publication No. CN 109402586 a reports "a corrosion-resistant and highly conductive composite coating for electrode", which is formed by depositing and sintering a copper alloy substrate in a magnetron sputtering manner; the electrode has the advantages of high manufacturing cost, thin coating, short service time and difficult batch industrialization of the manufacturing process.
Chinese patent with publication number CN 112899715A reports "a cobalt oxide nano-flake chlorine evolution electrode and its preparation method and application", which adopts a process of direct deposition of electrochemical deposition carrier; although the method avoids the generation of a large amount of organic pollutants, the catalyst anode is easy to oxidize and has unstable structure, the coating combination degree is poor, the coating is thin, the conductivity is poor, in addition, the catalyst layer has overlarge cracks, so that the catalyst electrode structure system is quickly collapsed, and the service time is short; the electrode is poor in acid and alkali resistance and limited in application range.
Disclosure of Invention
The invention aims to provide a preparation method of a composite coating electrocatalytic electrode material.
The invention solves the technical problems through the following technical scheme:
a preparation method of a composite coating electrocatalytic electrode material comprises the following steps:
(1) pretreatment of a titanium substrate:
a titanium plate is used as a substrate, and after polishing, drying, alkali liquor treatment and acid liquor treatment, high-temperature treatment under the protection of nitrogen is carried out, and high-voltage electric spark surface treatment is carried out to obtain a polar plate;
(2) preparing a conductive underlayer:
preparing an underlayer electrodeposition liquid A, wherein the underlayer electrodeposition liquid A comprises the following component formula:
transferring the bottom base layer electrodeposition liquid A into an electrodeposition reactor, performing electrodeposition on a polar plate, and cleaning and drying after electrodeposition to obtain a conductive bottom base layer plate;
(3) preparing an anti-oxidation intermediate layer:
preparing an underlayer electrodeposition liquid B, wherein the underlayer electrodeposition liquid B comprises the following component formula:
transferring the underlayer electrodeposition liquid B into an electrodeposition reactor, carrying out electrodeposition again on the conductive underlayer prepared in the step (2) in a constant-temperature water bath kettle with electromagnetic stirring, and cleaning and drying after electrodeposition to obtain an antioxidant intermediate layer plate;
(4) preparation of a conductive dense interlayer
Preparing alpha-PbO by electrodeposition method using electrodeposition liquid C2The intermediate layer comprises the following components:
NaOH 3-5moL/L
PbO 0.1-0.5moL/L
carbon black/TiN 1-2g/L
Transferring the electrodeposition liquid C into an electrodeposition reactor, carrying out electrodeposition again on the anti-oxidation layer plate prepared in the step (3) in a constant-temperature water bath kettle with electromagnetic stirring, and cleaning and drying after electrodeposition to obtain a compact oxide intermediate layer plate;
(5) preparing a catalytic layer:
preparing beta-PbO 2 by using electrodeposition solution D through an electrodeposition method, wherein the electrodeposition solution D comprises the following components:
transferring the electrodeposition liquid to an electrodeposition reactor, carrying out electrodeposition again on the compact intermediate layer plate prepared in the step (4) in a constant-temperature water bath kettle with electromagnetic stirring, introducing oxygen into a negative electrode in the electrodeposition process, and cleaning and drying after electrodeposition to obtain the catalytic layer plate.
Preferably, the method for preparing the base layer electrodeposition liquid a is as follows:
dissolving, stirring and ultrasonically dispersing the component formula of the bottom base layer electrodeposition liquid A for 30min, transferring to a constant-temperature water bath, heating and stirring for 30-60min, standing and aging for 12-24h to obtain the bottom base layer electrodeposition liquid A.
Preferably, the preparation method of the underlayer electrodeposition solution B is as follows:
dissolving, stirring and ultrasonically dispersing the component formula of the bottom base layer electrodeposition liquid B for 30min, transferring to a constant-temperature water bath, heating and stirring for 30-60min, standing and aging for 12-24h to obtain the bottom base layer electrodeposition liquid B.
Preferably, the preparation method of the electrodeposition solution C is as follows:
dissolving the electrodeposition liquid C component formula, stirring, ultrasonically dispersing for 30min, heating in a water bath, stirring for 30-60min, standing and aging for 12-24h to obtain the electrodeposition liquid C.
Preferably, the preparation method of the electrodeposition solution D is as follows:
dissolving the electrodeposition solution D, stirring, ultrasonically dispersing for 30min, heating and stirring in a water bath for 30-60min, standing and aging for 12-24h to obtain the electrodeposition solution D.
Preferably, the rare earth element solution contains any one rare earth element of La, Ce, Co and Nd or a mixed solution composed of more than two elements.
Preferably, in the step (1), the substrate is sequentially polished by 100 meshes, 500 meshes and 1000 meshes respectively to form a rough surface on the surface, and the rough surface is dried for later use;
cooking the polished titanium plate in 10% aqueous alkali for 1-2h, deoiling, and drying for later use;
steaming the titanium plate after alkali washing in 10 wt% acid solution for 1-2h, and carrying out corrosion treatment;
wherein the acid solution is any one of oxalic acid, hydrochloric acid, sulfuric acid and nitric acid or a mixed solution of more than two acid solutions;
and (3) washing the corroded titanium plate, treating for 2-6h under the condition of 500-800 ℃ nitrogen in a tubular furnace, and performing surface treatment by adopting high-voltage electric sparks to obtain the polar plate.
Preferably, in the step (2) of electro-deposition, the temperature of the water bath is controlled to be 40-50 ℃, and the deposition current density is controlled to be 0.5-1.0A/dm2The deposition time is 5-10 min;
controlling the temperature of the water bath to be 40-50 ℃ and the deposition current density to be 0.05-0.1A/dm in the electro-deposition in the step (3)2The deposition time is 0.5-1.0 h;
in the step (4), the temperature of the water bath is controlled to be 40-50 ℃ in the electro-deposition, and the deposition current density is 0.5-1.0A/dm2The deposition time is 1.0-3.0 h;
in the step (5), the temperature of the water bath is controlled to be 40-50 ℃ in the electro-deposition, and the deposition current density is 1.0-5.0A/dm2The deposition time is 1.0-2.0 h.
Preferably, after the deposition in the step (2), the cleaning and drying modes are as follows:
washing with distilled water or deionized water, and oven drying at 80-100 deg.C;
after deposition in the step (3), cleaning and drying are carried out in the following modes:
washing the anti-oxidation intermediate layer plate with distilled water or deionized water, transferring the anti-oxidation intermediate layer plate into an oven for drying at 80-100 ℃, and after drying, putting the intermediate layer plate into a muffle furnace for firing at 500-600 ℃ for 1.0 h.
After deposition in the step (4), cleaning and drying are carried out in the following modes:
washing with distilled water or deionized water, and oven drying at 80-100 deg.C;
after deposition in the step (5), cleaning and drying are carried out in the following modes:
washing the substrate by using distilled water or deionized water, and drying the substrate in an oven at the temperature of 200 ℃ and 300 ℃.
The invention also discloses the application of the preparation method of the composite coating electrocatalysis electrode material in the preparation of the catalysis electrode material.
Compared with the prior art, the invention has the following advantages:
the invention discloses a preparation method of an alloy catalytic electrode, which has the following beneficial effects:
1. the invention provides a simple and highly operable method for preparing a corrosion-resistant electrode with long service life, which adopts water as a solvent without generating volatile substances; the defects that the traditional brushing method has long process flow, VOCs pollution is generated by using an organic solvent in the production process, the working environment of workers is poor and the like are overcome.
2. The composite coating metal oxide electrode prepared by the invention has long service life, and the service life is 1A/cm in 4mol/L sulfuric acid solution2Inter-pole distanceThe invention has good stability under a 1cm reinforced deterioration test, and simultaneously has the characteristics of cheap and easily obtained raw materials.
3. The composite coating metal oxide electrode prepared by the invention has the characteristics of high mechanical strength and good activity, and can quickly reduce organic matters in wastewater and improve the biodegradability of the wastewater.
Drawings
FIG. 1 is a graph showing the enhanced lifetime of a composite coated DSA electrode in comparison with two commercially available electrode materials under a malignant condition;
FIG. 2 is an electron micrograph of a conductive dense interlayer in a comparative example of the present invention;
FIG. 3 is an electron micrograph of a catalytic layer according to a comparative example of the present invention;
FIG. 4 is an electron micrograph of a commercially available Pb/PbO2/Ti electrode material in a comparative example of the present invention
Fig. 5 is a schematic structural view of an alloy catalytic electrode prepared in a comparative example of the present invention, in which,
a: a titanium-based material B, a surface treatment coating material C, an anti-oxidation intermediate layer D, a conductive compact intermediate layer E and a high-activity catalytic coating.
FIG. 6 is a physical structure diagram of the composite coated electrocatalytic electrode material finally obtained in the example of the present invention.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
EXAMPLE 1 preparation of composite coated electrocatalytic electrode Material
Respectively polishing the titanium-based material by using 100-mesh, 500-mesh and 1000-mesh sand paper to form a certain roughness on the surface, washing the titanium-based material by using deionized water, then performing ultrasonic treatment for 30min, and airing the titanium-based material for later use;
carrying out alkali washing and oil removal on the treated base material, etching by using oxalic acid after cleaning and air drying, and heating by using high-purity nitrogen at 650 ℃ in a tubular furnace for later use after cleaning and air drying;
preparing a conductive underlayer:
the main components of the deposition solution are as follows: silver nitrate/copper chloride 0.02moL/L (total concentration of mixture), citric acid 0.1moL/L, HCl 10mL/L, TiO20.5g/L of nano particles;
the electrodeposition time is electrodeposition in a constant temperature water bath with electromagnetic stirring, wherein the water bath temperature is 40 ℃, and the deposition current density is 1.0A/dm2Deposition time 5 min. Washing the accumulated polar plate with distilled water or deionized water, and drying in oven at 80 deg.C
Preparing an anti-oxidation intermediate layer:
chloroplatinic acid 0.08moL/L, chloroiridic acid 0.01moL/L, tantalum pentachloride 0.2moL/L, ammonium metatungstate 0.1moL/L, TiO22.0g/L of particles and 0.2moL/L of citric acid;
the temperature of the electrodeposition water bath is 40 ℃, and the deposition current density is 0.1A/dm2And the deposition time is 1.0 h. And washing the deposited polar plate with distilled water or deionized water, drying in an oven at 100 ℃, and firing the dried polar plate (the anti-oxidation intermediate layer) in a muffle furnace at 500 ℃ for 1.0h to obtain the anti-oxidation intermediate layer.
Preparing an electro-deposition compact middle layer:
the main components of the deposition solution are NaOH 3.5moL/L, PbO 0.5.5 moL/L and carbon black/TiN 2g/L, the water bath temperature is 50 ℃, the deposition current density is 0.5A/dm2, and the deposition time is 3.0 h.
And washing the deposited polar plate by using distilled water or deionized water, and drying in an oven at 100 ℃ to obtain the electrodeposited compact middle layer.
Preparing a catalytic layer:
the composition of the prepared catalyst layer deposition solution is as follows: pb (NO)3)2160g/L, PTFE emulsion (60%) 5mL/L, La Ce Co total concentration 0.002moL/L, HNO30.1moL/L, 0.5moL/L citric acid, and 2g/L of nano tantalum-tungsten powder in total.
Dissolving the deposition solution, performing ultrasonic treatment, heating in water bath, stirring for 60min, aging, dissolving the deposition solution, performing ultrasonic treatment, heating in water bath, stirring for 30min, aging, and depositing a catalyst layer, wherein the water bath temperature is 40 deg.C, and the deposition current density is 3.0A ^ 4dm2The deposition time is 2.0 h; and washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 100 ℃ to obtain the composite coating electrocatalysis electrode material. The composition of the composite coated electrocatalytic electrode material is shown in fig. 5.
Example 2 preparation method of composite coating electrocatalytic electrode material
Pretreatment of titanium substrate
The adopted substrate is a titanium plate, the titanium plate is respectively polished by 100 meshes, 500 meshes and 1000 meshes, so that a certain rough surface is formed on the surface of the titanium plate, and the titanium plate is dried for later use;
cooking the polished titanium plate in a 10% aqueous alkali for 1h, performing deoiling treatment, and drying for later use;
the titanium plate after alkali washing is boiled in 10 wt% oxalic acid, hydrochloric acid, sulfuric acid, nitric acid or a mixed acid solution of a plurality of the oxalic acid, the hydrochloric acid, the sulfuric acid and the nitric acid for 2 hours for corrosion treatment;
after being washed clean and treated by a tube furnace with nitrogen at 800 ℃ for 2 hours, the surface of the tube furnace is treated by high-voltage electric sparks for standby; preparation of the conductive underlayer
Preparing an underlayer electrodeposition solution A, which mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), transferring to constant temperature water bath, heating, stirring for 30min, standing, and aging for 12 h;
transferring the solution A to an electrodeposition reactor, and performing electrodeposition in a constant-temperature water bath kettle with electromagnetic stirring, wherein the water bath temperature is 40 ℃, and the deposition current density is 0.5A/dm2Depositing for 5 min;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 80 deg.C;
preparation of an Oxidation resistant intermediate layer
Preparing an underlayer electrodeposition solution B, which mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), transferring to constant temperature water bath, heating, stirring for 60min, standing, and aging for 24 h;
transferring the solution B into an electrodeposition reactor, and performing electrodeposition in a constant-temperature water bath kettle with electromagnetic stirring, wherein the water bath temperature is 50 ℃, and the deposition current density is 0.1A/dm2The deposition time is 1.0 h;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 100 ℃;
and (4) putting the dried polar plate into a muffle furnace, and firing for 1.0h at 500 ℃ to obtain the anti-oxidation middle layer.
Preparation of a conductive dense interlayer
Preparation of alpha-PbO by electrodeposition2The intermediate layer mainly comprises the following components of electrodeposition solution C:
NaOH 5moL/L
PbO 0.5moL/L
carbon black/TiN 1g/L
Dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), heating in water bath, stirring for 60min, standing, and aging for 20 h;
transferring the solution C into an electrodeposition reactor, and electrodepositing a compact oxide intermediate layer on the prepared anti-oxidation layer in a constant-temperature water bath kettle with electromagnetic stirring; wherein the water bath temperature is 50 ℃, and the deposition current density is 1.0A/dm2The deposition time is 3.0 h;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 100 ℃ to obtain an intermediate layer;
(5) preparation of the catalytic layer
Preparation of beta-PbO by electrodeposition2The electrodeposition solution D mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), heating in water bath, stirring for 45min, standing, and aging for 18 h;
transferring the solution D to an electrodeposition reactor, and electrodepositing the catalyst layer in a constant-temperature water bath kettle with electromagnetic stirring (the prepared dense middle layer is at 50 ℃ in the water bath and the deposition current density is 4.0A/dm)2Depositing for 2.0h, and introducing oxygen into the cathode;
and washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 200 ℃ to obtain the catalytic layer, thus obtaining the composite coating electrocatalysis electrode material.
EXAMPLE 3 preparation of composite coated electrocatalytic electrode Material
Pretreatment of titanium substrate
The adopted substrate is a titanium plate, the titanium plate is respectively polished by 100 meshes, 500 meshes and 1000 meshes, so that a certain rough surface is formed on the surface of the titanium plate, and the titanium plate is dried for later use;
cooking the polished titanium plate in a 10% aqueous alkali for 2h, performing deoiling treatment, and drying for later use;
the titanium plate after alkali washing is boiled in 10 wt% oxalic acid, hydrochloric acid, sulfuric acid, nitric acid or a mixed acid solution of a plurality of the oxalic acid, the hydrochloric acid, the sulfuric acid and the nitric acid for 2 hours for corrosion treatment;
after being washed clean and treated by nitrogen in a tube furnace at 500 ℃ for 2 hours, the surface of the tube furnace is treated by high-voltage electric sparks for standby; preparation of the conductive underlayer
Preparing an underlayer electrodeposition solution A, which mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), transferring to constant temperature water bath, heating, stirring for 60min, standing, and aging for 24 h;
transferring the solution A to an electrodeposition reactor, and performing electrodeposition in a constant-temperature water bath kettle with electromagnetic stirring, wherein the water bath temperature is 50 ℃, and the deposition current density is 1.0A/dm2Depositing for 10 min;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 100 deg.C;
preparation of an Oxidation resistant intermediate layer
Preparing an underlayer electrodeposition solution B, which mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), transferring to constant temperature water bath, heating and stirring for 60min, standing and aging for 12 h;
transferring the solution B into an electrodeposition reactor, and performing electrodeposition in a constant-temperature water bath kettle with electromagnetic stirring, wherein the water bath temperature is 50 ℃, and the deposition current density is 0.05A/dm2The deposition time is 1.0 h;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 100 ℃;
and (4) putting the dried polar plate into a muffle furnace, and firing at 600 ℃ for 1.0h to obtain the anti-oxidation middle layer.
Preparation of a conductive dense interlayer
Preparation of alpha-PbO by electrodeposition2The intermediate layer mainly comprises the following components of electrodeposition solution C:
NaOH 5moL/L
PbO 0.1moL/L
carbon black/TiN 1g/L
Dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), heating in water bath, stirring for 60min, standing, and aging for 20 h;
transferring the solution C into an electrodeposition reactor, and electrodepositing a compact oxide intermediate layer on the prepared anti-oxidation layer in a constant-temperature water bath kettle with electromagnetic stirring;wherein the water bath temperature is 50 ℃, and the deposition current density is 0.8A/dm2The deposition time is 2.0 h;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 90 ℃ to obtain an intermediate layer;
preparation of the catalytic layer
Preparation of beta-PbO by electrodeposition2The electrodeposition solution D mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), heating in water bath, stirring for 60min, standing, and aging for 20 h;
transferring the solution D to an electrodeposition reactor, and electrodepositing the catalyst layer in a constant-temperature water bath kettle with electromagnetic stirring (the prepared dense middle layer is at 50 ℃ in the water bath and the deposition current density is 5.0A/dm)2Depositing for 2.0h, and introducing oxygen into the cathode;
and washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 300 ℃ to obtain a catalytic layer, thus obtaining the composite coating electrocatalysis electrode material.
Example 4 preparation of composite coated electrocatalytic electrode materials
Pretreatment of titanium substrate
The adopted substrate is a titanium plate, the titanium plate is respectively polished by 100 meshes, 500 meshes and 1000 meshes, so that a certain rough surface is formed on the surface of the titanium plate, and the titanium plate is dried for later use;
cooking the polished titanium plate in a 10% aqueous alkali for 1.5h, performing deoiling treatment, and drying for later use;
the titanium plate after alkali washing is boiled in 10 wt% oxalic acid, hydrochloric acid, sulfuric acid, nitric acid or a mixed acid solution of a plurality of the oxalic acid, the hydrochloric acid, the sulfuric acid and the nitric acid for 1.5 hours, and then corrosion treatment is carried out;
after washing and treating for 5 hours in a tubular furnace at 500 ℃ by nitrogen, performing surface treatment by adopting high-voltage electric sparks for later use; preparation of the conductive underlayer
Preparing an underlayer electrodeposition solution A, which mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), transferring to constant temperature water bath, heating and stirring for 50min, standing and aging for 20 h;
transferring the solution A to an electrodeposition reactor, and performing electrodeposition in a constant-temperature water bath kettle with electromagnetic stirring, wherein the water bath temperature is 45 ℃, and the deposition current density is 1.0A/dm2The deposition time is 8 min;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 90 deg.C;
preparation of an Oxidation resistant intermediate layer
Preparing an underlayer electrodeposition solution B, which mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), transferring to constant temperature water bath, heating and stirring for 50min, standing and aging for 20 h;
transferring the solution B into an electrodeposition reactor, and performing electrodeposition in a constant-temperature water bath kettle with electromagnetic stirring, wherein the water bath temperature is 45 ℃, and the deposition current density is 0.08A/dm2The deposition time is 1.0 h;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 100 ℃;
and (4) putting the dried polar plate into a muffle furnace, and firing at 550 ℃ for 1.0h to obtain the anti-oxidation middle layer.
Preparation of a conductive dense interlayer
Preparation of alpha-PbO by electrodeposition2The intermediate layer mainly comprises the following components of electrodeposition solution C:
NaOH 5moL/L
PbO 0.5moL/L
carbon black/TiN 2g/L
Dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), heating in water bath, stirring for 60min, standing, and aging for 20 h;
transferring the solution C into an electrodeposition reactor, and electrodepositing a compact oxide intermediate layer on the prepared anti-oxidation layer in a constant-temperature water bath kettle with electromagnetic stirring; wherein the water bath temperature is 45 ℃, and the deposition current density is 1.0A/dm2The deposition time is 2.0 h;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 100 ℃ to obtain an intermediate layer;
preparation of the catalytic layer
Preparation of beta-PbO by electrodeposition2The electrodeposition solution D mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), heating in water bath, stirring for 50min, standing, and aging for 12 h;
transferring the solution D to an electrodeposition reactor, and electrodepositing the catalyst layer in a constant-temperature water bath kettle with electromagnetic stirring (the prepared dense middle layer is at 50 ℃ in the water bath and the deposition current density is 4.0A/dm)2Depositing for 2.0h, and introducing oxygen into the cathode;
and washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 250 ℃ to obtain a catalytic layer, thereby obtaining the composite coating electrocatalysis electrode material.
EXAMPLE 5 preparation of composite coated electrocatalytic electrode Material
Pretreatment of titanium substrate
The adopted substrate is a titanium plate, the titanium plate is respectively polished by 100 meshes, 500 meshes and 1000 meshes, so that a certain rough surface is formed on the surface of the titanium plate, and the titanium plate is dried for later use;
cooking the polished titanium plate in a 10% aqueous alkali for 1.5h, performing deoiling treatment, and drying for later use;
the titanium plate after alkali washing is boiled in 10 wt% oxalic acid, hydrochloric acid, sulfuric acid, nitric acid or a mixed acid solution of a plurality of the oxalic acid, the hydrochloric acid, the sulfuric acid and the nitric acid for 1.5 hours, and then corrosion treatment is carried out;
after washing and treating for 3 hours in a tubular furnace at 600 ℃ by nitrogen, performing surface treatment by adopting high-voltage electric sparks for later use; preparation of the conductive underlayer
Preparing an underlayer electrodeposition solution A, which mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), transferring to constant temperature water bath, heating and stirring for 50min, standing and aging for 24 h;
transferring the solution A to an electrodeposition reactor, and performing electrodeposition in a constant-temperature water bath kettle with electromagnetic stirring, wherein the water bath temperature is 50 ℃, and the deposition current density is 1.0A/dm2Depositing for 10 min;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 100 deg.C;
preparation of an Oxidation resistant intermediate layer
Preparing an underlayer electrodeposition solution B, which mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), transferring to constant temperature water bath, heating, stirring for 30min, standing, and aging for 18 h;
transferring the solution B into an electrodeposition reactor, and performing electrodeposition in a constant-temperature water bath kettle with electromagnetic stirring, wherein the water bath temperature is 40 ℃, and the deposition current density is 0.08/dm2The deposition time is 1.0 h;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 90 ℃;
and (4) putting the dried polar plate into a muffle furnace to be fired for 1.0h at the temperature of 580 ℃, thus obtaining the anti-oxidation middle layer.
Preparation of a conductive dense interlayer
Preparation of alpha-PbO by electrodeposition2The intermediate layer mainly comprises the following components of electrodeposition solution C:
NaOH 4moL/L
PbO 0.5moL/L
carbon black/TiN 1.5g/L
Dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), heating in water bath, stirring for 60min, standing, and aging for 20 h;
transferring the solution C into an electrodeposition reactor, and electrodepositing a compact oxide intermediate layer on the prepared anti-oxidation layer in a constant-temperature water bath kettle with electromagnetic stirring; wherein the water bath temperature is 50 ℃, and the deposition current density is 0.8A/dm2The deposition time is 2.0 h;
washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 100 ℃ to obtain an intermediate layer;
preparation of the catalytic layer
The beta-PbO 2 is prepared by electrodeposition, and the electrodeposition solution D mainly comprises the following components:
dissolving the above medicinal materials, stirring, ultrasonically dispersing for 30min (30 deg.C), heating in water bath, stirring for 50min, standing, and aging for 12 h;
transferring the solution D to an electrodeposition reactor, and electrodepositing the catalyst layer (the prepared compact middle layer is in a constant-temperature water bath kettle with electromagnetic stirring; the catalyst layer is formed by the reaction of the prepared compact middle layer and the solution DThe temperature of the water bath is 45 ℃, and the deposition current density is 3A/dm2Depositing for 1.5 times, and introducing oxygen into the cathode;
and washing the deposited polar plate with distilled water or deionized water, and drying in an oven at 300 ℃ to obtain the catalytic layer. Obtaining the composite coating electrocatalysis electrode material.
Comparative examples
Firstly, the electrode material prepared in the embodiment 1 of the invention and two common electrode materials in the market are tested under the malignant condition, and the test conditions are as follows: 4mol/L sulfuric acid solution, 1.0A/cm2The distance between the electrodes is 10mm, the temperature is 50 ℃,
the test results are shown in fig. 1, and it can be seen from the data disclosed in fig. 1 that:
the electrode material prepared by the preparation method disclosed by the invention has more stable discharge performance and longer service life.
Secondly, electron microscope testing:
the morphology characteristics of the conductive compact intermediate layer prepared in the embodiment 1 of the present invention are observed by an electron microscope, the crystal image obtained by the electron microscope is shown in fig. 2, the morphology characteristics of the catalytic layer (composite coating electrocatalytic electrode material) prepared in the embodiment 1 of the present invention are observed by an electron microscope, and the crystal image obtained by the electron microscope is shown in fig. 3; conventional Pb/PbO is commercially available2The comparison of the/Ti electrode material shown in FIG. 4 shows that:
the electrode material disclosed by the invention is completely different from the conventional electrode material sold in the market in shape, and belongs to a completely different electrode material.
The shape of the final electrode material obtained by the present invention is shown in fig. 6.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a composite coating electrocatalytic electrode material is characterized by comprising the following steps:
(1) pretreatment of a titanium substrate:
a titanium plate is used as a substrate, and after polishing, drying, alkali liquor treatment and acid liquor treatment, high-temperature treatment under the protection of nitrogen is carried out, and high-voltage electric spark surface treatment is carried out to obtain a polar plate;
(2) preparing a conductive underlayer:
preparing an underlayer electrodeposition liquid A, wherein the underlayer electrodeposition liquid A comprises the following component formula:
transferring the bottom base layer electrodeposition liquid A into an electrodeposition reactor, performing electrodeposition on a polar plate, and cleaning and drying after electrodeposition to obtain a conductive bottom base layer plate;
(3) preparing an anti-oxidation intermediate layer:
preparing an underlayer electrodeposition liquid B, wherein the underlayer electrodeposition liquid B comprises the following component formula:
transferring the underlayer electrodeposition liquid B into an electrodeposition reactor, carrying out electrodeposition again on the conductive underlayer prepared in the step (2) in a constant-temperature water bath kettle with electromagnetic stirring, and cleaning and drying after electrodeposition to obtain an antioxidant intermediate layer plate;
(4) preparing a conductive compact middle layer:
preparing alpha-PbO by electrodeposition method using electrodeposition liquid C2The intermediate layer comprises the following components:
NaOH 3-5moL/L
PbO 0.1-0.5moL/L
carbon black/TiN 1-2g/L
Transferring the electrodeposition liquid C into an electrodeposition reactor, carrying out electrodeposition again on the anti-oxidation layer plate prepared in the step (3) in a constant-temperature water bath kettle with electromagnetic stirring, and cleaning and drying after electrodeposition to obtain a compact oxide intermediate layer plate;
(5) preparing a catalytic layer:
preparing beta-PbO 2 by using electrodeposition solution D through an electrodeposition method, wherein the electrodeposition solution D comprises the following components:
transferring the electrodeposition liquid to an electrodeposition reactor, carrying out electrodeposition again on the compact intermediate layer plate prepared in the step (4) in a constant-temperature water bath kettle with electromagnetic stirring, introducing oxygen into a negative electrode in the electrodeposition process, and cleaning and drying after electrodeposition to obtain the composite coating electrocatalysis electrode material.
2. The method for preparing the composite coating electrocatalytic electrode material as set forth in claim 1, wherein the method for preparing the base layer electrodeposition solution a is as follows:
dissolving, stirring and ultrasonically dispersing the component formula of the bottom base layer electrodeposition liquid A for 30min, transferring to a constant-temperature water bath, heating and stirring for 30-60min, standing and aging for 12-24h to obtain the bottom base layer electrodeposition liquid A.
3. The method for preparing the composite coating electrocatalytic electrode material as set forth in claim 1, wherein the method for preparing the base layer electrodeposition solution B is as follows:
dissolving, stirring and ultrasonically dispersing the component formula of the bottom base layer electrodeposition liquid B for 30min, transferring to a constant-temperature water bath, heating and stirring for 30-60min, standing and aging for 12-24h to obtain the bottom base layer electrodeposition liquid B.
4. The method for preparing the composite coating electrocatalytic electrode material as set forth in claim 1, wherein the electrodeposition bath C is prepared by the following method:
dissolving the electrodeposition liquid C component formula, stirring, ultrasonically dispersing for 30min, heating in a water bath, stirring for 30-60min, standing and aging for 12-24h to obtain the electrodeposition liquid C.
5. The method for preparing the composite coating electrocatalytic electrode material as set forth in claim 1, wherein the electrodeposition solution D is prepared by:
dissolving the electrodeposition solution D, stirring, ultrasonically dispersing for 30min, heating and stirring in a water bath for 30-60min, standing and aging for 12-24h to obtain the electrodeposition solution D.
6. The preparation method of the composite coating electrocatalytic electrode material as set forth in claim 1, wherein the rare earth element solution is a mixed solution containing any one of rare earth elements of La, Ce, Co and Nd or two or more elements.
7. The preparation method of the composite coating electrocatalytic electrode material as set forth in claim 1, wherein in the step (1), the substrate is sequentially polished with 100 mesh, 500 mesh and 1000 mesh, respectively, to form a rough surface on the surface, and the rough surface is dried for standby;
cooking the polished titanium plate in 10% aqueous alkali for 1-2h, deoiling, and drying for later use;
steaming the titanium plate after alkali washing in 10 wt% acid solution for 1-2h, and carrying out corrosion treatment;
wherein the acid solution is any one of oxalic acid, hydrochloric acid, sulfuric acid and nitric acid or a mixed solution of more than two acid solutions;
and (3) washing the corroded titanium plate, treating for 2-6h under the condition of 500-800 ℃ nitrogen in a tubular furnace, and performing surface treatment by adopting high-voltage electric sparks to obtain the polar plate.
8. The method for preparing the composite-coated electrocatalytic electrode material as set forth in claim 1, wherein in the step (2) of electrodeposition, the temperature of the water bath is controlled to be 40-50 ℃, and the deposition current density is controlled to be 0.5-1.0A/dm2The deposition time is 5-10 min;
controlling the temperature of the water bath to be 40-50 ℃ in the electrodeposition in the step (3), and controlling the deposition current density to be 0.05-0.1A/dm2The deposition time is 0.5-1.0 h;
in the step (4), the temperature of the water bath is controlled to be 40-50 ℃ in the electro-deposition, and the deposition current density is 0.5-1.0A/dm2The deposition time is 1.0-3.0 h;
in the step (5), the temperature of the water bath is controlled to be 40-50 ℃ in the electro-deposition, and the deposition current density is 1.0-5.0A/dm2The deposition time is 1.0-2.0 h.
9. The preparation method of the composite coating electrocatalytic electrode material as set forth in claim 1, wherein after the deposition in the step (2), the cleaning and drying manners are as follows:
washing with distilled water or deionized water, and oven drying at 80-100 deg.C;
after deposition in the step (3), cleaning and drying are carried out in the following modes:
washing the anti-oxidation intermediate layer plate with distilled water or deionized water, transferring the anti-oxidation intermediate layer plate into an oven for drying at 80-100 ℃, and after drying, putting the intermediate layer plate into a muffle furnace for firing at 500-600 ℃ for 1.0 h.
After deposition in the step (4), cleaning and drying are carried out in the following modes:
washing with distilled water or deionized water, and oven drying at 80-100 deg.C;
after deposition in the step (5), cleaning and drying are carried out in the following modes:
washing the substrate by using distilled water or deionized water, and drying the substrate in an oven at the temperature of 200 ℃ and 300 ℃.
10. Use of a method of making a composite coated electrocatalytic electrode material according to any one of claims 1 to 9 in the preparation of a catalytic electrode material.
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