CN117004992B - Preparation method of high-strength graphite anode - Google Patents
Preparation method of high-strength graphite anode Download PDFInfo
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- CN117004992B CN117004992B CN202311039390.9A CN202311039390A CN117004992B CN 117004992 B CN117004992 B CN 117004992B CN 202311039390 A CN202311039390 A CN 202311039390A CN 117004992 B CN117004992 B CN 117004992B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 99
- 239000010439 graphite Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007770 graphite material Substances 0.000 claims abstract description 64
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 238000000576 coating method Methods 0.000 claims abstract description 48
- CPOIJYXGUPKOCR-UHFFFAOYSA-N [Si][Sc] Chemical compound [Si][Sc] CPOIJYXGUPKOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 39
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 28
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004140 cleaning Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000011863 silicon-based powder Substances 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 11
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 244000137852 Petrea volubilis Species 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052706 scandium Inorganic materials 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 12
- 239000010405 anode material Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/04—Electrolytic production, recovery or refining of metals by electrolysis of melts of magnesium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
- C25C3/125—Anodes based on carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
Abstract
The invention discloses a preparation method of a high-strength graphite anode, which comprises the following steps: step 1, carrying out surface cleaning on a graphite blank to obtain a pretreated graphite material; step 2, preparing a silicon scandium carbide coating on the surface of the pretreated graphite material to obtain a silicon scandium carbide-graphite material; and step 3, coating an antioxidation layer on the surface of the silicon carbide scandium-graphite material, and thus obtaining the high-strength graphite anode. The invention prepares a high-strength graphite anode, firstly, a silicon carbide scandium coating is deposited on the surface of a graphite material in a reaction way, so that the strength of the graphite is enhanced and a certain corrosion resistance is achieved; and secondly, coating an oxidation resistant layer on the surface of the deposited graphite material, so as to further enhance the oxidation corrosion resistant effect. The finally obtained graphite anode material not only has high strength, but also has high oxidation resistance, and the service life is greatly prolonged.
Description
Technical Field
The invention relates to the field of graphite electrodes, in particular to a preparation method of a high-strength graphite anode.
Background
The electrolytic industry plays an important role in national economy and electrolytic processes have been widely used in the metallurgical industry, such as extracting metals from ores or compounds or purifying metals, and depositing metals from solutions. Many nonferrous and rare metals, such as sodium, potassium, magnesium, aluminum, zirconium, copper, zinc, lead, are produced mostly by electrolytic methods.
In the electrolysis process, the anode generates very strong oxidation reaction, and the electrolyte is generally a strong acid and alkali material and has stronger corrosiveness. This requires that the higher the strength and oxidation resistance of the anode material, the better. In particular to the electrolytic production process of magnesium aluminum, magnesium chloride and aluminum chloride are generally electrolyzed, and the anode generates chlorine with extremely strong corrosiveness and oxidability and has higher requirements on anode materials.
The graphite anode is an anode material commonly used in a metal magnesium aluminum electrolytic cell, and the most used artificial graphite material is the artificial graphite material, and the artificial graphite has the advantages of good conductivity, corrosion resistance, proper mechanical temperature, convenient processing, low price and the like, is suitable for electrolysis requirements, but has poor oxidation resistance, can be continuously consumed when being used as the anode, and has short service life. Therefore, there is a need to develop a graphite anode that is high in strength and oxidation resistant, thereby increasing its useful life.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of a high-strength graphite anode.
The aim of the invention is realized by adopting the following technical scheme:
the preparation method of the high-strength graphite anode comprises the following steps:
step 1, carrying out surface cleaning on a graphite blank to obtain a pretreated graphite material;
step 2, preparing a silicon scandium carbide coating on the surface of the pretreated graphite material to obtain a silicon scandium carbide-graphite material;
and step 3, coating an antioxidation layer on the surface of the silicon carbide scandium-graphite material, and thus obtaining the high-strength graphite anode.
Preferably, the surface cleaning in the step 1 is to cut the graphite blank into a required shape, then polish the graphite blank with 500-600 mesh sand paper to be flat, clean the surface with 70% -90% alcohol by mass fraction, and dry the surface.
Preferably, the preparation process of the scandium silicon carbide coating in the step 2 comprises the following steps:
and (3) uniformly mixing the silicon powder and the scandium powder to form a silicon scandium mixture, placing the silicon scandium mixture on one side of a high-temperature tube furnace, placing the pretreated graphite material on the other side of the high-temperature tube furnace, vacuumizing the high-temperature tube furnace, gradually heating, carrying out heat preservation treatment, and naturally cooling to normal temperature to obtain the silicon scandium carbide-graphite material.
Preferably, in the silicon scandium mixture, the mass ratio of the silicon powder to the scandium powder is 1.2-1.8:2.0-2.6; the addition amount of the silicon-scandium mixture is calculated according to the surface area of the graphite and accounts for 15-20g/cm of the surface area of the graphite 3 。
Preferably, in the silicon-scandium mixture, the purity of silicon powder and scandium powder is more than 99%, and the mesh number is 8000.
Preferably, the silicon powder and the scandium powder are mixed in a ball milling machine, the ball milling speed is 400-600rpm, the ball milling time is 1-5h, and the ball-to-material ratio is 5-8:1.
Preferably, the vacuum degree of the high-temperature tube furnace is 500-1000Pa, the temperature is raised to 1350-1550 ℃, the temperature raising speed is 10-20 ℃/min, and the heat preservation treatment is carried out for 4-8h.
Preferably, in the step 3, the coating thickness of the antioxidation layer is 25-100 μm.
Preferably, the composition of the antioxidation layer includes: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 2-4:1-3:8-12:5-10.
Preferably, after the antioxidation layer is coated, roasting is carried out in a high-temperature furnace, the roasting temperature is 400-500 ℃, the roasting time is 1-2h, and after the roasting is finished, the material is naturally cooled to room temperature.
The beneficial effects of the invention are as follows:
1. the invention prepares a high-strength graphite anode, firstly, a silicon carbide scandium coating is deposited on the surface of a graphite material in a reaction way, so that the strength of the graphite is enhanced and a certain corrosion resistance is achieved; and secondly, coating an antioxidation layer on the surface of the deposited graphite material, so as to further enhance the antioxidation and anticorrosion effects. The finally obtained graphite anode material not only has high strength, but also has high oxidation resistance, and the service life is greatly prolonged.
2. Experiments prove that the silicon scandium carbide coating deposited on the surface of the graphite by the method has better performance than the common silicon carbide layer or scandium carbide layer, has better strength increasing effect on the graphite, and has a certain antioxidation effect. The silicon carbide scandium-graphite material is finally obtained by utilizing the mixture of silicon powder and scandium powder to form vapor at high temperature and high pressure to react with carbon on the surface of graphite in a combined way to form a compound of silicon carbide and scandium carbide to deposit on the surface of the graphite.
3. The anti-oxidation layer is coated with a much thinner thickness than the common anti-oxidation coating, and the components are aluminum borate, zinc dihydrogen phosphate and sodium silicate which are uniformly mixed with deionized water to form a mixed solution, and the mixed solution is coated on the surface of a graphite material and sintered at a certain temperature to form the anti-oxidation layer, so that the three components complement each other to enhance the oxidation resistance of the graphite material.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a Scanning Electron Microscope (SEM) characterization of a graphite anode prepared according to example 1 of the present invention (10 μm);
FIG. 2 is a Scanning Electron Microscope (SEM) characterization of a graphite anode prepared according to example 1 of the present invention (1 μm).
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention is further described with reference to the following examples.
Example 1
The preparation method of the high-strength graphite anode comprises the following steps:
step 1, cleaning the surface of a graphite blank, cutting the graphite blank into a required shape, firstly polishing the graphite blank with 600-mesh sand paper to be smooth, then cleaning the surface with 80% alcohol by mass fraction, and drying to obtain a pretreated graphite material;
step 2, preparing a layer of silicon scandium carbide on the surface of the pretreated graphite materialThe coating comprises the following concrete steps: silicon powder and scandium powder are uniformly mixed in a ball milling machine to form a silicon-scandium mixture, the mass ratio of the silicon powder to the scandium powder is 1.5:2.3, the ball milling speed is 500rpm, the ball milling time is 3h, the ball material ratio is 6:1, the silicon-scandium mixture is placed on one side of a high-temperature tube furnace, a pretreated graphite material is placed on the other side of the high-temperature tube furnace, and the addition amount of the silicon-scandium mixture is calculated according to the surface area of graphite and accounts for 18g/cm of the surface area of the graphite 3 Vacuumizing a high-temperature tube furnace, gradually heating to 1450 ℃ at a vacuum degree of 800Pa, performing heat preservation treatment for 6 hours at a heating rate of 15 ℃/min, and naturally cooling to normal temperature to obtain a silicon carbide scandium-graphite material;
step 3, coating an antioxidation layer on the surface of the silicon carbide scandium-graphite material, wherein the antioxidation layer comprises the following components: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 3:2:10:8, wherein the coating thickness of the antioxidation layer is 70 mu m, roasting in a high-temperature furnace at the roasting temperature of 450 ℃ for 1.5h, and naturally cooling to room temperature after roasting is finished to obtain the high-strength graphite anode.
Example 2
The preparation method of the high-strength graphite anode comprises the following steps:
step 1, cleaning the surface of a graphite blank, cutting the graphite blank into a required shape, firstly polishing the graphite blank with 500-mesh sand paper to be smooth, then cleaning the surface with 70% alcohol by mass fraction, and drying to obtain a pretreated graphite material;
step 2, preparing a silicon scandium carbide coating on the surface of the pretreated graphite material, wherein the silicon scandium carbide coating comprises the following specific steps: silicon powder and scandium powder are uniformly mixed in a ball milling machine to form a silicon-scandium mixture, the mass ratio of the silicon powder to the scandium powder is 1.2:2.0, the ball milling speed is 400rpm, the ball milling time is 1h, the ball material ratio is 5:1, the silicon-scandium mixture is placed on one side of a high-temperature tube furnace, a pretreated graphite material is placed on the other side of the high-temperature tube furnace, and the addition amount of the silicon-scandium mixture is calculated according to the surface area of graphite and accounts for 15g/cm of the surface area of the graphite 3 Vacuumizing the high-temperature tube furnace to 500Pa, and gradually increasingHeating to 1350 ℃, wherein the heating speed is 10 ℃/min, carrying out heat preservation treatment for 4 hours, and naturally cooling to normal temperature to obtain the silicon carbide scandium-graphite material;
step 3, coating an antioxidation layer on the surface of the silicon carbide scandium-graphite material, wherein the antioxidation layer comprises the following components: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 2:1:8:5, wherein the coating thickness of the antioxidation layer is 25 mu m, roasting in a high-temperature furnace at 400 ℃ for 1h, and naturally cooling to room temperature after roasting is finished to obtain the high-strength graphite anode.
Example 3
The preparation method of the high-strength graphite anode comprises the following steps:
step 1, cleaning the surface of a graphite blank, cutting the graphite blank into a required shape, firstly polishing the graphite blank with 550-mesh sand paper to be smooth, then cleaning the surface with 75% alcohol by mass fraction, and drying to obtain a pretreated graphite material;
step 2, preparing a silicon scandium carbide coating on the surface of the pretreated graphite material, wherein the silicon scandium carbide coating comprises the following specific steps: silicon powder and scandium powder are uniformly mixed in a ball milling machine to form a silicon-scandium mixture, the mass ratio of the silicon powder to the scandium powder is 1.4:2.5, the ball milling speed is 500rpm, the ball milling time is 2h, the ball material ratio is 6:1, the silicon-scandium mixture is placed on one side of a high-temperature tube furnace, a pretreated graphite material is placed on the other side of the high-temperature tube furnace, and the addition amount of the silicon-scandium mixture is calculated according to the surface area of graphite and accounts for 15g/cm of the surface area of the graphite 3 Vacuumizing a high-temperature tube furnace, gradually heating to 1500 ℃ at a vacuum degree of 500Pa, performing heat preservation treatment for 5 hours at a heating rate of 12 ℃/min, and naturally cooling to normal temperature to obtain a silicon carbide scandium-graphite material;
step 3, coating an antioxidation layer on the surface of the silicon carbide scandium-graphite material, wherein the antioxidation layer comprises the following components: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 2:1:10:5, wherein the coating thickness of the antioxidation layer is 55 mu m, roasting in a high-temperature furnace at the roasting temperature of 450 ℃ for 2 hours, and naturally cooling to room temperature after roasting is finished to obtain the high-strength graphite anode.
Example 4
The preparation method of the high-strength graphite anode comprises the following steps:
step 1, cleaning the surface of a graphite blank, cutting the graphite blank into a required shape, firstly polishing the graphite blank with 600-mesh sand paper to be smooth, then cleaning the surface with 90% alcohol by mass fraction, and drying to obtain a pretreated graphite material;
step 2, preparing a silicon scandium carbide coating on the surface of the pretreated graphite material, wherein the silicon scandium carbide coating comprises the following specific steps: silicon powder and scandium powder are uniformly mixed in a ball milling machine to form a silicon-scandium mixture, the mass ratio of the silicon powder to the scandium powder is 1.8:2.6, the ball milling speed is 600rpm, the ball milling time is 5h, the ball material ratio is 8:1, the silicon-scandium mixture is placed on one side of a high-temperature tube furnace, a pretreated graphite material is placed on the other side of the high-temperature tube furnace, and the addition amount of the silicon-scandium mixture is calculated according to the surface area of graphite and accounts for 20g/cm of the surface area of the graphite 3 Vacuumizing a high-temperature tube furnace, gradually heating to 1550 ℃ at a vacuum degree of 1000Pa, performing heat preservation treatment for 8 hours at a heating rate of 20 ℃/min, and naturally cooling to normal temperature to obtain a silicon carbide scandium-graphite material;
step 3, coating an antioxidation layer on the surface of the silicon carbide scandium-graphite material, wherein the antioxidation layer comprises the following components: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 4:3:12:10, wherein the coating thickness of the antioxidation layer is 100 mu m, roasting in a high-temperature furnace at 500 ℃ for 2 hours, and naturally cooling to room temperature after roasting is finished to obtain the high-strength graphite anode.
Comparative example 1
The preparation method of the graphite anode is different from example 1 only in that the surface of the graphite blank body is not coated with the scandium silicon carbide coating, and the preparation method comprises the following steps:
step 1, cleaning the surface of a graphite blank, cutting the graphite blank into a required shape, firstly polishing the graphite blank with 600-mesh sand paper to be smooth, then cleaning the surface with 80% alcohol by mass fraction, and drying to obtain a pretreated graphite material;
step 2, coating an antioxidation layer on the surface of the pretreated graphite material, wherein the antioxidation layer comprises the following components: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 3:2:10, wherein the coating thickness of the antioxidation layer is 70 mu m, roasting in a high-temperature furnace at the roasting temperature of 450 ℃ for 1.5h, and naturally cooling to room temperature after roasting is finished to obtain the graphite anode.
Comparative example 2
The preparation method of the graphite anode is different from the embodiment 1 only in that the surface of the graphite blank body is coated with a silicon carbide coating, namely the prepared silicon carbide-graphite material comprises the following steps:
step 1, cleaning the surface of a graphite blank, cutting the graphite blank into a required shape, firstly polishing the graphite blank with 600-mesh sand paper to be smooth, then cleaning the surface with 80% alcohol by mass fraction, and drying to obtain a pretreated graphite material;
step 2, preparing a silicon carbide coating on the surface of the pretreated graphite material, wherein the silicon carbide coating comprises the following specific steps: silicon powder is placed on one side of a high-temperature tube furnace, and a pretreated graphite material is placed on the other side of the high-temperature tube furnace, wherein the addition amount of the silicon powder is calculated according to the surface area of graphite and accounts for 18g/cm of the surface area of the graphite 3 Vacuumizing a high-temperature tube furnace, gradually heating to 1450 ℃ under the vacuum degree of 800Pa, keeping the temperature at 15 ℃/min, and naturally cooling to normal temperature after heat preservation treatment for 6 hours to obtain a silicon carbide-graphite material;
step 3, coating an antioxidation layer on the surface of the silicon carbide-graphite material, wherein the antioxidation layer comprises the following components: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 3:2:10, wherein the coating thickness of the antioxidation layer is 70 mu m, roasting in a high-temperature furnace at the roasting temperature of 450 ℃ for 1.5h, and naturally cooling to room temperature after roasting is finished to obtain the graphite anode.
Comparative example 3
The preparation method of the graphite anode is different from example 1 only in that the scandium carbide coating is coated on the surface of the graphite blank, namely scandium carbide-graphite material is prepared, and the preparation method comprises the following steps:
step 1, cleaning the surface of a graphite blank, cutting the graphite blank into a required shape, firstly polishing the graphite blank with 600-mesh sand paper to be smooth, then cleaning the surface with 80% alcohol by mass fraction, and drying to obtain a pretreated graphite material;
step 2, preparing a scandium carbide coating on the surface of the pretreated graphite material, wherein the scandium carbide coating comprises the following specific steps: scandium powder is placed on one side of a high-temperature tube furnace, and a pretreated graphite material is placed on the other side of the high-temperature tube furnace, wherein the addition amount of scandium powder is calculated according to the surface area of graphite and accounts for 18g/cm of the surface area of the graphite 3 Vacuumizing a high-temperature tube furnace, gradually heating to 1450 ℃ at a vacuum degree of 800Pa, keeping the temperature at 15 ℃/min, naturally cooling to normal temperature after heat preservation treatment for 6 hours, roasting in the high-temperature furnace at a roasting temperature of 450 ℃ for 1.5 hours, and naturally cooling to room temperature after roasting to obtain scandium carbide-graphite material;
step 3, coating the surface of scandium carbide-graphite material with an antioxidation layer, wherein the antioxidation layer comprises the following components: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 3:2:10, wherein the coating thickness of the antioxidation layer is 70 mu m, and obtaining the graphite anode.
Comparative example 4
The preparation method of the graphite anode is different from example 1 only in that the silicon carbide/scandium carbide-graphite material is prepared by a magnetron sputtering method, and comprises the following steps:
step 1, cleaning the surface of a graphite blank, cutting the graphite blank into a required shape, firstly polishing the graphite blank with 600-mesh sand paper to be smooth, then cleaning the surface with 80% alcohol by mass fraction, and drying to obtain a pretreated graphite material;
step 2, preparing a silicon carbide/scandium carbide coating on the surface of the pretreated graphite material, wherein the silicon carbide/scandium carbide coating comprises the following specific steps: mixing silicon carbide and scandium carbide powder with the silicon-scandium ratio of example 1, preparing a layer of coating on the surface of a graphite material by a magnetron detection method, wherein the radio frequency power supply is 500W, and the model of a magnetron sputtering instrument is JCK-500A, so as to obtain the silicon carbide/scandium carbide-graphite material;
step 3, coating an antioxidation layer on the surface of the silicon carbide/scandium carbide-graphite material, wherein the antioxidation layer comprises the following components: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 3:2:10, wherein the coating thickness of the antioxidation layer is 70 mu m, roasting in a high-temperature furnace at the roasting temperature of 450 ℃ for 1.5h, and naturally cooling to room temperature after roasting is finished to obtain the graphite anode.
Experimental example
1. As can be seen from the SEM images of fig. 1 and 2, the graphite anode prepared in example 1 of the present invention has a better cladding structure.
2. For the detection of the strength and oxidation resistance of the graphite anode materials obtained in example 1 and comparative examples 1-4, the compressive strength detection standard is referred to in GB/T1431-2009, the flexural strength detection standard is referred to in GB/T3074.1-2008, the oxidation resistance detection adopts the reaction of producing metallic aluminum by a molten salt electrolysis method with high corrosiveness as a detection experiment, the molten salt electrolyte is alumina, the electrolysis temperature is 800 ℃, and the usable time of electrolysis is recorded. The results are shown in Table 1:
TABLE 1 results of measuring the strength and oxidation resistance of different graphite anode materials
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Compressive Strength (MPa) | 58.4 | 41.7 | 48.5 | 53.4 | 55.0 |
| Flexural strength (MPa) | 15.1 | 9.7 | 11.4 | 13.3 | 14.2 |
| Electrolysis pot life (h) | 65 | 47 | 53 | 58 | 55 |
Table 1 shows that the compressive strength and flexural strength of example 1 are much higher than those of the other comparative examples, and the usable time of molten salt electrolysis is also greatly improved than those of the other comparative examples, indicating that the strength is higher and the oxidation corrosion resistance is stronger.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the high-strength graphite anode is characterized by comprising the following steps of:
step 1, carrying out surface cleaning on a graphite blank to obtain a pretreated graphite material;
step 2, preparing a silicon scandium carbide coating on the surface of the pretreated graphite material to obtain a silicon scandium carbide-graphite material;
step 3, coating an antioxidation layer on the surface of the silicon carbide scandium-graphite material to obtain the high-strength graphite anode;
the preparation process of the scandium silicon carbide coating in the step 2 comprises the following steps:
silicon powder and scandium powder are uniformly mixed to form a silicon scandium mixture, the silicon scandium mixture is placed on one side of a high-temperature tube furnace, a pretreated graphite material is placed on the other side of the high-temperature tube furnace, the high-temperature tube furnace is vacuumized, gradually heated, subjected to heat preservation treatment, and naturally cooled to normal temperature to obtain a silicon scandium carbide-graphite material;
in the silicon-scandium mixture, the mass ratio of silicon powder to scandium powder is 1.2-1.8:2.0-2.6;
the vacuum degree of the high-temperature tube furnace is 500-1000Pa, and the temperature is raised to 1350-1550 ℃.
2. The method for preparing a high-strength graphite anode according to claim 1, wherein the surface cleaning in the step 1 is performed by cutting a graphite blank into a required shape, polishing the blank with 500-600 mesh sand paper to be flat, cleaning the surface with 70% -90% alcohol by mass fraction, and drying.
3. The method for preparing a high-strength graphite anode according to claim 1, wherein the silicon powder and the scandium powder are mixed in a ball mill at a ball milling speed of 400-600rpm for 1-5 hours at a ball-to-material ratio of 5-8:1.
4. The method for preparing the high-strength graphite anode according to claim 1, wherein the heating rate of the high-temperature tube furnace is 10-20 ℃/min, and the heat preservation treatment time is 4-8h.
5. The method for preparing a high-strength graphite anode according to claim 1, wherein the thickness of the antioxidation layer in the step 3 is 25-100 μm.
6. The method for preparing a high-strength graphite anode according to claim 1, wherein the components of the antioxidation layer include: mixing aluminum borate, zinc dihydrogen phosphate, sodium silicate and deionized water according to the mass ratio of 2-4:1-3:8-12:5-10.
7. The method for preparing a high-strength graphite anode according to claim 1, wherein after the antioxidation layer is coated, the high-strength graphite anode is baked in a high-temperature furnace at a baking temperature of 400-500 ℃ for 1-2h, and is naturally cooled to room temperature after the baking is finished.
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