CN117026278A - Method for preparing hydrogen evolution cathode based on nickel-chromium-titanium mixed oxide - Google Patents
Method for preparing hydrogen evolution cathode based on nickel-chromium-titanium mixed oxide Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 61
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 61
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- VHHVGPDQBHJHFB-UHFFFAOYSA-N [Ti].[Cr].[Ni] Chemical compound [Ti].[Cr].[Ni] VHHVGPDQBHJHFB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 32
- 239000010406 cathode material Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 23
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
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- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
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- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- -1 acryl anhydride Chemical class 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 9
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- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
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- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
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- 238000003763 carbonization Methods 0.000 description 2
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- 239000002803 fossil fuel Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910018502 Ni—H Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/067—Inorganic compound e.g. ITO, silica or titania
Abstract
The application belongs to the technical field of preparation of hydrogen evolution cathode materials, and particularly relates to a method for preparing a hydrogen evolution cathode based on nickel-chromium-titanium mixed oxide. The method comprises the following steps: mixing silicon dioxide, a solid carbon source and silicon carbide, dissolving in a concentrated sulfuric acid solution, stirring in an ice bath, filtering, washing, drying, performing microwave treatment, dispersing the obtained product in a soluble polymer solution, adding tetrabutyl titanate, uniformly mixing, reacting in an inert atmosphere, and filtering, washing, drying and grinding to obtain a porous material; mixing nickel powder, chromium powder and titanium powder, sintering, continuously introducing oxygen in the reaction process until the reaction is finished, and grinding to obtain nickel-chromium-titanium mixed oxide powder; mixing porous material and nickel-chromium-titanium mixed oxide powder, uniformly mixing the mixture with an ethanol solution of a double bond functionalization reagent, taking out the mixture after soaking, and calcining the mixture at a high temperature to obtain the hydrogen evolution cathode material. The material has higher specific surface area, higher porosity, low hydrogen evolution overpotential and good stability.
Description
Technical Field
The application belongs to the technical field of preparation of hydrogen evolution cathode materials, and particularly relates to a method for preparing a hydrogen evolution cathode based on nickel-chromium-titanium mixed oxide.
Background
At present, with the increase of energy demand, the development of renewable energy sources such as solar energy, wind energy, water energy, hydrogen energy and the like, and the development of sustainable development roads becomes the focus of research of various nationists. Among various renewable energy sources, renewable energy sources such as solar energy and wind energy generally have problems such as intermittence and territory, and the application of the renewable energy sources is severely limited. The hydrogen energy has the advantages of rich resources, recycling, high efficiency, environmental protection, wide application range and the like which are incomparable with fossil fuels and other new energy sources, is considered to be an ideal green energy source, and has great significance for promoting the economic development. The current hydrogen production methods mainly comprise fossil fuel hydrogen production, solar hydrogen production, biological hydrogen production, water electrolysis hydrogen production and the like. Thanks to the characteristics of simple process, abundant raw material (water) resources, no pollution and the like, the electrolytic water hydrogen production is a hydrogen production technology capable of directly obtaining high-purity hydrogen, is widely and ripely applied at present, and plays an extremely important role in the development of clean energy.
The electron arrangement of the transition metal Ni is [ Ar ]]3d 8 4s 2 The catalyst has unpaired 3d electrons, can be paired with hydrogen atom 1s orbitals in hydrogen evolution electrocatalytic reaction to form Ni-H adsorption bonds with moderate strength, and has excellent hydrogen evolution catalysis performance and price advantage, so that the catalyst is recognized as an ideal replacement material for noble metals. The current common nickel-based cathode materials such as nickel-chromium-titanium mixed oxide hydrogen evolution cathode have good hydrogen evolution activity and long-term stability and can resist reverse current impact, but have several disadvantages: 1. the oxide has poor conductivity, restricts the conductive path inside the plating layer under the condition of large current, and further influences the overpotential under the condition of large current; 2. the preparation cost of oxide powder is high, and the spraying efficiency is poor; 3. the oxide coating is brittle and lacks toughness. Meanwhile, the flexible woven nickel screen commonly used for the alkaline electrolytic tank has good flexibility, and the catalyst is easy to fall off in a large amount due to deformation in the nickel screen carrying process after spraying.
Based on the above, the inventor of the present application has developed a nickel-chromium-titanium mixed oxide hydrogen evolution cathode material based on the original one, which has higher electrochemical performance than the former one.
Disclosure of Invention
Based on the problems, the application aims to provide a hydrogen evolution cathode prepared based on nickel-chromium-titanium mixed oxide. The cathode material obtained by the method has the advantages of higher specific surface area, high porosity, large aperture, lower hydrogen evolution overpotential and good stability.
In order to achieve the purpose, the application is realized by adopting the following technical scheme:
in one aspect, the present application provides a method for preparing a hydrogen evolving cathode based on a nickel chromium titanium mixed oxide, the method comprising the steps of:
mixing silicon dioxide, a solid carbon source and silicon carbide according to a mass volume ratio of 1g:2-4ml of the mixture is dissolved in concentrated sulfuric acid solution with the mass fraction of 80-90 wt%, then the mixture is placed in ice bath at the temperature of-5~0 ℃ for stirring for 30-60 min, after the reaction is finished, the obtained precipitate is filtered, the obtained precipitate is washed for 2-3 times by deionized water, dried and then subjected to microwave treatment at the temperature of 600-800W for 5-10min to obtain carbonized products, the obtained carbonized products are dispersed in soluble polymer solution with the concentration of 5-10wt%, then tetrabutyl titanate is added and uniformly mixed, and then reacted for 1-3h at the temperature of 200-300 ℃, then the obtained precipitate is filtered and washed, and the obtained precipitate is dried and ground into powder with the particle size of 50-100 mu m to obtain porous materials;
mixing nickel powder, chromium powder and titanium powder, sintering at 400-600 ℃ for 1-3h, continuously introducing oxygen at the speed of 2 ml/s in the reaction process until the reaction is finished, and grinding into powder with the particle size of 80-100nm to obtain nickel-chromium-titanium mixed oxide powder;
mixing the obtained porous material and nickel-chromium-titanium mixed oxide powder, uniformly mixing the mixture with an ethanol solution of a double bond functionalization reagent according to the mass volume ratio of 1g to 10-20ml, soaking for 4-6 days at normal temperature, taking out, calcining at 1000-1500 ℃ for 10-16h at high temperature, and cooling to room temperature after the reaction is finished, thus obtaining the hydrogen evolution cathode material.
Preferably, the solid carbon source is selected from any one of carbon, charcoal, graphite.
Preferably, the silica, solid carbon source and silicon carbide are mixed in an amount of 1:2 to 4:1 to 5 by mass ratio.
Preferably, the soluble polymer is selected from any one of carboxymethyl cellulose, gelatin, sodium alginate, polyvinyl alcohol and polyethylene glycol.
Preferably, the carbonisation product, tetrabutyl titanate and soluble polymer solution are added in an amount of 1g:0.02-0.04ml:3-5ml mass to volume ratio.
Preferably, the inert atmosphere is selected from one of argon, nitrogen and hydrogen.
Preferably, the nickel powder, the chromium powder and the titanium powder are mixed according to the mass ratio of 90-95:4-7:1-3.
Preferably, the porous material and the nickel chromium titanium mixed oxide powder are mixed according to the mass ratio of 1:0.5-0.9.
Preferably, the double bond functionalizing agent is selected from any one of acryl chloride, methacryl chloride, acrylic anhydride, methacrylic anhydride, and glycidyl methacrylate.
Preferably, the preparation method of the ethanol solution of the double bond functionalization reagent comprises the following steps: the double bond functionalization reagent and ethanol are mixed according to the volume ratio of 1-2: 10.
Compared with the prior art, the application has the following beneficial effects:
the hydrogen evolution cathode material is a composite material based on the nickel-chromium-titanium mixed oxide loaded on a porous material, has high specific surface area and rich three-dimensional pore structure, has high porosity and large pore diameter, can provide more reaction interfaces for the hydrogen evolution process of an electrode, ensures that the reaction is easier to carry out, can further reduce the reaction activation energy through the modification of the nickel-chromium-titanium mixed oxide on the porous surface, is beneficial to reducing hydrogen evolution passing points, improves the catalytic activity of the electrode and further reduces the energy consumption. The cathode material disclosed by the application is high in stability, long in service life and excellent in mechanical property. The method is economical and environment-friendly, and can be used for industrial production.
In one aspect, the application uses silicon dioxide, solid carbon source and silicon carbide as the preparation raw materials of the porous material, wherein the solid carbon source is selected from carbon, charcoal or graphite, the raw materials are abundant in source and low in cost. Firstly, carbonizing three raw materials through concentrated sulfuric acid solution, and then pore-forming the carbonized product through tetrabutyl titanate; the environment of the soluble polymer solution can facilitate manufacturingThe pore reaction is carried out, so that the carbonized product generates a large number of pore structures and high specific surface area, and the three raw materials are fully integrated through the low viscosity effect of the soluble polymer solution. The low-temperature ice bath reaction can reduce the temperature of carbonization reaction and improve the reaction safety. The microwave treatment can improve the activity of carbonized products, reduce the activation energy of the reaction, promote the subsequent pore-forming reaction to be carried out smoothly, and the obtained porous material is a micron-sized material with the particle size distribution of 50-100 mu m, and has the advantages of high porosity, large pore diameters of micron-sized material, high pore volume and micron-sized porous structure, and is convenient for gas transmission and favorable for hydrogen evolution reaction. In another aspect, nickel powder, chromium powder, and titanium powder are mixed and sintered in an oxygen atmosphere to oxidize the three metals to obtain nano-scale nickel-chromium-titanium mixed oxide powder. Finally, mixing the micron-sized porous material and the nano-sized nickel-chromium-titanium mixed oxide powder, soaking the mixture in an ethanol solution containing a double bond functionalization reagent, loading the nano-sized nickel-chromium-titanium mixed oxide powder on the surface of the porous material through double bond modification, wherein the double bond modification can enhance the binding force between the nano-powder and the porous material, and the ethanol solution provides rich OH for the whole reaction system - Avoiding the damage of H+ to the material structure, and finally further improving the stability of the material by high-temperature calcination.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1:
mixing silicon dioxide, charcoal and silicon carbide according to the mass ratio of 1:3:3 to obtain a mixture. Then according to the mass volume ratio of 1g: the mixture is dissolved in concentrated sulfuric acid solution with the mass fraction of 85wt percent in the amount of 3ml, then the mixture is placed in ice bath with the temperature of-5~0 ℃ for stirring for 45min, the mixture is filtered after the reaction is finished, the obtained precipitate is washed for 2-3 times by deionized water, and the obtained precipitate is dried and then subjected to microwave treatment for 8min under the condition of 700W, so that a carbonized product is obtained. Dispersing the obtained carbonized product in 7wt% carboxymethyl cellulose solution, adding tetrabutyl titanate, mixing uniformly, reacting for 2 hours at 250 ℃ in nitrogen atmosphere, filtering, washing, drying the obtained precipitate, and grinding into powder with the particle size of 50-100 mu m to obtain the porous material. The carbonized product, tetrabutyl titanate and carboxymethyl cellulose solution are added according to the mass-volume ratio of 1g to 0.03ml to 4 ml.
Mixing nickel powder, chromium powder and titanium powder according to the mass ratio of 93:5:2, sintering for 2 hours at 500 ℃, continuously introducing oxygen at the speed of 2 ml/s in the reaction process to the end of the reaction, and grinding into powder with the particle size of 80-100nm to obtain the nickel-chromium-titanium mixed oxide powder.
Mixing the obtained porous material and nickel-chromium-titanium mixed oxide powder according to the mass ratio of 1:0.7 to obtain a mixture. And then uniformly mixing the mixture with an ethanol solution of acrylic anhydride according to the mass volume ratio of 1g to 15ml (the preparation method is that the acrylic anhydride and the ethanol are mixed according to the volume ratio of 1.5 to 10), soaking for 5 days at normal temperature, taking out, calcining at a high temperature of 1250 ℃ for 13 hours, and cooling to the room temperature after the reaction is finished, thus obtaining the hydrogen evolution cathode material.
Example 2:
silicon dioxide, carbon and silicon carbide are mixed according to the mass ratio of 1:4:1 to obtain a mixture. Then according to the mass volume ratio of 1g: and (3) dissolving the mixture in an amount of 2ml in a concentrated sulfuric acid solution with the mass fraction of 80wt%, then placing the mixture in an ice bath at the temperature of-5~0 ℃ for stirring for 60min, filtering after the reaction is finished, washing the obtained precipitate with deionized water for 2-3 times, drying, and then carrying out microwave treatment at the temperature of 800W for 5min to obtain a carbonized product. Dispersing the obtained carbonized product in gelatin solution with the concentration of 10wt%, adding tetrabutyl titanate, uniformly mixing, reacting for 3 hours at 200 ℃ in nitrogen atmosphere, filtering, washing, drying the obtained precipitate, and grinding into powder with the particle size of 50-100 mu m to obtain the porous material. The carbonized product, tetrabutyl titanate and gelatin solution are added in the mass-volume ratio of 1g to 0.02ml to 3 ml.
Mixing nickel powder, chromium powder and titanium powder according to the mass ratio of 90:7:3, sintering at 400 ℃ for 3 hours, continuously introducing oxygen at the speed of 2 ml/s in the reaction process to the end of the reaction, and grinding into powder with the particle size of 80-100nm to obtain the nickel-chromium-titanium mixed oxide powder.
Mixing the obtained porous material and nickel-chromium-titanium mixed oxide powder according to the mass ratio of 1:0.9 to obtain a mixture. And then uniformly mixing the mixture with an ethanol solution of methacryloyl chloride according to the mass volume ratio of 1g to 10ml (the preparation method is that the methacryloyl chloride and the ethanol are mixed according to the volume ratio of 2 to 10), soaking for 4 days at normal temperature, taking out, calcining at a high temperature of 1500 ℃ for 10 hours, and cooling to the room temperature after the reaction is finished, thus obtaining the hydrogen evolution cathode material.
Example 3:
silicon dioxide, graphite and silicon carbide are mixed according to the mass ratio of 1:2:5 to obtain a mixture. Then according to the mass volume ratio of 1g: the mixture is dissolved in concentrated sulfuric acid solution with the mass fraction of 90wt percent in the amount of 4ml, then the mixture is placed in ice bath with the temperature of-5~0 ℃ for stirring for 30min, the mixture is filtered after the reaction is finished, the obtained precipitate is washed for 2-3 times by deionized water, and the obtained precipitate is dried and then subjected to microwave treatment for 10min at 600W, so that a carbonized product is obtained. Dispersing the carbonized product into a polyvinyl alcohol solution with the concentration of 5wt%, adding tetrabutyl titanate, uniformly mixing, reacting for 1h at 300 ℃ in a nitrogen atmosphere, filtering, washing, drying the obtained precipitate, and grinding into powder with the particle size of 50-100 mu m to obtain the porous material. The carbonized product, tetrabutyl titanate and polyvinyl alcohol solution were added in a mass-to-volume ratio of 1g to 0.04ml to 5 ml.
Mixing nickel powder, chromium powder and titanium powder according to the mass ratio of 95:4:1, sintering at 600 ℃ for 1h, continuously introducing oxygen at the speed of 2 ml/s in the reaction process to the end of the reaction, and grinding into powder with the particle size of 80-100nm to obtain the nickel-chromium-titanium mixed oxide powder.
Mixing the obtained porous material and nickel-chromium-titanium mixed oxide powder according to the mass ratio of 1:0.5 to obtain a mixture. And then uniformly mixing the mixture with an ethanol solution of the acryloyl chloride according to the mass volume ratio of 1g to 20ml (the preparation method is that the acryloyl chloride and the ethanol are mixed according to the volume ratio of 1 to 10), soaking for 6 days at normal temperature, taking out, calcining at 1000 ℃ for 16 hours at high temperature, and cooling to the room temperature after the reaction is finished, thus obtaining the hydrogen evolution cathode material.
Comparative example 1:
mixing silicon dioxide, charcoal and silicon carbide according to the mass ratio of 1:3:3 to obtain a mixture. Then according to the mass volume ratio of 1g: the mixture is dissolved in concentrated sulfuric acid solution with the mass fraction of 85wt percent in the amount of 3ml, then the mixture is placed in ice bath with the temperature of-5~0 ℃ for stirring for 45min, the mixture is filtered after the reaction is finished, the obtained precipitate is washed for 2-3 times by deionized water, dried and then subjected to microwave treatment for 8min under the condition of 700W, a carbonized product is obtained, and finally the carbonized product is ground into powder with the particle size of 50-100 mu m, so that the carbonized material is obtained.
Mixing nickel powder, chromium powder and titanium powder according to the mass ratio of 93:5:2, sintering for 2 hours at 500 ℃, continuously introducing oxygen at the speed of 2 ml/s in the reaction process to the end of the reaction, and grinding into powder with the particle size of 80-100nm to obtain the nickel-chromium-titanium mixed oxide powder.
Mixing the carbonized material obtained above and nickel-chromium-titanium mixed oxide powder according to the mass ratio of 1:0.7 to obtain a mixture. And then uniformly mixing the mixture with an ethanol solution of acrylic anhydride according to the mass volume ratio of 1g to 15ml (the preparation method is that the acrylic anhydride and the ethanol are mixed according to the volume ratio of 1.5 to 10), soaking for 5 days at normal temperature, taking out, calcining at a high temperature of 1250 ℃ for 13 hours, and cooling to the room temperature after the reaction is finished, thus obtaining the hydrogen evolution cathode material.
Comparative example 2:
mixing silicon dioxide, charcoal and silicon carbide according to the mass ratio of 1:3:3 to obtain a mixture. Then according to the mass volume ratio of 1g: the mixture is dissolved in concentrated sulfuric acid solution with the mass fraction of 85wt percent in the amount of 3ml, then the mixture is placed in ice bath with the temperature of-5~0 ℃ for stirring for 45min, the mixture is filtered after the reaction is finished, the obtained precipitate is washed for 2-3 times by deionized water, and the obtained precipitate is dried and then subjected to microwave treatment for 8min under the condition of 700W, so that a carbonized product is obtained. Dispersing the obtained carbonized product in 7wt% carboxymethyl cellulose solution, adding tetrabutyl titanate, mixing uniformly, reacting for 2 hours at 250 ℃ in nitrogen atmosphere, filtering, washing, drying the obtained precipitate, and grinding into powder with the particle size of 50-100 mu m to obtain the porous material. The carbonized product, tetrabutyl titanate and carboxymethyl cellulose solution are added according to the mass-volume ratio of 1g to 0.03ml to 4 ml.
Mixing nickel powder, chromium powder and titanium powder according to the mass ratio of 93:5:2, sintering for 2 hours at 500 ℃, continuously introducing oxygen at the speed of 2 ml/s in the reaction process to the end of the reaction, and grinding into powder with the particle size of 80-100nm to obtain the nickel-chromium-titanium mixed oxide powder.
Mixing the obtained porous material and nickel-chromium-titanium mixed oxide powder according to the mass ratio of 1:0.7, calcining the obtained mixture at 1250 ℃ for 13 hours at high temperature, and cooling to room temperature after the reaction is finished, thus obtaining the hydrogen evolution cathode material.
Comparative example 3:
mixing nickel powder, chromium powder and titanium powder according to the mass ratio of 93:5:2, sintering for 2 hours at 500 ℃, continuously introducing oxygen at the speed of 2 ml/s in the reaction process to the end of the reaction, and grinding into powder with the particle size of 80-100nm to obtain nickel-chromium-titanium mixed oxide powder serving as a hydrogen evolution cathode material.
Test example 1 physical and chemical properties detection of hydrogen evolution cathode material:
the experimental object: examples 1-3 and comparative examples 1-3
The experimental method comprises the following steps: the specific surface area, pore size distribution and porosity of each sample were determined using a specific surface area analyzer (BSD-660) and a pore analyzer (PORUXTM Cito series, germany), respectively.
Experimental results: see table 1.
TABLE 1 specific surface area and pore size distribution and porosities for different samples
As can be seen from the results of Table 1, the hydrogen-evolving cathode materials obtained in examples 1 to 3 of the present application have a high specific surface area and porosity, and a large pore size, both being of the order of micrometers, as compared with comparative examples 1 to 3. Comparative example 2 is only a process of treating an ethanol solution without acrylic anhydride compared with example 1, which shows that the former process is critical in determining the structural morphology of the cathode material.
Test example 2 hydrogen evolution overpotential detection of hydrogen evolution cathode material:
the experimental object: examples 1-3 and comparative examples 1-3
The experimental method comprises the following steps: the materials of the respective samples were used as materials for hydrogen production by electrolysis of water, and polarization current was 400 mA.cm in 33wt% NaOH solution -2 Electrochemical testing was performed under the conditions. The initial hydrogen evolution overpotential is detected. And simultaneously, under the intermittent electrolysis conditions of 1h electrolysis and 0.5h power failure, the electrolysis is repeatedly carried out for 100 times, and then the hydrogen evolution overpotential is detected.
Experimental results: see table 2.
TABLE 2 hydrogen evolution overpotential for different hydrogen evolution cathode materials
As can be seen from the results in table 2, the hydrogen evolution overpotential of the cathode materials of examples 1 to 3 of the present application is significantly lower compared with comparative examples 1 to 3, which indicates that the hydrogen evolution performance of the cathode materials is high; after repeating the electrolysis 100 times, the hydrogen evolution overpotential of the materials in examples 1 to 3 of the present application is not greatly changed, which indicates that the electrode can maintain good stability during intermittent electrolysis.
The present application is not described in detail in the present application, and is well known to those skilled in the art.
While the application has been described with respect to preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the application, and that any such changes and modifications as described in the above embodiments are intended to be within the scope of the application.
Claims (10)
1. A method for preparing a hydrogen evolution cathode based on nickel-chromium-titanium mixed oxide, which is characterized by comprising the following steps:
mixing silicon dioxide, a solid carbon source and silicon carbide according to a mass volume ratio of 1g:2-4ml of the mixture is dissolved in concentrated sulfuric acid solution with the mass fraction of 80-90 wt%, then the mixture is placed in ice bath at the temperature of-5~0 ℃ for stirring for 30-60 min, after the reaction is finished, the obtained precipitate is filtered, the obtained precipitate is washed for 2-3 times by deionized water, dried and then subjected to microwave treatment at the temperature of 600-800W for 5-10min to obtain carbonized products, the obtained carbonized products are dispersed in soluble polymer solution with the concentration of 5-10wt%, then tetrabutyl titanate is added and uniformly mixed, and then reacted for 1-3h at the temperature of 200-300 ℃, then the obtained precipitate is filtered and washed, and the obtained precipitate is dried and ground into powder with the particle size of 50-100 mu m to obtain porous materials;
mixing nickel powder, chromium powder and titanium powder, sintering at 400-600 ℃ for 1-3h, continuously introducing oxygen at the speed of 2 ml/s in the reaction process until the reaction is finished, and grinding into powder with the particle size of 80-100nm to obtain nickel-chromium-titanium mixed oxide powder;
mixing the obtained porous material and nickel-chromium-titanium mixed oxide powder, uniformly mixing the mixture with an ethanol solution of a double bond functionalization reagent according to the mass volume ratio of 1g to 10-20ml, soaking for 4-6 days at normal temperature, taking out, calcining at 1000-1500 ℃ for 10-16h at high temperature, and cooling to room temperature after the reaction is finished, thus obtaining the hydrogen evolution cathode material.
2. The method for producing a hydrogen evolving cathode based on nickel chromium titanium mixed oxide according to claim 1, wherein the solid carbon source is selected from any one of carbon, charcoal, graphite.
3. The method for producing a hydrogen evolving cathode based on a nickel chromium titanium mixed oxide according to claim 1, wherein the silica, solid carbon source and silicon carbide are mixed in the mass ratio of 1:2 to 4:1 to 5.
4. The method for preparing a hydrogen evolution cathode based on nickel-chromium-titanium mixed oxide according to claim 1, wherein the soluble polymer is selected from any one of carboxymethyl cellulose, gelatin, sodium alginate, polyvinyl alcohol, polyethylene glycol.
5. The method for producing a hydrogen evolving cathode based on nickel chromium titanium mixed oxide according to claim 1, wherein the carbonized product, tetrabutyl titanate and soluble polymer solution are added in the mass volume ratio of 1g:0.02-0.04ml:3-5 ml.
6. The method for preparing a hydrogen evolving cathode based on nickel chromium titanium mixed oxide according to claim 1, wherein the inert atmosphere is one selected from argon, nitrogen and hydrogen.
7. The method for preparing a hydrogen evolution cathode based on nickel-chromium-titanium mixed oxide according to claim 1, wherein the nickel powder, the chromium powder and the titanium powder are mixed in an amount of 90-95:4-7:1-3 by mass ratio.
8. The method for producing a hydrogen evolving cathode based on a nickel chromium titanium mixed oxide according to claim 1, wherein the porous material, nickel chromium titanium mixed oxide powder are mixed in an amount of 1:0.5 to 0.9 by mass ratio.
9. The method for producing a hydrogen evolution cathode based on a nickel-chromium-titanium mixed oxide according to claim 1, wherein the double bond functionalizing agent is selected from any one of acryl chloride, methacryl chloride, acryl anhydride, methacryl anhydride, glycidyl methacrylate.
10. The method for preparing a hydrogen evolution cathode based on nickel-chromium-titanium mixed oxide according to claim 1, wherein the method for preparing the ethanol solution of the double bond functionalization reagent comprises the following steps: the double bond functionalization reagent and ethanol are mixed according to the volume ratio of 1-2: 10.
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