CN110732333A - Preparation method of electrocatalytic material, electrocatalytic material and application thereof - Google Patents
Preparation method of electrocatalytic material, electrocatalytic material and application thereof Download PDFInfo
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- CN110732333A CN110732333A CN201911036337.7A CN201911036337A CN110732333A CN 110732333 A CN110732333 A CN 110732333A CN 201911036337 A CN201911036337 A CN 201911036337A CN 110732333 A CN110732333 A CN 110732333A
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 88
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 44
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 32
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims abstract description 31
- 229910052786 argon Inorganic materials 0.000 claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 229910052711 selenium Inorganic materials 0.000 claims description 17
- 239000011669 selenium Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- OXYOQBAZFDHPBM-UHFFFAOYSA-N [P].[Se] Chemical compound [P].[Se] OXYOQBAZFDHPBM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 15
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- POTRNMJIMIESGR-UHFFFAOYSA-L cobalt(2+);diacetate;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O POTRNMJIMIESGR-UHFFFAOYSA-L 0.000 description 4
- DTNVUQFDRPOYFY-UHFFFAOYSA-L nickel(2+);diacetate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O DTNVUQFDRPOYFY-UHFFFAOYSA-L 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- CZAYMIVAIKGLOR-UHFFFAOYSA-N [Ni].[Co]=O Chemical class [Ni].[Co]=O CZAYMIVAIKGLOR-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to a preparation method of electrocatalytic materials, the electrocatalytic materials and the application thereof, the preparation method comprises the steps of preparing nickel cobalt hydroxide by hydrothermal reaction, annealing the nickel cobalt hydroxide and selenium powder in argon to obtain selenium-doped nickel cobaltate, annealing the selenium-doped nickel cobaltate and sodium hypophosphite in argon to obtain the electrocatalytic materials, and the amorphous selenium-phosphorus double-doped nickel cobaltate material prepared by the preparation method has a three-dimensional amorphous structure, greatly increases active sites, is beneficial to the exposure of the active sites, has good activity in HER and OER reactions of water electrolysis in alkaline electrolyte, and is used as cathode and anode catalyst total-hydrolytic water to drive an electrolytic cell to generate 10mA/cm2Only a voltage of 1.54V is required for the current density of (a).
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a preparation method of electrocatalytic materials, an electrocatalytic material and application thereof.
Background
The push and the use of clean energy sources such as wind energy, solar energy, hydrogen energy and the like are important for the sustainable development and the balance of ecological environment in the future, wherein the wind energy and the solar energy are not easy to store and transport and have the characteristic of intermittency, and the hydrogen energy is the most ideal clean energy source at present.
The technology for producing hydrogen by electrocatalysis decomposition has high efficiency and can work continuously, and is considered to be the most promising and efficient hydrogen production way for relieving energy crisis and environmental pollution. Therefore, designing and developing a high-efficiency electrocatalytic material has great significance for relieving the energy crisis, and the activity of the electrocatalytic material in the Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) in the alkaline electrolyte is low at present, so that the efficiency of the current electrolysis technology is relatively low.
Disclosure of Invention
The application provides preparation methods for electrocatalytic materials, electrocatalytic materials and applications thereof, which are used for solving the technical problem that the electrocatalytic materials in the prior art are low in activity in HER and OER reactions, so that the water electrolysis efficiency is low.
In accordance with an aspect of the present application, there is provided a method of preparing electrocatalytic materials, the method comprising:
preparing nickel cobalt hydroxide by using a hydrothermal reaction;
annealing the nickel-cobalt hydroxide and selenium powder in argon to obtain selenium-doped nickel cobaltate;
and annealing the selenium-doped nickel cobaltate and sodium hypophosphite in argon to obtain the electro-catalytic material.
, the preparing nickel cobalt hydroxide by hydrothermal reaction includes:
dissolving soluble nickel salt, soluble cobalt salt, ammonium fluoride and hexamethylenetetramine in a solvent according to a molar ratio of 5:10:20:2 to obtain th solution, wherein the solvent is a mixed solution of ethanol and water in a volume ratio of 1: 1;
and (3) keeping the th solution at 140 ℃, heating for 8h, cooling to room temperature, washing with water, washing with alcohol, and drying to obtain the nickel cobalt hydroxide.
, annealing the nickel cobalt hydroxide and selenium powder in argon to obtain selenium-doped nickel cobaltate comprises:
and mixing the nickel cobalt hydroxide with selenium powder, and heating the mixture for 2 hours at 400 ℃ in an argon environment to obtain the selenium-doped nickel cobaltate.
, annealing the selenium-doped nickel cobaltate and sodium hypophosphite in argon to obtain the electrocatalytic material comprises:
and mixing the selenium-doped nickel cobaltate with sodium hypophosphite, and heating the mixture for 15-90 min at 400 ℃ in an argon environment to obtain the electro-catalytic material.
Preferably, the selenium-doped nickel cobaltate and the sodium hypophosphite are heated in argon for 30 min.
In a second aspect, the present application provides electrocatalytic materials prepared according to the method of preparing any electrocatalytic materials provided in aspect .
, the mass ratio of cobalt in the electrocatalytic material is 18.13-23.68%, the mass ratio of nickel is 4.57-11.28%, the mass ratio of oxygen is 41-53.95%, the mass ratio of selenium is 2.76-4.95%, and the mass ratio of phosphorus is 5.35-8.2%.
Further , the electrocatalytic material is in a sheet-like structure.
In a third aspect of the present application there is provided the use of any of the electrocatalytic materials described in the second aspect in the electrolysis of water.
From the embodiments of the present invention, the preparation method of the electrocatalytic material, the electrocatalytic material and the application thereof provided by the present application can be known, and the preparation method comprises preparing nickel cobalt hydroxide by hydrothermal reaction; annealing the nickel-cobalt hydroxide and selenium powder in argon to obtain selenium-doped nickel cobaltate; and annealing the selenium-doped nickel cobaltate and sodium hypophosphite in argon to obtain selenium-phosphorus double-doped nickel cobaltate. The electrocatalytic material prepared by the preparation method has a three-dimensional amorphous structure, greatly increases active sites and is beneficial to the exposure of the active sites, so that the material prepared by the method has extremely strong activity and can effectively improve the efficiency of water electrolysis.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing an electrocatalytic material provided by an embodiment of the present application;
FIG. 2 is a surface topography SEM image of a nickel cobaltate spinel structure provided in example 1 of the present application;
FIG. 3 is a SEM image of the surface topography of amorphous selenium and phosphorus double doped nickel cobalt oxide as provided in example 4 of the present application;
figure 4 is a graph comparing HER polarization curves for 4 materials prepared in accordance with the examples provided herein;
FIG. 5 is a graph comparing OER polarization curves for materials prepared in 4 examples provided herein;
FIG. 6 is a Tafel slope plot of FIG. 4 provided herein;
FIG. 7 is a Tafel slope plot of FIG. 5 provided herein;
FIG. 8 is a graph showing the relationship between the current and the required voltage when the electrocatalytic material provided by the embodiment of the application is used for electrolyzing water.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the embodiments of the present invention will be described in detail and completely with reference to the accompanying drawings, it is obvious that the described embodiments are only a part of the embodiments of the present invention, but not all embodiments.
In accordance with an aspect of the present application, there is provided a method of preparing electrocatalytic materials, the method comprising:
and 103, annealing the selenium-doped nickel cobaltate and sodium hypophosphite in argon to obtain the electro-catalytic material.
Specifically, the step 101 of preparing the nickel cobalt hydroxide by using the hydrothermal reaction includes:
dissolving soluble nickel salt, soluble cobalt salt, ammonium fluoride and hexamethylenetetramine in a solvent according to a molar ratio of 5:10:20:2 to obtain th solution, wherein the solvent is a mixed solution of ethanol and water in a volume ratio of 1: 1;
and (3) keeping the th solution at 140 ℃, heating for 8h, cooling to room temperature, washing with water, washing with alcohol, and drying to obtain the nickel cobalt hydroxide.
Specifically, 0.5mmol of nickel acetate hexahydrate, 1mmol of cobalt acetate hexahydrate, 2mmol of ammonium fluoride and 0.2mmol of hexamethylenetetramine are dissolved in a solution obtained by mixing 15ml of ethanol and 15ml of water, and the mixture is sufficiently stirred to obtain a mixed solution. And (3) placing the mixed solution in a polytetrafluoroethylene inner container, placing the polytetrafluoroethylene inner container in a stainless steel high-pressure kettle, sealing, heating for 8 hours at the temperature of 140 ℃ in an electric heating forced air drying oven, cooling to room temperature, washing the obtained material with water, washing with alcohol, and drying to obtain the nickel-cobalt hydroxide.
The specific operation may be to mix the nickel-cobalt hydroxide prepared in step 101 with selenium powder, place the mixture in a tube furnace, heat the mixture to 400 ℃ in an argon protective atmosphere, and keep the temperature for 2 hours to obtain selenium-doped nickel cobaltate.
and mixing the selenium-doped nickel cobaltate with sodium hypophosphite, and heating the mixture for 15-90 min at 400 ℃ in an argon environment to obtain the electro-catalytic material.
The specific operation may be that the selenium-doped nickel cobaltate prepared in step 102 and sodium hypophosphite are placed into a tube furnace according to a mass ratio of 1:5, annealing is performed at 400 ℃ for 15-90 minutes in an argon atmosphere, and amorphous selenium and phosphorus double-doped nickel cobalt oxide is obtained, and the amorphous selenium and phosphorus double-doped nickel cobalt oxide is the electro-catalytic material to be prepared.
Preferably, the selenium-doped nickel cobaltate and the sodium hypophosphite are heated in argon for 30 min.
The preparation method of the electrocatalytic material provided by the embodiment of the application comprises the steps of preparing nickel cobalt hydroxide by hydrothermal reaction; annealing the nickel-cobalt hydroxide and selenium powder in argon to obtain selenium-doped nickel cobaltate; and annealing the selenium-doped nickel cobaltate and sodium hypophosphite in argon to obtain the selenium-phosphorus double-doped nickel-cobalt oxide. The electrocatalytic material selenium and phosphorus double-doped nickel-cobalt oxide prepared by the preparation method has a three-dimensional amorphous structure, greatly increases active sites and is beneficial to the exposure of the active sites, so that the material prepared by the method has extremely strong activity and can effectively improve the efficiency of water electrolysis.
In another aspect of the present application, electrocatalytic materials are provided, and the electrocatalytic materials are amorphous selenium and phosphorus double-doped nickel-cobalt oxides prepared by the preparation method of the electrocatalytic material provided in the aspect.
, the mass ratio of cobalt in the electrocatalytic material is 18.13-23.68%, the mass ratio of nickel is 4.57-11.28%, the mass ratio of oxygen is 41-53.95%, the mass ratio of selenium is 2.76-4.95%, and the mass ratio of phosphorus is 5.35-8.2%.
Further , the electrocatalytic material is in a sheet-like structure.
The third aspect of the application also provides the application of any electrocatalytic materials selenium and phosphorus double-doped nickel-cobalt oxide provided by the second aspect in electrolytic water.
The following is described in detail with reference to specific examples:
example 1: preparation of nickel cobaltate spinel structure
(1) A hydrothermal solution containing ammonium fluoride, nickel ions, cobalt ions and hexamethylenetetramine is filled into a polytetrafluoroethylene inner container. The hydrothermal solution comprises the following components: 15ml of deionized water, 15ml of ethanol, 0.1244g of nickel acetate hexahydrate, 0.219g of cobalt acetate hexahydrate, 0.074g of ammonium fluoride and 0.033g of hexamethylenetetramine. Then placing the polytetrafluoroethylene inner container in a stainless steel autoclave and sealing, heating for 8 hours in an electrothermal blowing drying oven at the temperature of 140 ℃, then cooling to room temperature, washing with water, washing with alcohol and drying;
(2) independently placing the nickel cobalt hydroxide prepared in the step (1) in a tube furnace, and annealing and heating in an argon atmosphere to obtain a nickel cobaltate spinel structure; the technological parameters are as follows: the annealing temperature is 400 ℃, and the holding time is 2 h.
As shown in fig. 2, a surface topography SEM image of a nickel cobaltate spinel structure is provided for the examples of the present application.
Example 2: preparation of selenium-doped nickel cobaltate structure
(1) A hydrothermal solution containing ammonium fluoride, nickel ions, cobalt ions and hexamethylenetetramine is filled into a polytetrafluoroethylene inner container. The hydrothermal solution comprises the following components: 15ml of deionized water, 15ml of ethanol, 0.1244g of nickel acetate hexahydrate, 0.219g of cobalt acetate hexahydrate, 0.074g of ammonium fluoride and 0.033g of hexamethylenetetramine. Then placing the polytetrafluoroethylene inner container in a stainless steel autoclave and sealing, heating for 8 hours in an electrothermal blowing drying oven at the temperature of 140 ℃, then cooling to room temperature, washing with water, washing with alcohol and drying;
(2) placing the nickel cobalt hydroxide prepared in the step (1) and selenium powder in a tubular furnace according to the mass ratio of 1:5, placing the selenium powder at the upstream of the atmosphere of the tubular furnace, while the nickel cobalt hydroxide at the downstream, and annealing and heating in the argon atmosphere to obtain a selenium-doped nickel cobaltate spinel structure; the technological parameters are as follows: the annealing temperature is 400 ℃, and the holding time is 2 h.
Example 3: preparation of phosphorus-doped nickel cobaltate structure
(1) A hydrothermal solution containing ammonium fluoride, nickel ions, cobalt ions and hexamethylenetetramine is filled into a polytetrafluoroethylene inner container. The hydrothermal solution comprises the following components: 15ml of deionized water, 15ml of ethanol, 0.1244g of nickel acetate hexahydrate, 0.219g of cobalt acetate hexahydrate, 0.074g of ammonium fluoride and 0.033g of hexamethylenetetramine. Then placing the polytetrafluoroethylene inner container in a stainless steel autoclave and sealing, heating for 8 hours in an electrothermal blowing drying oven at the temperature of 140 ℃, then cooling to room temperature, washing with water, washing with alcohol and drying;
(2) placing the nickel cobalt hydroxide prepared in the step (1) and sodium hypophosphite in a mass ratio of 1:5 in a tubular furnace, placing the sodium hypophosphite at the upstream of the atmosphere of the tubular furnace, placing the nickel cobalt hydroxide at the downstream, and annealing and heating in an argon atmosphere to obtain a selenium-doped nickel cobaltate spinel structure; the technological parameters are as follows: the annealing temperature is 400 ℃, and the heat preservation time is 30 min.
Example 4: preparation of amorphous selenium and phosphorus double-doped nickel-cobalt oxide
Placing the selenium-doped nickel cobaltate structure prepared in the embodiment 2 as a precursor and sodium hypophosphite in a mass ratio of 1:5 in a tubular furnace, placing the sodium hypophosphite at the upstream of the atmosphere of the tubular furnace, placing the selenium-doped nickel cobaltate at the downstream, and annealing and heating in an argon atmosphere to obtain an amorphous nanostructure, selenium-phosphorus double-doped nickel cobalt oxide; the technological parameters are as follows: the annealing temperature is 400 ℃, and the heat preservation time is 30 min.
As shown in fig. 3, an SEM image of the surface topography of amorphous selenium and phosphorus double doped nickel cobalt oxide is provided for the examples of the present application.
As shown in FIG. 4, the comparative graph of HER polarization curves for the materials prepared in the four examples provided herein shows that the current density gradually increases with increasing voltage, and the required voltage for the selenium and phosphorus double-doped nickel cobalt oxide provided in the fourth example of the present application is the smallest, i.e., the material is most active in the HER reaction, when the current density is 10. similarly, as shown in FIG. 5, the comparative graph of OER polarization curves for the materials prepared in the 4 examples provided herein shows that the required voltage for the selenium and phosphorus double-doped nickel cobalt oxide provided in the fourth example of the present application is the smallest, i.e., the material is most active in the OER reaction, when the current density is 10. As shown in FIG. 6, the graph of Tafel slope of FIG. 4 provided herein shows that the slope of the graph represents the catalytic kinetics of the material, and the lower the slope of the graph is more favorable for the generation of more gas at the overpotential of The Tafel slope corresponding to the selenium and phosphorus double-doped nickel-cobalt oxide provided by the fourth embodiment is the lowest, namely the material has better activity when being used as a catalyst. As shown in fig. 7, the tafel slope diagram of fig. 5 provided in the present application shows the same slope as the slope corresponding to the selenium and phosphorus double-doped nickel-cobalt oxide, which has better activity. The invention utilizes selenium and phosphorus double-doped nickel cobalt oxide as an anode and a cathode respectively to assemble a full-electrolysis water electrolyzer in alkaline electrolyte, and as shown in figure 8, the selenium and phosphorus double-doped amorphous nickel cobalt oxide drives the electrolyzer to generate 10mA/cm2The voltage required for current density of 1.54V only.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
In view of the above description of the technical solutions provided by the present invention, those skilled in the art will recognize that there may be variations in the technical solutions and the application ranges according to the concepts of the embodiments of the present invention, and in summary, the content of the present specification should not be construed as limiting the present invention.
Claims (9)
- A method of preparing electrocatalytic materials, said method comprising:preparing nickel cobalt hydroxide by using a hydrothermal reaction;annealing the nickel-cobalt hydroxide and selenium powder in argon to obtain selenium-doped nickel cobaltate;and annealing the selenium-doped nickel cobaltate and sodium hypophosphite in argon to obtain the electro-catalytic material.
- 2. The method of preparing an electrocatalytic material as set forth in claim 1, wherein the preparing the nickel cobalt hydroxide using the hydrothermal reaction comprises:dissolving soluble nickel salt, soluble cobalt salt, ammonium fluoride and hexamethylenetetramine in a solvent according to a molar ratio of 5:10:20:2 to obtain th solution, wherein the solvent is a mixed solution of ethanol and water in a volume ratio of 1: 1;and (3) keeping the th solution at 140 ℃, heating for 8h, cooling to room temperature, washing with water, washing with alcohol, and drying to obtain the nickel cobalt hydroxide.
- 3. The method of claim 1, wherein annealing the nickel cobalt hydroxide and selenium powder in argon to obtain the selenium-doped nickel cobaltate comprises:and mixing the nickel cobalt hydroxide with selenium powder, and heating the mixture for 2 hours at 400 ℃ in an argon environment to obtain the selenium-doped nickel cobaltate.
- 4. The method of claim 1, wherein annealing the selenium-doped nickel cobaltate with sodium hypophosphite in argon to obtain the electrocatalytic material comprises:and mixing the selenium-doped nickel cobaltate with sodium hypophosphite, and heating the mixture for 15-90 min at 400 ℃ in an argon environment to obtain the electro-catalytic material.
- 5. The method of claim 4, wherein the selenium-doped nickel cobaltate and the sodium hypophosphite are heated in argon for 30 min.
- 6, kinds of electrocatalytic materials, characterized in that, the electrocatalytic materials are prepared by the method of any kinds of electrocatalytic materials of claims 1-5.
- 7. The electrocatalytic material as set forth in claim 6, wherein the electrocatalytic material comprises 18.13 to 23.68% by mass of cobalt, 4.57 to 11.28% by mass of nickel, 41 to 53.95% by mass of oxygen, 2.76 to 4.95% by mass of selenium, and 5.35 to 8.2% by mass of phosphorus.
- 8. The electrocatalytic material of claim 6 or 7, wherein the electrocatalytic material is a sheet-like structure.
- 9. Use of an electrocatalytic material as claimed in any of claims 6 to 8 at in electrolysis of water.
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