CN113186558A - Sponge nickel/octa-sulfide nine-nickel composite material and preparation method and application thereof - Google Patents
Sponge nickel/octa-sulfide nine-nickel composite material and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 229940078494 nickel acetate Drugs 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- XTUNVEMVWFXFGV-UHFFFAOYSA-N [C].CCO Chemical compound [C].CCO XTUNVEMVWFXFGV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- JLQNHALFVCURHW-UHFFFAOYSA-N cyclooctasulfur Chemical compound S1SSSSSSS1 JLQNHALFVCURHW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000010295 mobile communication Methods 0.000 abstract description 3
- 238000010248 power generation Methods 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000002070 nanowire Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003491 array Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a sponge nickel/octa-nickel sulfide composite material, a preparation method thereof and application of the composite material as a hydrogen evolution electrocatalyst material. The material has larger specific surface area, the nickel sponge is loaded with the octasulfide nine-nickel nanowire array, the contact area of electrolyte and a motor can be increased, a larger and more effective active reaction area is provided, meanwhile, the electron conduction rate is accelerated, and the electrochemistry is improvedAnd (4) performance. Sponge nickel/Ni of the invention9S8The material has the characteristics of long cycle life and low overpotential, and has wide application prospect in the fields of mobile communication, electric automobiles, solar power generation, aerospace and the like.
Description
Technical Field
The invention relates toThe technical field of electrocatalyst materials, in particular to sponge nickel/octa-nickel sulfide (Ni)9S8) Composite materials, methods of making the same and their use as electrocatalysts.
Background
The current energy crisis is becoming more serious, and the development of renewable hydrogen energy sources is the subject of the world at present. The hydrogen comes from water, and the water molecules are driven to be degraded into the hydrogen by electric energy, so that the hydrogen is an effective strategy for environmental protection. In order to reduce the use of electrical energy, advanced electrocatalysts need to be designed to reduce the overpotential. Currently, the noble metal platinum and its alloys exhibit very good catalytic properties. However, their development is hampered by the high price and low natural abundance of noble metal catalysts and by their poor cycle stability. Therefore, there is a need to develop advanced non-noble metal electrocatalysts to replace noble metals. The sponge nickel/octa-sulfur nonanickel composite material has rich active sites and sulfur vacancies and high conductivity, thereby showing good electrocatalytic performance, and not only having relatively low overpotential but also having high stability.
The sponge nickel coated by graphene is used as a substrate, and nine nickel octasulfide (Ni) is loaded and grown on the substrate9S8) The nanowire array can effectively improve the electron conduction rate and the specific surface area of the nickel nonasulfide, thereby improving the electrochemical performance of the nickel nonasulfide. The sponge nickel/octa-nickel sulfide composite material can be used as an electrocatalyst with high efficiency for hydrogen evolution.
Disclosure of Invention
The invention aims to provide sponge nickel/nonanickel octasulfide (Ni) aiming at the problem that the development of the noble metal catalysts is hindered by high price, low natural abundance and poor cycling stability of the prior noble metal catalysts9S8) The sponge nickel/octasulfide nonanickel electrode material has low over potential, low Tafel slope and high safety and stability.
Sponge nickel/octa-nickel sulfide (Ni)9S8) The preparation method of the composite material comprises the following steps:
(1) taking nickel acetate as a nickel source and hydrazine hydrate as a reducing agent to carry out hydrothermal reaction to obtain a sponge nickel scaffold;
(2) and (2) putting the sponge nickel support prepared in the step (1) into a tubular furnace, continuously introducing a mixed gas of argon and hydrogen, taking ethanol as a carbon source, and reacting by a one-step CVD (chemical vapor deposition) method to obtain the graphene-coated sponge nickel.
(3) And (3) taking the graphene-coated sponge nickel prepared in the step (2) as a nickel source and thiourea as a sulfur source, and obtaining the sponge nickel/octasulfide nonanickel composite material by a hydrothermal method.
According to the invention, a sponge nickel support coated by graphene is prepared by a hydrothermal method and a CVD method, and the sponge nickel support is used as a carrier to prepare the octa-sulfide nonanickel nanowire array electrode material by the hydrothermal method. The material has a large specific surface area, and the nickel sponge is loaded with the octa-sulfide nine-nickel nanowire array, so that the contact area of electrolyte and a motor can be increased, a larger and more effective active reaction area is provided, meanwhile, the electron conduction rate is accelerated, and the electrochemical performance is improved.
The following are preferred technical schemes of the invention:
the step (1) specifically comprises the following steps:
dissolving nickel acetate in deionized water, adding hydrazine hydrate, and carrying out hydrothermal reaction to obtain a sponge nickel scaffold;
the dosage ratio of the nickel acetate, the deionized water and the hydrazine hydrate is 1.24-1.28 g: 60-80 mL: 5-7 mL.
The conditions of the hydrothermal reaction are as follows: the hydrothermal reaction temperature is 150 ℃ and 220 ℃, and the hydrothermal reaction time is maintained for 5-16 h.
In step (2), the flow rates of argon and hydrogen are respectively 140 sccm and 180sccm and 10-20 sccm.
The reaction conditions of the one-step CVD (chemical vapor deposition) method are as follows: heating the reaction to 600-900 ℃, keeping the temperature for 8-20min, then opening a switch of the bubbler, introducing an ethanol carbon source, and finishing the reaction after 8-20 min.
The step (3) specifically comprises the following steps:
and (3) dissolving thiourea and polyvinylpyrrolidone (PVP) in deionized water to form a mixed solution, transferring the mixed solution to a reaction kettle, adding the graphene-coated sponge nickel prepared in the step (2), and performing hydrothermal reaction to obtain the sponge nickel/octa-nickel sulfide composite material.
The usage ratio of thiourea, polyvinylpyrrolidone (PVP) and deionized water is 0.2-0.6 g: 0.3-0.6 g: 40-80 mL, most preferably 0.4 g: 0.5 g: 60 mL.
The reaction kettle is a polytetrafluoroethylene high-pressure kettle;
carrying out hydrothermal reaction for 6-20h at 150-230 ℃. Further preferably, the hydrothermal reaction is carried out at 160 ℃ to 200 ℃ for 10 to 20 hours.
The sponge nickel/octa-sulfur nonanickel composite material (namely sponge nickel/Ni) prepared by the invention9S8Material) has low overpotential, good electronic conductivity and high safety and stability, Ni9S8The nanowires have an average diameter of about 10-100 nm. The sponge nickel/Ni9S8The material is used as a new nickel sulfide composite material. Particularly as electrocatalyst materials (i.e., hydrogen-producing electrocatalysts).
Compared with the prior art, the invention has the following advantages:
the method prepares the sponge nickel substrate coated by the graphene by a hydrothermal method and a chemical vapor deposition method, and then prepares the sponge nickel/Ni by a simple hydrothermal method9S8And (4) obtaining a target product. The preparation method is simple and convenient, and is easy to control.
Sponge nickel/Ni prepared by the invention9S8Electrode material with large specific surface area and Ni loaded on sponge nickel9S8The nanowire array can increase the contact area of electrolyte and an electrode, provide a larger and more effective active reaction area, accelerate the electron conduction rate and improve the electrochemical performance. The invention overcomes the defects of stability and reaction kinetics, thereby realizing that a certain hydrogen yield can be obtained by adopting low overpotential.
Sponge nickel/Ni of the invention9S8The composite material has larger specific surface area, and Ni is loaded on the bacterial cellulose9S8The nanowire array can increase the contact area of electrolyte and a motor, provide a larger and more effective active reaction area,meanwhile, the electron conduction rate is accelerated, and the electrochemical performance is improved. Preparation of sponge Nickel/Ni by hydrothermal method and CVD method9S8An electrode material. Sponge nickel/Ni of the invention9S8The material has high cycle stability, low overpotential and low Tafel slope, and has great application prospect in the field of hydrogen energy electro-catalysts.
Sponge nickel/Ni of the invention9S8The material has the characteristics of long cycle life and low overpotential, and has wide application prospect in the fields of mobile communication, electric automobiles, solar power generation, aerospace and the like.
Drawings
FIG. 1 shows the sponge Ni/Ni obtained in example 19S8XRD pattern of the target product.
FIG. 2 shows the sponge Ni/Ni obtained in example 29S8Scanning electron micrograph of target product, FIG. 2 (a) is sponge nickel/Ni prepared in example 2 at high resolution of 500nm9S8Scanning electron micrograph of target product, FIG. 2 (b) is sponge nickel/Ni prepared in example 2 at low resolution of 2 μm9S8Scanning electron microscope images of the target product.
FIG. 3 shows the sponge Ni/Ni obtained in example 39S8Transmission electron microscopy images of the target product.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
1.243g of nickel acetate was dissolved in 69mL of deionized water, stirred to a clear solution, 6mL of hydrazine hydrate was slowly added, and stirring was continued to a clear solution. Transferring the solution into the inner liner of a hydrothermal reaction kettle, installing a stainless steel shell, screwing the stainless steel shell, and placing the stainless steel shell in an oven at 150 ℃ for reaction for 7 hours. After the reaction is finished, after the reaction kettle is cooled to room temperature, the sponge nickel growing in the lining is taken out. The dried sponge nickel sample was placed in a quartz boat and then placed in the middle of the CVD tube furnace while the bubbler was charged with an appropriate ethanol solution as the carbon source for the reaction. And introducing argon into the tubular furnace, evacuating, continuously introducing a mixed gas of argon (160sccm) and hydrogen (20sccm), heating the furnace to 850 ℃ within 40min, keeping the temperature for 15min, opening a switch of a bubbler, introducing an ethanol carbon source, and reacting for 15 min. And after the tubular furnace is cooled to the room temperature, taking out the tubular furnace to obtain the sponge nickel sample coated with the graphene. 0.4g of thiourea and 0.5g of polyvinylpyrrolidone (PVP) were dissolved in 60mL of deionized water to form a mixed solution, which was then transferred to the inner liner of a reaction vessel, the prepared SNG sample was added, and the reaction vessel was covered with a stainless steel outer shell and placed in an oven to react at 180 ℃ for 14 hours. And taking out the sample after the reaction kettle is cooled to room temperature, and washing with deionized water and absolute ethyl alcohol and drying in an oven to obtain the nickel sponge sulfide sample.
Sponge Nickel/Ni prepared in example 19S8Target product (abbreviated as Ni)9S8@ SNG) is shown in figure 1.
Example 2
1.343g of nickel acetate was dissolved in 69mL of deionized water, stirred until a clear solution was obtained, then 7mL of hydrazine hydrate was slowly added, and stirring was continued until a clear solution was obtained. Transferring the solution into the inner liner of a hydrothermal reaction kettle, installing a stainless steel shell, screwing down, and placing in an oven at 180 ℃ for reaction for 9 hours. After the reaction is finished, after the reaction kettle is cooled to the room temperature of 25 ℃, the sponge nickel growing in the lining is taken out. The dried sponge nickel sample was placed in a quartz boat and then placed in the middle of the CVD tube furnace while the bubbler was charged with an appropriate ethanol solution as the carbon source for the reaction. And introducing argon into the tubular furnace, evacuating, continuously introducing a mixed gas of argon (165sccm) and hydrogen (15sccm), heating the furnace to 950 ℃ within 40min, preserving the temperature for 20min, opening a switch of a bubbler, introducing an ethanol carbon source, and reacting for 20 min. And after the tubular furnace is cooled to the room temperature of 25 ℃, taking out the tubular furnace to obtain the sponge nickel sample coated with the graphene. 0.4g of thiourea and 0.5g of polyvinylpyrrolidone (PVP) were dissolved in 60mL of deionized water to form a mixed solution, which was then transferred to the inner liner of a reaction vessel, the prepared SNG sample was added, and the reaction vessel was covered with a stainless steel shell and placed in an oven to react at 190 ℃ for 18 hours. And taking out the sample after the reaction kettle is cooled to room temperature of 25 ℃, and obtaining the nickel sponge sulfide sample after the sample is washed by deionized water and absolute ethyl alcohol and dried by an oven.
Sponge Nickel/Ni prepared in example 29S8The scanning electron micrograph of the target product is shown in FIG. 2, and the target product has a large specific surface area, and Ni is loaded on the sponge nickel9S8Nanowire arrays, Ni9S8The nanowire arrays have an average diameter of about 10-100 nm.
Example 3
1.343g of nickel acetate was dissolved in 69mL of deionized water, stirred until a clear solution was obtained, then 7mL of hydrazine hydrate was slowly added, and stirring was continued until a clear solution was obtained. Transferring the solution into the inner liner of a hydrothermal reaction kettle, installing a stainless steel shell, screwing the stainless steel shell, and placing the stainless steel shell in a 185 ℃ oven for reaction for 6 hours. After the reaction is finished, after the reaction kettle is cooled to the room temperature of 25 ℃, the sponge nickel growing in the lining is taken out. The dried sponge nickel sample was placed in a quartz boat and then placed in the middle of the CVD tube furnace while the bubbler was charged with an appropriate ethanol solution as the carbon source for the reaction. And introducing argon into the tubular furnace, evacuating, continuously introducing a mixed gas of argon (155sccm) and hydrogen (25sccm), heating the furnace to 950 ℃ within 40min, preserving the temperature for 20min, opening a switch of a bubbler, introducing an ethanol carbon source, and reacting for 20 min. And after the tubular furnace is cooled to the room temperature of 25 ℃, taking out the tubular furnace to obtain the sponge nickel sample coated with the graphene. 0.4g of thiourea and 0.5g of polyvinylpyrrolidone (PVP) were dissolved in 60mL of deionized water to form a mixed solution, which was then transferred to the inner liner of a reaction vessel, the prepared SNG sample was added, and the reaction vessel was covered with a stainless steel outer shell and placed in an oven to react at 200 ℃ for 14 hours. And taking out the sample after the reaction kettle is cooled to room temperature of 25 ℃, and obtaining the nickel sponge sulfide sample after the sample is washed by deionized water and absolute ethyl alcohol and dried by an oven.
Sponge Nickel/Ni prepared in example 39S8The transmission electron micrograph of the target product is shown in FIG. 3.
Performance testing
Sponge Nickel/Ni prepared as described in examples 1-3 above9S8The material is used as a working electrode, the carbon rod is used as a counter electrode, the calomel electrode is used as a reference electrode, and 1M KOH solution is respectively used as the counter electrodeElectrocatalytic performance tests were performed and all voltages were converted to reversible hydrogen potentials. The cell performance was tested separately in the electrochemical workstation. The test voltage range is 0 to-1.6V, and the sponge nickel/Ni is measured in the environment of 25 +/-1 DEG C9S8LSV curve and electrochemical stability of the material.
The performance test results are as follows:
sponge Nickel/Ni of examples 1, 2 and 39S8The material was at 10mA cm-2At current density of (2), sponge nickel/Ni9S8The material showed the most excellent hydrogen evolution activity, with the minimum overpotential (120mV,118mV and 140mV), and without any significant increase in voltage for 30 hours, even at high current density (50mA cm)-2) And still good cycle stability.
This is the sponge nickel/Ni prepared in accordance with the invention9S8Electrode material with large specific surface area and Ni loaded on sponge nickel9S8The nanowire array can increase the contact area of electrolyte and an electrode, provide a larger and more effective active reaction area, accelerate the electron conduction rate and improve the electrochemical performance. Thus, the sponge of the invention is nickel/Ni9S8The material has the characteristics of long cycle life and low overpotential, and has wide application prospect in the fields of mobile communication, electric automobiles, solar power generation, aerospace and the like.
Claims (10)
1. A preparation method of a sponge nickel/octa-nickel sulfide composite material is characterized by comprising the following steps:
(1) taking nickel acetate as a nickel source and hydrazine hydrate as a reducing agent to carry out hydrothermal reaction to obtain a sponge nickel scaffold;
(2) and (2) putting the sponge nickel support prepared in the step (1) into a tubular furnace, continuously introducing a mixed gas of argon and hydrogen, taking ethanol as a carbon source, and reacting by a one-step chemical vapor deposition method to obtain the graphene-coated sponge nickel.
(3) And (3) taking the graphene-coated sponge nickel prepared in the step (2) as a nickel source and thiourea as a sulfur source, and obtaining the sponge nickel/octasulfide nonanickel composite material by a hydrothermal method.
2. The preparation method of the sponge nickel/octa-nickel sulfide composite material as claimed in claim 1, wherein the step (1) specifically comprises:
dissolving nickel acetate in deionized water, adding hydrazine hydrate, and carrying out hydrothermal reaction to obtain a sponge nickel scaffold;
the dosage ratio of the nickel acetate, the deionized water and the hydrazine hydrate is 1.24-1.28 g: 60-80 mL: 5-7 mL.
3. The method for preparing a sponge nickel/octa-nickel sulfide composite material as claimed in claim 2, wherein the hydrothermal reaction conditions are as follows: the hydrothermal reaction temperature is 150 ℃ and 220 ℃, and the hydrothermal reaction time is maintained for 5-16 h.
4. The method as claimed in claim 1, wherein the flow rates of argon and hydrogen in step (2) are respectively 140-180sccm and 10-20 sccm.
5. The method for preparing a sponge nickel/octa-nonanickel sulfide composite material as claimed in claim 1, wherein in the step (2), the reaction conditions of the one-step chemical vapor deposition method are as follows: heating the reaction to 600-900 ℃, keeping the temperature for 8-20min, then opening a switch of the bubbler, introducing an ethanol carbon source, and finishing the reaction after 8-20 min.
6. The preparation method of the sponge nickel/octa-nickel sulfide composite material as claimed in claim 1, wherein the step (3) specifically comprises:
and (3) dissolving thiourea and polyvinylpyrrolidone in deionized water to form a mixed solution, transferring the mixed solution to a reaction kettle, adding the graphene-coated sponge nickel prepared in the step (2), and performing hydrothermal reaction to obtain the sponge nickel/octa-nickel sulfide composite material.
7. The preparation method of the sponge nickel/octa-nickel sulfide composite material as claimed in claim 6, wherein the usage ratio of the thiourea, the polyvinylpyrrolidone (PVP) and the deionized water is 0.2-0.6 g: 0.3-0.6 g: 40-80 mL.
8. The preparation method of the sponge nickel/octa-sulfur nonanickel composite material as claimed in claim 6, characterized in that the hydrothermal reaction is carried out for 6-20h at 150 ℃ -230 ℃.
9. The sponge nickel/octa-nickel sulfide composite material prepared by the preparation method according to any one of claims 1 to 8.
10. Use of a sponge nickel/nonanickel octasulfide composite material according to claim 9 as hydrogen-producing electrocatalyst.
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| CN114146712A (en) * | 2021-11-24 | 2022-03-08 | 沈阳化工大学 | Preparation method of nickel sulfide and nonanickel octasulfide composite phase |
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| CN114146712B (en) * | 2021-11-24 | 2023-11-28 | 沈阳化工大学 | Preparation method of composite phase of nickel sulfide and nickel octasulfide |
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