CN110021757B - Preparation method of nanorod material wrapped by nickel selenide sulfide film growing on surface of foamed nickel - Google Patents
Preparation method of nanorod material wrapped by nickel selenide sulfide film growing on surface of foamed nickel Download PDFInfo
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Abstract
The invention relates to a method for preparing a nano rod material wrapped by a nickel selenide sulfide film growing on the surface of foamed nickel, which comprises the steps of adding a thiourea solution and ammonium fluoride into a dissolved selenium powder mixed solution, and then adding absolute ethyl alcohol and deionized water to obtain a mixed solution; activating the surface of the foamed nickel to obtain pretreated foamed nickel; pouring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, putting the pretreated foamed nickel into the reaction kettle, and placing the reaction kettle in a drying oven for hydrothermal treatment; and after cooling, washing with deionized water, and drying to obtain the nano rod wrapped by the nickel selenide sulfide film on the surface of the foamed nickel. The nano rod material wrapped by the nickel selenide sulfide film consists of a phase of nickel selenide sulfide, wherein the length of the nano rod is 1-6 mu m, the diameter is 100-300nm, and the nano rod is uniformly distributed on the nickel foam. The preparation method provided by the invention has the advantages of simple required equipment, convenient operation, controllable conditions, high repeatability and low preparation cost, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of new materials and chemical synthesis, particularly relates to a preparation method of a nanorod material wrapped by a nickel selenide sulfide film growing on the surface of foam nickel, and provides a preparation method with simple process and low cost.
Background
With the development of modern society, energy problems and environmental problems become more serious, and therefore, the development and utilization of new energy sources are imminent. The development of high performance fuel cells and metal air cells remains a significant challenge due to the slow kinetics of hydrogen evolution reactions, oxygen evolution reactions, and large overpotentials. The anode with high performance for catalyzing hydrogen evolution reaction and the cathode with high performance for catalyzing oxygen evolution reaction can accelerate the reaction kinetics characteristic, thereby improving the performance of fuel cells and metal air cells. It is well known that Pt/C catalysts are highly efficient hydrogen evolution catalysts, IrO2/RuO2The catalyst is a high-efficiency oxygen precipitation catalyst, but has no prospect of large-scale application due to the problems of high price, scarce resources, poor stability and the like. Therefore, the search for electrode materials with low cost, high stability and bifunctional catalysis is currently the focus and focus of research in this field.
In addition, in the process of practical application and catalysis, in order to further improve the activity of the material: on one hand, the material is subjected to micro-nano treatment to form a nano-level structure, so that the electrochemical active area of the electrode material is increased to a certain extent, and the reaction is promoted. However, the conventional method for preparing the metal compound is a solid-phase method, and the method usually needs to be subjected to a high-temperature high-pressure heat treatment process, so that not only is the energy consumption high, but also the product size is generally large, and the nano-scale material cannot be obtained through control; on the other hand, the electrical conductivity of the catalyst is generally poor, and the method of adding conductive carbon is generally adopted to overcome the problem of low intrinsic electron conduction efficiency, but this causes the loss of active substances and causes some side reactions, which is also the key to limit the practical application of the catalyst as an electrode material. In addition, the traditional electrode preparation method is to mix and mechanically grind active substances, conductive carbon black, a binder and the like and then coat the mixture on a conductive substrate (such as carbon paper and carbon cloth). The integral electrode can expose more active sites, facilitating charge transport and gas diffusion. The foam nickel has good conductivity, and the nickel element has certain catalytic property and low price, and the like, so that the foam nickel is a catalyst substrate material which is well selected in the integrated electrode. There is a need for an inexpensive, highly active, integrated electrode that is catalytic. In addition, the homogeneous structure can reduce ohmic effects, reduce contact resistance, and improve the conductivity of the catalytic material.
As a non-noble metal catalyst, the transition metal nickel-based sulfide becomes one of the substitutes of noble metal catalytic materials due to the advantages of low cost, abundant resources, good environmental compatibility and the like, and is widely concerned by researchers. However, the active site of the metal sulfide electrode material is single, and the activity is lower. Selenium is a semimetal element in group six of the periodic table and has chemical properties similar to sulfur. However, selenium atoms have lower electronegativity and larger atomic radius compared with sulfur atoms, and these characteristics endow selenium elements with high chemical reactivity, and transition metal nickel dianion chalcogenide composite materials become a new development trend. The nickel selenide sulfide as a transition metal double anion sulfur family compound has a good application prospect in the aspects of full water-splitting fuel cells and the like, however, from the existing reports, a single nickel selenide sulfide substance is rarely synthesized, and as the selenium atom radius is larger than the sulfur atom radius, lattice distortion is easily caused, so that the selenium atom cannot enter crystal lattices to replace sulfur, the nickel selenide sulfide and the nickel selenide sulfide are generally researched and generated into a mixed substance. Therefore, it is a very significant task to find a simple and feasible preparation method for forming an integrated electrode with a nickel selenide sulfide homogeneous structure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a nanorod material wrapped by a nickel selenide sulfide film growing on the surface of foam nickel; the preparation process is simple, convenient to operate and high in repeatability; the nano rods wrapped by the nickel selenide sulfide thin film grown in situ by the foamed nickel are uniformly distributed and have larger length-diameter ratio; can be directly used as an electrode for application, does not need to additionally add a binder and a conductive agent, and has excellent energy catalysis application prospect.
The purpose of the invention is realized by the following technical scheme:
a nickel selenide sulfide thin film coated nanorod material growing on the surface of foamed nickel is characterized in that: the nano rod material wrapped by the nickel selenide sulfide film consists of a phase of nickel selenide sulfide, wherein the length of the nano rod is 1-6 mu m, the diameter is 100-300nm, and the nano rod is uniformly distributed on the nickel foam.
The invention relates to a preparation method of a nickel selenide sulfide film coated nanorod material growing on the surface of foam nickel, which comprises the following steps:
(1) weighing selenium powder, dissolving the selenium powder in hydrazine hydrate, and mechanically stirring at room temperature;
(2) adding a thiourea solution and ammonium fluoride into the dissolved selenium powder mixed solution, then adding absolute ethyl alcohol and deionized water, and mechanically stirring at room temperature to obtain a mixed solution;
(3) activating the surface of the foamed nickel, placing the foamed nickel in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 5-40min, taking out the foamed nickel, placing the foamed nickel in an acid solution, soaking for 0.5-12h, taking out the foamed nickel, placing the foamed nickel in deionized water, and ultrasonically cleaning for 5-40min to obtain pretreated foamed nickel;
(4) pouring the mixed solution prepared in the step (2) into a reaction kettle with a polytetrafluoroethylene lining, putting the foam nickel pretreated in the step (3) into the reaction kettle, putting the reaction kettle into an oven, and carrying out hydrothermal treatment on the foam nickel;
(5) and repeatedly washing the cooled nano-rods by using deionized water, and drying the nano-rods in an oven to obtain the nano-rods wrapped by the nickel selenide sulfide thin film on the surface of the foamed nickel.
Preferably, in the step (1), the selenium powder has a purity of 80.0-99.999% and a concentration of 2-12g/L and the hydrazine hydrate has a purity of 80.0% -98.0% and a concentration of 1-5 mol/L.
In the preferable step (2), the thiourea has a purity of 80.0% -99.0% and a concentration of 2-12g/L, the ammonium fluoride has a purity of 80.0% -99% and a concentration of 4-16g/L, the absolute ethyl alcohol has a purity of 80.0% -99.7% and a concentration of 2-8mol/L, and the volume ratio of the absolute ethyl alcohol solution to the deionized water is 3: 4-1.
Preferably, in the step (2), the stirring speed is 600-2000r/min, and the stirring time is 20-60 min.
Preferably, in the step (4), the reaction temperature of the reaction kettle in the oven is 140-260 ℃, and the reaction time is 10-48 h.
Preferably, in the step (5), the drying temperature in the oven is 40-100 ℃, and the drying time is 6-48 h.
The nickel selenide sulfide film growing on the surface of the foam nickel wraps the nano rod material and is directly used as an integrated electrode of the full-hydrolytic fuel cell.
The sulfur nickel selenide film grown on the surface of the foamed nickel wraps the nano rod material without adding a conductive agent, a binder and an electrode preparation process, and is directly used as an electrode to directly form a full water fuel cell in an alkaline system, the sulfur nickel selenide film grown on the surface of the foamed nickel wraps the nano rod material to be used as a negative and positive working electrode, and 1.0mol/L KOH solution is used as electrolyte to form the full water fuel cell system.
Compared with the prior art, the invention has the following advantages: (1) the nickel selenide sulfide film growing on the surface of the foamed nickel provided by the invention wraps the nano rod material, the shape is uniform, and the nano rod material consists of a nickel selenide sulfide homogeneous structure, the length of the nano rod is 1-6 mu m, the diameter of the nano rod is 100-500 nm, the nano rod material is uniformly distributed on the foamed nickel, and the unique microstructure is beneficial to the exposure of an active site and the increase of conductivity, so that the improvement of electrochemical performance is promoted; (2) the preparation method provided by the invention has the advantages of simple required equipment, convenient operation, controllable conditions, high repeatability and low preparation cost, and is suitable for industrial large-scale production; (3) the foam nickel is used as a substrate to provide a three-dimensional conductive network channel, so that the obtained nickel selenide sulfide thin film coated nanorod material on the surface of the foam nickel can be directly used as an electrode for electrochemical performance test, other binders, conductive agents and an electrode preparation process are not required to be additionally added, and the loading capacity of active substances is improved to the greatest extent. Meanwhile, the bonding force between the in-situ grown nickel selenide sulfide film coated nanorod and the substrate is firm, the contact resistance is reduced, and the technical problem that the active substance is easy to fall off in the traditional process is solved. By the advantages, the electrode shows excellent dual-function hydrogen evolution activity, oxygen evolution activity and stability in alkaline solution, and has wide application prospect in the aspects of full water-splitting fuel cells and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a low power of the nickel selenide sulfide thin film coated nanorod material growing on the surface of the foamed nickel prepared by the invention.
FIG. 2 is a high-power scanning electron microscope picture of a nickel selenide sulfide thin film coated nanorod material growing on the surface of foamed nickel prepared by the invention.
FIG. 3 is a scanning image of a TEM of a nano-rod material wrapped by a thin film of nickel selenide sulfide grown on the surface of nickel foam.
FIG. 4 is an XRD curve of the nickel selenide sulfide thin film coated nanorod material grown on the surface of the nickel foam prepared by the invention.
FIG. 5 is an LSV diagram of HER of a nickel selenide sulfide thin film coated nanorod material grown on the surface of foamed nickel in a 1M KOH electrolyte.
Fig. 6 is a long-period HER stability test result diagram of the nickel selenide sulfide thin film coated nanorod material grown on the surface of the nickel foam according to the present invention in a 1M KOH electrolyte.
FIG. 7 is an LSV diagram of OER of the nickel selenide sulfide thin film coated nanorod material grown on the surface of the foamed nickel in a 1M KOH electrolyte.
FIG. 8 is a long-period OER stability test result of the nickel selenide sulfide thin film coated nanorod material grown on the surface of the foamed nickel in a 1M KOH electrolyte.
Fig. 9 is an LSV diagram of total hydrolysis of the nickel selenide sulfide thin film coated nanorod material grown on the surface of the nickel foam in 1M KOH electrolyte.
Fig. 10 is a long-period full-hydrolysis stability test result diagram of the nickel selenide sulfide thin film coated nanorod material growing on the surface of the foamed nickel in the 1M KOH electrolyte.
Detailed Description
The present invention is described in detail below with reference to specific embodiments and accompanying drawings. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
(1) Weighing 5.76g/L selenium powder, taking hydrazine hydrate solution with the concentration of 2.5mol/L to dissolve the selenium powder, and mechanically stirring at the room temperature at the rotating speed of 1200r/min for 30 min;
(2) adding 5.56g/L thiourea and 8g/L ammonium fluoride into the selenium powder dissolved mixed solution, then adding 15mL of absolute ethyl alcohol with the concentration of 4mol/L and 9mL of deionized water, and mechanically stirring at the rotating speed of 1200r/min for 30min at room temperature to obtain a mixed solution;
(3) activating the surface of the foamed nickel, placing the foamed nickel in acetone, alcohol and deionized water respectively, and ultrasonically cleaning for 20min, taking out the foamed nickel, placing the foamed nickel in an acid solution for soaking for 6h, taking out the foamed nickel, placing the foamed nickel in deionized water, and ultrasonically cleaning for 20min to obtain pretreated foamed nickel;
(4) pouring the mixed solution prepared in the step 2 into a reaction kettle with 50ml of polytetrafluoroethylene lining, putting the foamed nickel pretreated in the step 3 into the reaction kettle, putting the reaction kettle into an oven, preserving the heat for 20 hours at the temperature of 200 ℃,
(5) and repeatedly washing the cooled nickel substrate by using deionized water, and drying the nickel substrate in an oven for 24 hours at the temperature of 60 ℃ to obtain the nickel selenide sulfide thin film coated nanorod material growing on the surface of the foamed nickel.
Fig. 1 is a macroscopic scanning electron microscope picture of the nickel selenide sulfide thin film coated nanorod material growing on the surface of the nickel foam prepared in the invention, which shows that the nickel selenide sulfide thin film coated nanorods are uniformly distributed on the nickel foam.
FIG. 2 is a high-power scanning electron microscope picture of the nano-rod material coated with the nickel selenide sulfide thin film growing on the surface of the nickel foam, which shows that the nano-rod material coated with the nickel selenide sulfide thin film has a length of about 2 μm and a diameter of about 150-180 nm.
FIG. 3 is a transmission electron microscope image of the nickel selenide sulfide thin film coated nanorod material grown on the surface of the nickel foam prepared in the invention, which shows that the synthesized nanorod structure is formed by densely coating the nanorod with a thin film, the diameter of the nanorod is about 150-180nm, and the nanorod has a larger length-diameter ratio, so that the structure facilitates the exposure of active sites and is beneficial to the improvement of electrochemical performance.
FIG. 4 is an XRD spectrum of a nickel selenide sulfide thin film coated nanorod material grown on the surface of the foamed nickel prepared in the invention, which shows that the material is composed of nickel selenide sulfide, is in the middle of JCPDS standard card No.02-0892 and 02-1280 phases, has no other impurity peaks, and shows that the purity of the sample is high.
Fig. 5 is an LSV diagram of HER of the nickel selenide sulfide thin film coated nanorod material growing on the surface of the nickel foam in 1M KOH electrolyte, and the nickel selenide sulfide thin film coated nanorod material can reduce hydrogen evolution overpotential to 87mV or less, thereby effectively reducing additional energy consumption.
Fig. 6 is a long-period HER stability test result of the nickel selenide sulfide thin film-coated nanorod material grown on the surface of the nickel foam in the 1M KOH electrolyte, which shows that the material can continuously catalyze hydrogen evolution in an alkaline environment for 100 hours and then can still maintain a low overpotential, indicating that the material has good stability.
FIG. 7 is an LSV diagram of OER of the nickel selenide sulfide thin film coated nanorod material grown on the surface of the foamed nickel in 1M KOH electrolyte, compared with the noble metal IrO2More excellent, the nickel selenide sulfide film coated nano rod material can reduce the oxygen evolution overpotential to below 246mV, and effectively reduce the additional energy consumption.
Fig. 8 is a long-period OER stability test result of the nickel selenide sulfide thin film coated nanorod material grown on the surface of the nickel foam in the 1M KOH electrolyte, and the material can continuously catalyze and evolve oxygen in an alkaline environment for 100 hours and then can still maintain a low overpotential, indicating that the material has good stability.
FIG. 9 shows sulfur grown on the surface of nickel foam prepared by the present inventionThe LSV diagram of the total hydrolysis of the nickel selenide film coated nano rod material in the 1M KOH electrolyte is compared with the noble metal Pt/C IrO2More excellent, the nickel selenide sulfide film coated nano rod material can reduce hydrogen evolution overpotential to below 1.56V, and effectively reduce extra energy consumption.
Fig. 10 is a long-period total hydrolysis stability test result diagram of the nickel selenide sulfide thin film coated nanorod material growing on the surface of the foamed nickel in the 1M KOH electrolyte, and the material can continuously catalyze the total hydrolysis in an alkaline environment for 100 hours and then can still maintain a low potential, indicating that the material has good stability.
Example 2
(1) Weighing selenium powder with the concentration of 2.88g/L, taking hydrazine hydrate solution with the concentration of 1.5mol/L to dissolve the selenium powder, and mechanically stirring at the rotating speed of 600r/min for 20min at room temperature;
(2) adding thiourea with the concentration of 8.34g/L and ammonium fluoride with the concentration of 10g/L into the selenium powder dissolved mixed solution, then adding 12mL of absolute ethyl alcohol with the concentration of 3mol/L and 15mL of deionized water, and mechanically stirring at the rotating speed of 600r/min for 20min at room temperature to obtain a mixed solution;
(3) activating the surface of the foamed nickel, placing the foamed nickel in acetone, alcohol and deionized water respectively, and ultrasonically cleaning for 5min, taking out the foamed nickel, placing the foamed nickel in an acid solution for soaking for 12h, taking out the foamed nickel, placing the foamed nickel in deionized water, and ultrasonically cleaning for 40min to obtain pretreated foamed nickel;
(4) pouring the mixed solution prepared in the step 2 into a 50ml reaction kettle with a polytetrafluoroethylene lining, putting the foam nickel pretreated in the step 3 into the reaction kettle, putting the reaction kettle into an oven, preserving heat for 10 hours at the temperature of 140 ℃,
(5) and repeatedly washing the cooled nickel substrate by using deionized water, and drying the nickel substrate in an oven at 40 ℃ for 6 hours to obtain the nickel selenide sulfide thin film coated nanorod material growing on the surface of the foamed nickel.
The characterization results of the morphology and the structure of the nickel selenide film by scanning, a transmission electron microscope and XRD show that the nickel selenide sulfide film wrapping nanorod material growing on the surface of the foamed nickel is prepared. The nickel selenide film coated nanorod material prepared in the embodiment is composed of NiSSe, the length of the nanorod is 1 mu m, the diameter of the nanorod is 100-120nm, and the nanorod is uniformly distributed on the nickel foam.
The polarization curve (LSV) diagram of the nickel selenide sulfide film coated nanorod material prepared in the embodiment in a 1M KOH electrolyte is that the hydrogen evolution overpotential of the nickel selenide sulfide film coated nanorod material is about 134mV, the oxygen evolution overpotential is about 320mV, and the total electrolysis water potential is about 1.68V, so that the extra energy consumption is effectively reduced, and the stability is good.
Example 3
(1) Weighing selenium powder with the concentration of 8.64g/L, taking hydrazine hydrate solution with the concentration of 5mol/L to dissolve the selenium powder, and mechanically stirring at the rotating speed of 1600r/min for 40min at room temperature;
(2) adding thiourea with the concentration of 2.78g/L and ammonium fluoride with the concentration of 10mol/L into the selenium powder dissolved mixed solution, then adding 15mL of absolute ethyl alcohol with the concentration of 6mol/L and 5mL of deionized water, and mechanically stirring at the rotating speed of 1600r/min for 40min at room temperature to obtain a mixed solution;
(3) activating the surface of the foamed nickel, placing the foamed nickel in acetone, alcohol and deionized water respectively, and ultrasonically cleaning for 40min, taking out the foamed nickel, placing the foamed nickel in an acid solution, soaking for 0.5h, taking out the foamed nickel, placing the foamed nickel in deionized water, and ultrasonically cleaning for 5min to obtain pretreated foamed nickel;
(4) pouring the mixed solution prepared in the step 2 into a 50ml reaction kettle with a polytetrafluoroethylene lining, putting the foam nickel pretreated in the step 3 into the reaction kettle, putting the reaction kettle into an oven, preserving heat for 18h at 160 ℃,
(5) and repeatedly washing the cooled nickel substrate by using deionized water, and drying the nickel substrate in an oven for 48 hours at 40 ℃ to obtain the nickel selenide sulfide thin film coated nanorod material growing on the surface of the foamed nickel.
The characterization results of the morphology and the structure of the nickel selenide film by scanning, a transmission electron microscope and XRD show that the nickel selenide sulfide film wrapping nanorod material growing on the surface of the foamed nickel is prepared. The nickel sulfide film coated nanorod material prepared in the embodiment is composed of NiSSe, the length of the nanorod is 3 microns, the diameter of the nanorod is 270-300nm, and the nanorod is uniformly distributed on the nickel foam.
The polarization curve (LSV) diagram of the nickel selenide sulfide film coated nanorod material prepared in the embodiment in a 1M KOH electrolyte is that the hydrogen evolution overpotential of the nickel selenide sulfide film coated nanorod material is about 124mV, the oxygen evolution overpotential is about 300mV, and the total electrolysis water potential is about 1.65V, so that the extra energy consumption is effectively reduced, and the stability is good.
Example 4
(1) Weighing selenium powder with the concentration of 2g/L, taking hydrazine hydrate solution with the concentration of 1mol/L to dissolve the selenium powder, and mechanically stirring at the room temperature at the rotating speed of 1500r/min for 25 min;
(2) adding 12g/L thiourea and 16g/L ammonium fluoride, then adding 13mL of absolute ethyl alcohol with the concentration of 2mol/L and 15mL of deionized water, and mechanically stirring at the rotating speed of 1500r/min for 25min at room temperature to obtain a mixed solution;
(3) activating the surface of the foamed nickel, placing the foamed nickel in acetone, alcohol and deionized water respectively, and ultrasonically cleaning for 20min, taking out the foamed nickel, placing the foamed nickel in an acid solution for soaking for 6h, taking out the foamed nickel, placing the foamed nickel in deionized water, and ultrasonically cleaning for 20min to obtain pretreated foamed nickel;
(4) pouring the mixed solution prepared in the step 2 into a 50ml reaction kettle with a polytetrafluoroethylene lining, putting the foam nickel pretreated in the step 3 into the reaction kettle, putting the reaction kettle into an oven, preserving the heat for 10 hours at 260 ℃,
(5) and repeatedly washing the cooled nickel substrate by using deionized water, and drying the nickel substrate in an oven at 75 ℃ for 10 hours to obtain the nickel selenide sulfide thin film coated nanorod material growing on the surface of the foamed nickel.
The characterization results of the morphology and the structure of the nickel selenide film by scanning, a transmission electron microscope and XRD show that the nickel selenide sulfide film wrapping nanorod material growing on the surface of the foamed nickel is prepared. The nickel selenide sulfide thin film coated nanorod material prepared in the embodiment is composed of NiSSe, the length of the nanorod is 1 mu m, the diameter of the nanorod is 100-120nm, and the nanorod is uniformly distributed on the nickel foam.
The polarization curve (LSV) diagram of the nickel selenide sulfide film coated nanorod material prepared in the embodiment in a 1M KOH electrolyte is that the hydrogen evolution overpotential of the nickel selenide sulfide film coated nanorod material is about 94mV, the oxygen evolution overpotential is about 270mV, and the total electrolysis water potential is about 1.29V, so that the extra energy consumption is effectively reduced, and the stability is good.
Example 5
(1) Weighing 12g/L selenium powder, taking hydrazine hydrate solution with the concentration of 5mol/L to dissolve the selenium powder, and mechanically stirring at the rotating speed of 2000r/min for 60min at room temperature;
(2) adding thiourea with the concentration of 2g/L and ammonium fluoride with the concentration of 4g/L into the selenium powder dissolved mixed solution, adding 10mL of absolute ethyl alcohol with the concentration of 8mol/L and 10mL of deionized water, and mechanically stirring at the rotating speed of 2000r/min for 60min at room temperature to obtain a mixed solution;
(3) activating the surface of the foamed nickel, placing commercial foamed nickel in acetone, alcohol and deionized water respectively, and ultrasonically cleaning for 5min, taking out the foamed nickel, placing the foamed nickel in an acid solution, soaking for 0.5h, taking out the foamed nickel, placing the foamed nickel in deionized water, and ultrasonically cleaning for 5min to obtain pretreated foamed nickel;
(4) pouring the mixed solution prepared in the step 2 into a 50ml reaction kettle with a polytetrafluoroethylene lining, putting the foam nickel pretreated in the step 3 into the reaction kettle, putting the reaction kettle into an oven, preserving heat for 48 hours at 160 ℃,
(5) and repeatedly washing the cooled nickel substrate by using deionized water, and drying the nickel substrate in an oven for 6 hours at the temperature of 100 ℃ to obtain the nickel selenide sulfide film coated nanorod material growing on the surface of the foamed nickel.
The characterization results of the morphology and the structure of the nickel selenide film by scanning, a transmission electron microscope and XRD show that the nickel selenide sulfide film wrapping nanorod material growing on the surface of the foamed nickel is prepared. The nickel selenide sulfide thin film coated nanorod material prepared in the embodiment is composed of NiSSe, the length of the nanorod is 6 microns, the diameter of the nanorod is 260-300nm, and the nanorod is uniformly distributed on the nickel foam.
The polarization curve (LSV) diagram of the nickel selenide sulfide film coated nanorod material prepared in the embodiment in a 1M KOH electrolyte is that the hydrogen evolution overpotential of the nickel selenide sulfide film coated nanorod material is about 100mV, the oxygen evolution overpotential is about 280mV, and the total electrolysis water potential is about 1.61V, so that the extra energy consumption is effectively reduced, and the stability is good.
Although the method and the manufacturing technique of the present invention have been described with reference to the preferred embodiments, it will be apparent to those skilled in the art that the method and the manufacturing technique described herein can be modified or recombined to realize the final manufacturing technique without departing from the scope, spirit and scope of the present invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (5)
1. A preparation method of a nickel selenide sulfide film coated nanorod material growing on the surface of foamed nickel is characterized by comprising the following steps: the film and the nano-rod both have the shapes consisting of a nickel selenide sulfide phase, the length of the nano-rod is 1-2 mu m, the diameter is 100-300nm, and the nano-rod is uniformly distributed on the nickel foam; the method comprises the following steps:
(1) weighing selenium powder, dissolving the selenium powder in hydrazine hydrate, and mechanically stirring at room temperature;
(2) adding a thiourea solution and ammonium fluoride into the dissolved selenium powder mixed solution, then adding absolute ethyl alcohol and deionized water, and mechanically stirring at room temperature to obtain a mixed solution;
(3) activating the surface of the foamed nickel, placing commercial foamed nickel in acetone, absolute ethyl alcohol and deionized water in sequence, ultrasonically cleaning for 5-40min, taking out the foamed nickel, placing the foamed nickel in an acid solution, soaking for 0.5-12h, taking out the foamed nickel, placing the foamed nickel in deionized water, and ultrasonically cleaning for 5-40min to obtain pretreated foamed nickel;
(4) pouring the mixed solution prepared in the step 2) into a reaction kettle with a polytetrafluoroethylene lining, putting the foam nickel pretreated in the step 3) into the reaction kettle, putting the reaction kettle into an oven, and carrying out hydrothermal treatment on the foam nickel; the reaction temperature of the reaction kettle in the oven is 140-260 ℃, and the reaction time is 10-48 h;
(5) and repeatedly washing the cooled nano-rods by using deionized water, and drying the nano-rods in an oven to obtain the nano-rods wrapped by the nickel selenide sulfide thin film growing on the surface of the foamed nickel.
2. The method as claimed in claim 1, wherein in step 2), the stirring speed is 600-2000r/min, and the stirring time is 20-60 min.
3. The preparation method of claim 1, wherein in the step 5), the drying temperature in the oven is 40-100 ℃ and the drying time is 6-48 h.
4. The application of the nickel selenide sulfide thin film grown on the surface of the foamed nickel prepared by the preparation method of claim 1 to wrapping a nano rod material as an integrated electrode catalyst of a full-hydrolytic fuel cell.
5. The application of claim 4, wherein the nickel selenide sulfide thin film grown on the surface of the foamed nickel wraps the nanorod material to directly serve as a cathode and an anode working electrode, and a KOH solution of 1.0mol/L is used as an electrolyte to form a full-hydrolytic fuel cell system.
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| CN111111706A (en) * | 2019-07-24 | 2020-05-08 | 天津大学 | Nickel selenide sulfide nanorod coated by tungsten-doped nickel selenide sulfide film growing on surface of nickel foam and preparation method and application thereof |
| CN112447953B (en) * | 2019-09-03 | 2022-03-18 | 中南大学 | Metal selenide sulfide nanocrystalline @ porous carbon sphere material, preparation thereof and application thereof in lithium metal battery |
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| CN112614992B (en) * | 2020-12-10 | 2022-08-16 | 三峡大学 | Nickel composite positive electrode material of water-based zinc-nickel battery and preparation method of nickel composite positive electrode material |
| CN113089013B (en) * | 2021-03-29 | 2023-06-16 | 商洛学院 | NiSeP/NF composite electrode material and preparation method and application thereof |
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| CN114715857B (en) * | 2022-03-30 | 2023-08-25 | 蚌埠学院 | Preparation method and application of bimetal nickel molybdenum selenide electrode material |
| CN114774958B (en) * | 2022-04-20 | 2023-07-07 | 天津大学 | Corrosion-resistant nickel-iron electrode and preparation method and application thereof |
| CN115198304B (en) * | 2022-07-14 | 2023-03-24 | 青岛中石大新能源科技有限公司 | Nickel selenide sulfide composite seawater electrocatalyst and preparation method and application thereof |
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