CN110484934B - Preparation method of nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material - Google Patents
Preparation method of nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material Download PDFInfo
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Abstract
The invention relates to a preparation method of a nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material, belonging to the technical field of hydrogen electrode material preparation. The invention has the advantages of simple technical process, low cost and easy industrial application, the electrode material prepared by the method has rich and intercommunicated inner pore canals, excellent conductivity, large specific surface area and many electrocatalytic active point sites, and the prepared nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material has good application prospect in the field of hydrogen energy development and application.
Description
Technical Field
The invention relates to a preparation method of a nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material, belonging to the technical field of hydrogen electrode material preparation.
Background
The rapid development of social economy causes the problems of serious environmental pollution, rapid energy consumption, resource shortage and the like, the development and application of clean renewable energy sources are urgently needed, and among a plurality of clean energy sources, hydrogen energy is used as economic, efficient and sustainable green energy source, is one of the most ideal energy carriers, and receives more and more extensive attention. Among the various hydrogen production technologies, hydro-electric dissociation hydrogen production is considered to be one of the most effective routes to "hydrogen economy". However, in practical application, hydrogen production by water and electricity dissociation usually needs to overcome a higher overpotential of hydrogen evolution, so that higher energy loss is caused, and in order to effectively solve the technical bottleneck that the overpotential of hydrogen evolution by water and electricity dissociation is too high, the application of the high-efficiency catalytic material is a technical key for breaking through the bottleneck. The Pt family material has the highest electro-catalytic hydrogen evolution activity, but has limited reserves and high price, and is difficult to popularize and apply in a large scale. Therefore, the development of a hydrogen evolution electrocatalytic material with low cost, high activity and environmental friendliness is the key to realizing the development and engineering application of hydrogen energy.
Among numerous non-noble metal electrocatalytic materials, transition metal phosphide is one of hydrogen evolution electrocatalytic materials with high catalytic reaction activity, good stability and good cost effectiveness due to the unique electronic structure and metalloid characteristics thereof, and has the potential of replacing a Pt-based electrocatalytic material. Among a plurality of metal phosphides, nickel phosphide has the activity of water dissociation hydrogen evolution similar to that of [ NiFe ] hydrogenase, and is a potential hydrogen evolution catalytic material. Nickel-phosphorus alloys were previously used as protective coatings and in recent years have received attention for their application in the separation of hydrogen by hydroelectric dissociation. The nickel-phosphorus alloy coating for hydrogen evolution by water and electricity dissociation is generally in an amorphous or mixed crystal form, and has the characteristics of bright and uniform surface, high hardness, good wear resistance, non-magnetism and the like. In the aspect of nickel-phosphorus alloy coating preparation, electroplating and chemical plating processes are applied more, and the plating solution is mostly a nickel sulfate-phosphite system, and the method is characterized in that the plating solution is simple to prepare and has good stability, the obtained coating is compact and has good binding force, but the nickel-phosphorus alloy coatings prepared by the electroplating and chemical plating processes have few active point sites, and the hydrogen evolution performance has a gap from the engineering application requirements. At present, most phosphide catalytic materials for hydrogen evolution through water and electricity dissociation are prepared by a solution hydrothermal synthesis process and a high-temperature solid-phase reduction process, most phosphide catalytic materials are powder, and need to be fully dispersed in a solvent, and then the phosphide catalytic materials are fixed on a conductive carrier by utilizing binders such as a Nafion solution and a polyvinylidene fluoride organic solution, so that the catalyst loading capacity of a catalytic electrode is limited, the electrical conductivity of the electrode material can be reduced by the binders, and meanwhile, partial active point positions of the catalyst can be coated and shielded by the binders, so that the catalytic performance of the electrode material is reduced; in addition, in the long-time electrolysis process, the active catalytic material is easy to fall off from the surface of the electrode, so that the stability of the catalytic electrode for hydrogen evolution through water and electricity dissociation is poor. Therefore, the porous conductive material is used as a carrier, the active area of the electrode is increased, the in-situ growth technology is applied to load an active catalytic component on the surface of the electrode material, the use of a binder and a conductive agent is avoided and reduced, the preparation of the three-dimensional self-supporting electrode with excellent hydrogen evolution performance is an important development trend in the field of hydrogen evolution through water and electricity dissociation, and researchers at home and abroad develop a lot of research work. The patent with publication number CN108380227 discloses a hydrogen evolution electro-catalytic material and a preparation method thereof, which takes red phosphorus, self-made spherical metal nickel powder and 3% graphene by mass as main raw materials, performs the pre-forming treatment on the raw materials by using a tablet press, and then performs in-situ reaction at high temperature to prepare the three-dimensional porous self-supporting nickel phosphide hydrogen evolution electro-catalytic material. The patent with publication number CN106498434 discloses a preparation method of an integrated nickel-based porous nickel phosphide electrode, which comprises the steps of taking foamed nickel as a substrate, carrying out chemical etching on the foamed nickel substrate to prepare a nickel-based porous nickel precursor, and then carrying out in-situ phosphorization by adopting a solid-phase reduction method, wherein the prepared material shows excellent hydrogen evolution performance, but the hydrogen evolution electrode active material has poor stability and is easy to run off. Based on the technical defects that in the preparation process of the existing hydrogen evolution catalytic electrode, a catalyst needs to be bonded and fixed by using a binder, the conductivity of a nickel phosphide component is poor, and the number of hydrogen evolution active sites of the electrode is small, the design and preparation method of the three-dimensional self-supporting hydrogen evolution electrode material which is good in conductivity, large in active area, high in active component loading, high in liquid phase mass transfer rate and simple and convenient in process is explored, and the method is an important development content of hydrogen production through water and electricity dissociation.
Disclosure of Invention
The invention aims to provide a preparation method of a nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material, which has the effects of simple preparation process, low cost and excellent electrocatalytic hydrogen evolution performance. Firstly, carrying out acid dipping hydrophilic modification on a carbon cloth substrate, then growing nickel hydroxide on the carbon cloth through a hydrothermal process, then phosphorizing the surface of the carbon cloth at a low temperature by taking sodium hypophosphite as a phosphorus source to convert the nickel hydroxide into nickel phosphide, and then depositing a nickel-phosphorus alloy on the surface of the nickel phosphide, thereby preparing the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material which does not need a binder and has excellent electrocatalytic hydrogen evolution performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
the preparation method of the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material comprises the following steps:
step one, adding nickel nitrate and hexamethylenetetramine into a beaker filled with deionized water in sequence, placing the beaker on a magnetic stirrer, and stirring at room temperature to dissolve the nickel nitrate and the hexamethylenetetramine;
step two, transferring the solution stirred in the step one to a stainless steel reaction kettle with a polytetrafluoroethylene lining, simultaneously putting the carbon cloth subjected to acid soaking treatment into the stainless steel reaction kettle, screwing a sealing cover of the stainless steel reaction kettle, transferring the stainless steel reaction kettle to an electric furnace, and reacting for a period of time; after the reaction is finished, turning off the power supply of the electric furnace, taking out the stainless steel reaction kettle from the electric furnace after the temperature of the hearth is cooled to room temperature, opening a sealing cover of the reaction kettle, taking out the carbon cloth from the reaction kettle, washing the carbon cloth by using the additionally moved deionized water, and then washing the carbon cloth by using absolute ethyl alcohol;
thirdly, placing the carbon cloth washed cleanly in the second step into a vacuum drying oven for drying treatment for a period of time to obtain a nickel hydroxide-carbon cloth precursor material;
step four, respectively putting the nickel hydroxide-carbon cloth precursor material prepared in the step three and sodium hypophosphite powder into two porcelain boats, then putting the two porcelain boats filled with the samples into the center of a tube furnace, and connecting a nitrogen inlet pipe to the sample placing inlet end of the tube furnace;
connecting a working gas path, connecting a gas outlet end of the tube furnace with a mechanical pump, vacuumizing to negative pressure, evacuating a corundum tube and a gas pipeline of the tube furnace, then opening a nitrogen cylinder switch knob, opening an air inlet valve of the tube furnace, slowly introducing nitrogen into the tube furnace, and opening an air outlet valve of the tube furnace when a pressure gauge of the tube furnace gas is stabilized at 0 MPa; simultaneously, starting a heating switch of the tubular furnace, raising the temperature of the hearth from room temperature to a certain temperature at a constant heating rate under the protection of nitrogen, and preserving the heat for a period of time at the temperature to ensure that the nickel hydroxide loaded on the surface of the carbon cloth is phosphated to generate nickel phosphide;
step six, after the phosphating reaction in the step five is finished, closing the power supply of the tubular furnace and still keeping nitrogen gas introduction, naturally cooling the temperature in the tubular furnace to room temperature under the protection of the nitrogen gas, and then taking out the nickel hydroxide/carbon cloth after phosphating treatment from the tubular furnace to obtain the nickel phosphide-carbon cloth self-supporting material;
step seven, adding nickel chloride, trisodium citrate, ammonium sulfate and sodium hypophosphite into a beaker filled with 50mL of deionized water in sequence, placing the beaker on a magnetic stirrer, starting a stirring control knob switch, stirring the solution to completely dissolve all the added reagents, and obtaining nickel-phosphorus alloy electroplating solution after the reagents are dissolved and the solution is uniformly stirred;
step eight, constructing a three-electrode system by using the nickel phosphide-carbon cloth self-supporting material prepared in the step six as a working electrode, a clean graphite rod as an auxiliary electrode, an Ag/AgCl electrode as a reference electrode and the nickel phosphorus alloy electroplating solution prepared in the step seven as an electrolyte;
step nine, after the working electrode, the auxiliary electrode and the reference electrode in the step eight are connected with a constant potential rectifier, a power switch of the constant potential rectifier is turned on, and a constant current control mode is adopted to electrodeposit nickel-phosphorus alloy on the surface of the nickel phosphide-carbon cloth small piece;
and step ten, after the electrodeposition in the step nine is finished, taking out the nickel phosphide-carbon cloth loaded with nickel and phosphorus on the surface from the nickel-phosphorus alloy electroplating solution, respectively cleaning the nickel phosphide-carbon cloth with deionized water and absolute ethyl alcohol, and then placing the cleaned sample in a vacuum drying oven for drying treatment to obtain the nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material.
The technical scheme of the invention is further improved as follows: the carbon cloth in the second step is prepared through the following steps;
step I, adding concentrated nitric acid with the volume of 100mL and the mass concentration of 65-68% into a 250mL beaker, then cutting eight carbon cloths into 2cm multiplied by 2cm, adding the carbon cloths into the beaker containing the concentrated nitric acid, sealing the opening of the beaker by using a preservative film, and standing at room temperature for 45-48 h to carry out acid-soaking hydrophilic modification on the carbon cloths;
step II, after standing, placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein deionized water with the temperature of 20-30 ℃ is filled in the ultrasonic cleaner, the power of the cleaner is 450W, and the ultrasonic treatment time is 1-2 h;
step III, taking the carbon cloth subjected to ultrasonic treatment out of the beaker, and washing the carbon cloth by using deionized water until the pH value of the washing water is neutral; then, soaking and washing the carbon cloth twice by using absolute ethyl alcohol at room temperature, wherein the soaking time is 10-15 min each time, so as to ensure that the surface of the carbon cloth is clean, and washing the carbon cloth by using the absolute ethyl alcohol and then washing the carbon cloth by using deionized water for three times;
and step IV, after the carbon cloth is washed clean, placing the carbon cloth in a vacuum drying oven for drying at the temperature of 60-80 ℃, wherein the vacuum degree is-0.1 MPa, and the drying time is 10-12 h, so that the carbon cloth subjected to acid dipping treatment is obtained.
The technical scheme of the invention is further improved as follows: carbon cloth in the first step to the sixth step: nickel nitrate: hexamethylenetetramine: sodium hypophosphite: the mass proportion relation of the deionized water = 0.055-0.06: 0.7-0.75: 0.7-0.75: 0.25-0.3: 15 to 20.
The technical scheme of the invention is further improved as follows: in the second step, the temperature of the hearth of the electric furnace is 100-110 ℃, and the hydrothermal reaction is carried out for 10-12 h at the temperature
The technical scheme of the invention is further improved as follows: and in the third step and the tenth step, the drying temperature of the vacuum drying oven is 60-80 ℃, the drying time is 10-12 hours, and the vacuum degree is-0.1 MPa.
The technical scheme of the invention is further improved as follows: in the fourth step, the porcelain boat filled with the sodium hypophosphite is placed at one side close to the nitrogen gas inlet of the tube furnace, and the porcelain boat filled with the nickel hydroxide/carbon cloth precursor is placed at one side of the gas outlet.
The technical scheme of the invention is further improved as follows: step five, vacuumizing to enable the vacuum surface to be-0.1 MPa; the temperature of the hearth is increased from room temperature to 280-300 ℃ at the temperature increasing rate of 2-3 ℃/min, and the temperature is kept for 2-3 h at the temperature.
The technical scheme of the invention is further improved as follows: the mass proportion relation of the raw materials in the seventh step is that nickel chloride: trisodium citrate: ammonium sulfate: sodium hypophosphite: deionized water = 1.0-1.25: 2.75-3.0: 3.0-3.25: 2.75-3.0: 45-55, wherein the deionized water is 50 mL.
The technical scheme of the invention is further improved as follows: and step eight, fully soaking the working electrode, the auxiliary electrode and the reference electrode in the nickel-phosphorus alloy electroplating solution.
The technical scheme of the invention is further improved as follows: in the ninth step, the current density of the constant potential rectifier is 1-5 mAcm-2The electrodeposition temperature is room temperature, and the electrodeposition time is 60-180 s.
Due to the adoption of the technical scheme, the invention has the following technical effects:
1. the technical process is simple and convenient, has low cost and is easy for industrial production and application;
2. the carbon cloth is used as a substrate to prepare the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode, so that the large load area and the excellent electric conduction characteristic of the carbon cloth are fully utilized and exerted, the bonding strength of the nickel phosphide active component and the carbon cloth is improved, and the electrode is prepared without additional bonding;
3. the technology of the patent effectively fuses the advantages of two hydrogen evolution materials of nickel-phosphorus alloy and nickel phosphide, and meanwhile, the nickel-phosphorus alloy deposition also realizes the effective utilization of the nickel phosphide loading residual sites, the prepared nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material has rich and intercommunicated pore channel structures, the specific surface area is large, the catalytic activity sites are many, the hydrogen evolution performance is excellent, and the engineering application prospect is good;
4. this patent will be equipped with the porcelain boat of sodium hypophosphite and put in being close to tube furnace nitrogen gas inlet one side, and the porcelain boat that is equipped with nickel hydroxide carbon cloth precursor is put in gas outlet one side, and the phosphine gas that produces of sodium hypophosphite pyrolysis like this under the nitrogen protection can fully contact with the nickel hydroxide particle on the nickel hydroxide carbon cloth precursor along with the nitrogen gas air current, and then fully phosphorizes the nickel hydroxide particle.
Drawings
FIG. 1 is an XRD diffraction pattern of the three-dimensional self-supporting electrode material prepared in example 1;
FIG. 2 is a scanning electron microscope image of the nickel phosphide-carbon cloth uniformly grown on the carbon cloth manufactured in example 1;
FIG. 3 is a scanning electron microscope image of a nickel phosphide-carbon cloth non-uniformly grown on a carbon cloth manufactured in example 1;
FIG. 4 is a scanning electron microscope image of the Ni-P/Ni-P-C cloth prepared in example 1;
FIG. 5 is a plot of cathode linear scan polarization for the nickel phosphide-carbon cloth prepared in example 1 and the nickel phosphide/nickel phosphide-carbon hydrogen evolution electrodes prepared in examples 1, 2 and 3, respectively;
FIG. 6 is a graph showing the Tafel slopes of the nickel phosphide-carbon cloth prepared in example 1 and the nickel phosphide/nickel phosphide-carbon hydrogen evolution electrodes prepared in examples 1, 2 and 3, respectively.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific embodiments:
the invention discloses a preparation method of a nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material, which comprises the following steps of acid-dipping carbon cloth required to be acid-dipped:
step I, adding concentrated nitric acid with the volume of 100mL and the mass concentration of 65-68% into a 250mL beaker, cutting eight pieces of carbon cloth into 2cm multiplied by 2cm and the thickness of 0.33mm, adding the carbon cloth into the 250mL beaker filled with the concentrated nitric acid, sealing the mouth of the beaker by using a preservative film, and standing at room temperature for 45-48 h to carry out acid-soaking hydrophilic modification on the carbon cloth;
step II, after standing, placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein deionized water with the temperature of 20-30 ℃ is filled in the ultrasonic cleaner, the power of the cleaner is 450W, and the ultrasonic treatment time is 1-2 h;
step III, taking the carbon cloth subjected to ultrasonic treatment out of the beaker, and washing the carbon cloth for multiple times by using deionized water until the pH value of the washing water is neutral; then, soaking and washing the carbon cloth twice by using absolute ethyl alcohol at room temperature, wherein the soaking time is 10-15 min each time, so as to ensure that the surface of the carbon cloth is clean, and washing the carbon cloth by using the absolute ethyl alcohol and then washing the carbon cloth by using deionized water for three times;
and step IV, after the carbon cloth is washed clean, placing the carbon cloth in a vacuum drying oven for drying at the temperature of 60-80 ℃, wherein the vacuum degree is-0.1 MPa, and the drying time is 10-12 h, so that the carbon cloth subjected to acid dipping treatment is obtained.
The preparation method of the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material comprises the following steps:
step one, adding nickel nitrate and hexamethylenetetramine into a beaker filled with deionized water in sequence, placing the beaker on a magnetic stirrer, and stirring at room temperature to dissolve the nickel nitrate and the hexamethylenetetramine;
step two, transferring the solution stirred in the step one to a stainless steel reaction kettle with a polytetrafluoroethylene lining, simultaneously putting the carbon cloth subjected to acid dipping treatment into the stainless steel reaction kettle, screwing a sealing cover of the stainless steel reaction kettle and transferring the stainless steel reaction kettle into an electric furnace, wherein the hearth temperature of the electric furnace is 100-110 ℃, and carrying out hydrothermal reaction for 10-12 hours at the temperature; after the reaction is finished, turning off the power supply of the electric furnace, taking out the stainless steel reaction kettle from the electric furnace after the temperature of the hearth is cooled to room temperature, opening a sealing cover of the reaction kettle, taking out the carbon cloth from the reaction kettle, washing the carbon cloth with additionally moved deionized water for three times, and then washing the carbon cloth with absolute ethyl alcohol for three times;
thirdly, drying the carbon cloth washed cleanly in the second step in a vacuum drying oven at the drying temperature of 60-80 ℃ for 10-12 h under the vacuum degree of-0.1 MPa to obtain a nickel hydroxide-carbon cloth precursor material;
step four, respectively placing the nickel hydroxide-carbon cloth precursor material and the sodium hypophosphite powder prepared in the step three into two porcelain boats, then placing the two porcelain boats filled with the samples in the center of a tube furnace, wherein the inlet end of the sample placement of the tube furnace is connected with a nitrogen gas inlet pipe, the porcelain boat filled with the sodium hypophosphite is placed at one side close to the nitrogen gas inlet of the tube furnace, and the porcelain boat filled with the nickel hydroxide/carbon cloth precursor is placed at one side of a gas outlet;
connecting a working gas path, connecting a gas outlet end of the tube furnace with a mechanical pump, vacuumizing until the vacuum gauge reaches-0.1 MPa, evacuating the corundum tube and the gas pipeline of the tube furnace, then opening a nitrogen cylinder switch knob, opening an air inlet valve of the tube furnace to enable nitrogen to slowly enter the tube furnace, and opening an air outlet valve of the tube furnace when a pressure gauge of the tube furnace is stabilized at 0 MPa; simultaneously starting a heating switch of the tubular furnace, heating the temperature of the hearth from room temperature to 280-300 ℃ at a heating rate of 2-3 ℃/min under the protection of nitrogen, and preserving the heat for 2-3 h at the temperature to ensure that the nickel hydroxide loaded on the surface of the carbon cloth is phosphated to generate nickel phosphide;
step six, after the phosphating reaction in the step five is finished, closing the power supply of the tubular furnace and still keeping nitrogen gas introduction, naturally cooling the temperature in the tubular furnace to room temperature under the protection of the nitrogen gas, and then taking out the nickel hydroxide/carbon cloth after phosphating treatment from the tubular furnace to obtain the nickel phosphide-carbon cloth self-supporting material;
and step seven, sequentially adding nickel chloride, trisodium citrate, ammonium sulfate and sodium hypophosphite into a beaker filled with 50mL of deionized water, wherein the dosage of the raw materials is in the following mass ratio relationship: trisodium citrate: ammonium sulfate: sodium hypophosphite: deionized water = 1.0-1.25: 2.75-3.0: 3.0-3.25: 2.75-3.0: 45-55; then placing the beaker on a magnetic stirrer, starting a stirring control knob switch, stirring the solution to completely dissolve all the added reagents, and obtaining the nickel-phosphorus alloy electroplating solution after the reagents are dissolved and the solution is uniformly stirred;
step eight, cutting the nickel phosphide-carbon cloth self-supporting material prepared in the step six into 1cm multiplied by 1cm slices serving as a working electrode, a clean graphite rod serving as an auxiliary electrode, an Ag/AgCl electrode serving as a reference electrode and a nickel-phosphorus alloy electroplating solution prepared in the step seven serving as an electrolyte to construct a three-electrode system, wherein the working electrode, the auxiliary electrode and the reference electrode need to be fully soaked in the nickel-phosphorus alloy electroplating solution;
step nine, the working electrode and the auxiliary electrode are connectedAfter the electrode and the reference electrode are connected with the ZF-9 potentiostat, a power switch of the potentiostat is turned on, and a constant current control mode is adopted to electrodeposit nickel-phosphorus alloy on the surface of the nickel phosphide-carbon cloth chip, wherein the current density is 1mAcm-2The electrodeposition temperature is room temperature, and the electrodeposition time is 60-180 s;
and step ten, after the electrodeposition in the step nine is finished, taking out the nickel phosphide-carbon cloth chips loaded with nickel and phosphorus on the surfaces from the nickel-phosphorus alloy electroplating solution, respectively cleaning the nickel phosphide-carbon cloth chips with deionized water and absolute ethyl alcohol, then placing the cleaned samples in a vacuum drying oven for drying treatment, wherein the drying temperature is 60-80 ℃, the drying time is 10-12 hours, and the vacuum degree is-0.1 MPa, so as to obtain the nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material.
Decomposing hexamethylenetetramine in the aqueous solution to generate ammonia water, and generating nickel hydroxide by the generated ammonia water and nickel metal ions and depositing the nickel hydroxide on the carbon cloth;
the following are specific examples:
the carbon cloth after the acid impregnation treatment used in each example was prepared by the above method.
Example 1
Firstly, 0.7270g of nickel nitrate and 0.7010g of hexamethylenetetramine are sequentially added into a beaker filled with 18mL of deionized water, and then the beaker is placed on a magnetic stirrer and stirred at room temperature to be dissolved;
step two, transferring the solution stirred in the step one to a stainless steel reaction kettle with a volume of 25mL and a polytetrafluoroethylene lining, simultaneously putting square carbon cloth with the length and the width of 2cm after acid soaking treatment into the stainless steel reaction kettle, screwing a sealing cover of the stainless steel reaction kettle and transferring the stainless steel reaction kettle into an electric furnace, wherein the temperature of a hearth of the electric furnace is 100 ℃, and carrying out hydrothermal reaction for 10 hours at the temperature; after the reaction is finished, turning off the power supply of the electric furnace, taking out the stainless steel reaction kettle from the electric furnace after the temperature of the hearth is cooled to room temperature, opening a sealing cover of the reaction kettle, taking out the carbon cloth from the reaction kettle, washing the carbon cloth with additionally moved deionized water for three times, and then washing the carbon cloth with absolute ethyl alcohol for three times;
step three, placing the carbon cloth washed cleanly in the step two in a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the drying time is 12 hours, and the vacuum degree is-0.1 MPa, so as to obtain a nickel hydroxide-carbon cloth precursor material;
step four, respectively putting the nickel hydroxide-carbon cloth precursor material prepared in the step three and 0.25g of sodium hypophosphite powder into two porcelain boats, then putting the two porcelain boats filled with the samples in the center of a tube furnace, and connecting a nitrogen gas inlet pipe to the sample placing inlet end of the tube furnace, wherein the porcelain boat filled with the sodium hypophosphite is placed at one side close to the nitrogen gas inlet of the tube furnace, and the porcelain boat filled with the nickel hydroxide/carbon cloth precursor is placed at one side of a gas outlet;
connecting a working gas path, connecting a gas outlet end of the tube furnace with a mechanical pump, vacuumizing until the vacuum gauge reaches-0.1 MPa, evacuating a corundum tube and a gas pipeline of the tube furnace, then opening a nitrogen cylinder switch knob, opening an air inlet valve of the tube furnace to enable nitrogen to enter the tube furnace at 300mL/min, and opening an air outlet valve of the tube furnace when a pressure gauge of the tube furnace is stabilized at 0 MPa; simultaneously starting a heating switch of the tubular furnace, raising the temperature of the hearth from room temperature to 300 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and preserving the heat for 2 hours at the temperature to ensure that the nickel hydroxide loaded on the surface of the carbon cloth is phosphated to generate nickel phosphide;
step six, after the phosphating reaction in the step five is finished, closing the power supply of the tubular furnace and still keeping nitrogen gas introduction, naturally cooling the temperature in the tubular furnace to room temperature under the protection of the nitrogen gas, and then taking out the nickel hydroxide/carbon cloth after phosphating treatment from the tubular furnace to obtain the nickel phosphide-carbon cloth self-supporting material;
step seven, 1.1885g of nickel chloride, 2.9410g of trisodium citrate, 3.0392g of ammonium sulfate and 2.9677g of sodium hypophosphite are sequentially added into a beaker filled with 50mL of deionized water; then placing the beaker on a magnetic stirrer, starting a stirring control knob switch, stirring the solution to completely dissolve all the added reagents, and obtaining the nickel-phosphorus alloy electroplating solution after the reagents are dissolved and the solution is uniformly stirred;
step eight, cutting the 2cm multiplied by 2cm nickel phosphide-carbon cloth self-supporting material prepared in the step six into 1cm multiplied by 1cm small pieces serving as working electrodes, clean graphite rods serving as auxiliary electrodes, Ag/AgCl electrodes serving as reference electrodes and the nickel-phosphorus alloy electroplating solution prepared in the step seven serving as electrolyte to construct a three-electrode system, wherein the working electrodes, the auxiliary electrodes and the reference electrodes need to be fully soaked in the nickel-phosphorus alloy electroplating solution;
step nine, after the working electrode, the auxiliary electrode and the reference electrode are connected with the ZF-9 potentiostat, a power switch of the potentiostat is turned on, and the nickel-phosphorus alloy is electrodeposited on the surface of the nickel phosphide-carbon cloth chip in a constant current control mode, wherein the current density is 1mAcm-2The electrodeposition temperature is room temperature, and the electrodeposition time is 60 s;
and step ten, after the electrodeposition in the step nine is finished, taking out the nickel phosphide-carbon cloth chips loaded with nickel and phosphorus on the surfaces from the nickel-phosphorus alloy electroplating solution, respectively cleaning the nickel phosphide-carbon cloth chips with deionized water and absolute ethyl alcohol, and then placing the cleaned samples in a vacuum drying oven for drying treatment at the drying temperature of 60 ℃ for 12h under the vacuum degree of-0.1 MPa to obtain the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material.
The prepared nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode is used as a working electrode, a graphite rod is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode, a testing instrument is a Shanghai Chenghua CHI650C type electrochemical workstation, and a cathode linear voltammetry scanning test is carried out at room temperature to detect the electrochemical hydrogen evolution performance of the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode; introducing nitrogen into the electrolyte for 30min before electrochemical test, and calibrating the measured Ag/AgCl potential value to be the potential relative to the reversible hydrogen electrode in all tests; the potential window of linear volt-ampere scanning is-0.3-0V, and the scanning rate is 2mVs-1(ii) a The tafel curve graph is obtained by drawing a logarithmic relation curve of overpotential and current density, and the linear part of the tafel curve meets the tafel formula:η=blog(j)+awhereinηThe indication of the over-potential is,jit is shown that the current density is,bwhich represents the slope of the tafel slope,arepresenting intercept, the overpotential window of a Tafel plot is 0-0.4V, and the scanning rate is 2mVs-1。
As shown in fig. 1, the XRD diffraction pattern of the three-dimensional self-supporting electrode material prepared in this example is that, from the XRD test curve, it can be clearly observed that the crystallinity of the nickel phosphide-carbon cloth is relatively good, the diffraction angles 2 θ =40.7 °, 44.6 °, 47.4 °, 54.2 ° and 55 ° correspond to the (111), (201), (210), (300) and (211) diffraction crystal planes of nickel phosphide, respectively, and are consistent with the XRD standard card jcpdsno.74-1385 of nickel phosphide, and the position of the spectrum with the diffraction angle 2 θ =26.2 ° corresponds to the (002) diffraction crystal plane of the carbon cloth, which is consistent with the XRD card of carbon cloth being jcpdsno.75-1621; because the time for electrodepositing the nickel and the phosphorus is short, the load capacity is small, and the interference and shielding effect of nickel phosphide exist, the XRD characteristic diffraction peak of the electrodeposited nickel and the phosphorus is not obvious and is not easy to be identified.
Fig. 2, fig. 3 and fig. 4 are scanning electron microscope morphology diagrams of the three-dimensional self-supporting electrode material manufactured in the embodiment, the nickel phosphide-carbon cloth sample shown in fig. 2 is in a flower-like structure, and nickel phosphide uniformly grows on a carbon cloth conductive substrate; as can be observed from the interpolated graph in fig. 2, the nickel phosphide flower-like structure is formed by stacking nanosheets. Fig. 3 is a scanned image of different parts of the same material as shown in fig. 2, and it can be seen from fig. 3 that the distribution of nickel phosphide on the carbon cloth is not very uniform, i.e. there is no nickel phosphide at some points. As can be seen from fig. 4, the nickel-phosphorus/nickel phosphide-carbon cloth sample also has a flower-like structure, and as can be seen from the enlarged interpolation chart, compared with fig. 2, the surface of the nickel phosphide nanosheet is rough, which is caused by the nickel-phosphorus alloy coating loaded on the vacant part of the nickel phosphide on the surface.
Example 2
Step one, sequentially adding 0.70g of nickel nitrate and 0.70g of hexamethylenetetramine into a beaker filled with 15mL of deionized water, then placing the beaker on a magnetic stirrer, and stirring at room temperature to dissolve the nickel nitrate and the hexamethylenetetramine;
step two, transferring the solution stirred in the step one to a stainless steel reaction kettle with a volume of 25mL and a polytetrafluoroethylene lining, simultaneously putting square carbon cloth with the length and the width of 2cm after acid soaking treatment into the stainless steel reaction kettle, screwing a sealing cover of the stainless steel reaction kettle and transferring the stainless steel reaction kettle into an electric furnace, wherein the temperature of a hearth of the electric furnace is 100 ℃, and carrying out hydrothermal reaction for 10 hours at the temperature; after the reaction is finished, turning off the power supply of the electric furnace, taking out the stainless steel reaction kettle from the electric furnace after the temperature of the hearth is cooled to room temperature, opening a sealing cover of the reaction kettle, taking out the carbon cloth from the reaction kettle, washing the carbon cloth with additionally moved deionized water for three times, and then washing the carbon cloth with absolute ethyl alcohol for three times;
step three, placing the carbon cloth washed cleanly in the step two in a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the drying time is 12 hours, and the vacuum degree is-0.1 MPa, so as to obtain a nickel hydroxide-carbon cloth precursor material;
step four, respectively putting the nickel hydroxide-carbon cloth precursor material prepared in the step three and 0.25g of sodium hypophosphite powder into two porcelain boats, then putting the two porcelain boats filled with the samples in the center of a tube furnace, and connecting a nitrogen gas inlet pipe to the sample placing inlet end of the tube furnace, wherein the porcelain boat filled with the sodium hypophosphite is placed at one side close to the nitrogen gas inlet of the tube furnace, and the porcelain boat filled with the nickel hydroxide/carbon cloth precursor is placed at one side of a gas outlet;
connecting a working gas path, connecting a gas outlet end of the tube furnace with a mechanical pump, vacuumizing until the vacuum gauge reaches-0.1 MPa, evacuating a corundum tube and a gas pipeline of the tube furnace, then opening a nitrogen cylinder switch knob, opening an air inlet valve of the tube furnace to enable nitrogen to enter the tube furnace at 300mL/min, and opening an air outlet valve of the tube furnace when a pressure gauge of the tube furnace is stabilized at 0 MPa; simultaneously starting a heating switch of the tubular furnace, raising the temperature of the hearth from room temperature to 300 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and preserving the heat for 2 hours at the temperature to ensure that the nickel hydroxide loaded on the surface of the carbon cloth is phosphated to generate nickel phosphide;
step six, after the phosphating reaction in the step five is finished, closing the power supply of the tubular furnace and still keeping nitrogen gas introduction, naturally cooling the temperature in the tubular furnace to room temperature under the protection of the nitrogen gas, and then taking out the nickel hydroxide/carbon cloth after phosphating treatment from the tubular furnace to obtain the nickel phosphide-carbon cloth self-supporting material;
step seven, sequentially adding 1.0g of nickel chloride, 2.75g of trisodium citrate, 3.0g of ammonium sulfate and 2.75g of sodium hypophosphite into a beaker containing 45mL of deionized water; then placing the beaker on a magnetic stirrer, starting a stirring control knob switch, stirring the solution to completely dissolve all the added reagents, and obtaining the nickel-phosphorus alloy electroplating solution after the reagents are dissolved and the solution is uniformly stirred;
step eight, cutting the 2cm multiplied by 2cm nickel phosphide-carbon cloth self-supporting material prepared in the step six into 1cm multiplied by 1cm small pieces serving as working electrodes, clean graphite rods serving as auxiliary electrodes, Ag/AgCl electrodes serving as reference electrodes and the nickel-phosphorus alloy electroplating solution prepared in the step seven serving as electrolyte to construct a three-electrode system, wherein the working electrodes, the auxiliary electrodes and the reference electrodes need to be fully soaked in the nickel-phosphorus alloy electroplating solution;
step nine, after the working electrode, the auxiliary electrode and the reference electrode are connected with the ZF-9 potentiostat, a power switch of the potentiostat is turned on, and the nickel-phosphorus alloy is electrodeposited on the surface of the nickel phosphide-carbon cloth chip in a constant current control mode, wherein the current density is 2mAcm-2The electrodeposition temperature is room temperature, and the electrodeposition time is 120 s;
and step ten, after the electrodeposition in the step nine is finished, taking out the nickel phosphide-carbon cloth chips loaded with nickel and phosphorus on the surfaces from the nickel-phosphorus alloy electroplating solution, respectively cleaning the nickel phosphide-carbon cloth chips with deionized water and absolute ethyl alcohol, and then placing the cleaned samples in a vacuum drying oven for drying treatment at the drying temperature of 60 ℃ for 12h under the vacuum degree of-0.1 MPa to obtain the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material.
The prepared nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode is used as a working electrode, a graphite rod is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode, a testing instrument is a Shanghai Chenghua CHI650C type electrochemical workstation, and a cathode linear voltammetry scanning test is carried out at room temperature to detect the electrochemical hydrogen evolution performance of the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode; introducing nitrogen into the electrolyte for 30min before electrochemical test, and calibrating the measured Ag/AgCl potential value to be the potential relative to the reversible hydrogen electrode in all tests; the potential window of linear volt-ampere scanning is-0.3-0V, and the scanning rate is 2mVs-1(ii) a The tafel curve graph is obtained by drawing a logarithmic relation curve of overpotential and current density, and the linear part of the tafel curve meets the tafel formula:η=blog(j)+awhereinηThe indication of the over-potential is,jit is shown that the current density is,bwhich represents the slope of the tafel slope,arepresenting intercept, the overpotential window of a Tafel plot is 0-0.4V, and the scanning rate is 2mVs-1。
The crystal plane structure and the morphology of the nickel-phosphorus/nickel phosphide-carbon cloth electrode material prepared in the embodiment are not significantly different from those of the sample prepared in the embodiment 1, and therefore, the description is omitted.
Example 3
Step one, sequentially adding 0.75g of nickel nitrate and 0.75g of hexamethylenetetramine into a beaker filled with 20mL of deionized water, then placing the beaker on a magnetic stirrer, and stirring at room temperature to dissolve the beaker;
step two, transferring the solution stirred in the step one to a stainless steel reaction kettle with a volume of 25mL and a polytetrafluoroethylene lining, simultaneously putting square carbon cloth with the length and the width of 2cm after acid soaking treatment into the stainless steel reaction kettle, screwing a sealing cover of the stainless steel reaction kettle and transferring the stainless steel reaction kettle into an electric furnace, wherein the temperature of a hearth of the electric furnace is 100 ℃, and carrying out hydrothermal reaction for 10 hours at the temperature; after the reaction is finished, turning off the power supply of the electric furnace, taking out the stainless steel reaction kettle from the electric furnace after the temperature of the hearth is cooled to room temperature, opening a sealing cover of the reaction kettle, taking out the carbon cloth from the reaction kettle, washing the carbon cloth with additionally moved deionized water for three times, and then washing the carbon cloth with absolute ethyl alcohol for three times;
step three, placing the carbon cloth washed cleanly in the step two in a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the drying time is 12 hours, and the vacuum degree is-0.1 MPa, so as to obtain a nickel hydroxide-carbon cloth precursor material;
step four, respectively putting the nickel hydroxide-carbon cloth precursor material prepared in the step three and 0.25g of sodium hypophosphite powder into two porcelain boats, then putting the two porcelain boats filled with the samples in the center of a tube furnace, and connecting a nitrogen gas inlet pipe to the sample placing inlet end of the tube furnace, wherein the porcelain boat filled with the sodium hypophosphite is placed at one side close to the nitrogen gas inlet of the tube furnace, and the porcelain boat filled with the nickel hydroxide/carbon cloth precursor is placed at one side of a gas outlet;
connecting a working gas path, connecting a gas outlet end of the tube furnace with a mechanical pump, vacuumizing until the vacuum gauge reaches-0.1 MPa, evacuating a corundum tube and a gas pipeline of the tube furnace, then opening a nitrogen cylinder switch knob, opening an air inlet valve of the tube furnace to enable nitrogen to enter the tube furnace at 300mL/min, and opening an air outlet valve of the tube furnace when a pressure gauge of the tube furnace is stabilized at 0 MPa; simultaneously starting a heating switch of the tubular furnace, raising the temperature of the hearth from room temperature to 300 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, and preserving the heat for 2 hours at the temperature to ensure that the nickel hydroxide loaded on the surface of the carbon cloth is phosphated to generate nickel phosphide;
step six, after the phosphating reaction in the step five is finished, closing the power supply of the tubular furnace and still keeping nitrogen gas introduction, naturally cooling the temperature in the tubular furnace to room temperature under the protection of the nitrogen gas, and then taking out the nickel hydroxide/carbon cloth after phosphating treatment from the tubular furnace to obtain the nickel phosphide-carbon cloth self-supporting material;
step seven, sequentially adding 1.25g of nickel chloride, 3.0g of trisodium citrate, 3.25g of ammonium sulfate and 3g of sodium hypophosphite into a beaker filled with 55mL of deionized water; then placing the beaker on a magnetic stirrer, starting a stirring control knob switch, stirring the solution to completely dissolve all the added reagents, and obtaining the nickel-phosphorus alloy electroplating solution after the reagents are dissolved and the solution is uniformly stirred;
step eight, cutting the 2cm multiplied by 2cm nickel phosphide-carbon cloth self-supporting material prepared in the step six into 1cm multiplied by 1cm small pieces serving as working electrodes, clean graphite rods serving as auxiliary electrodes, Ag/AgCl electrodes serving as reference electrodes and the nickel-phosphorus alloy electroplating solution prepared in the step seven serving as electrolyte to construct a three-electrode system, wherein the working electrodes, the auxiliary electrodes and the reference electrodes need to be fully soaked in the nickel-phosphorus alloy electroplating solution;
step nine, after the working electrode, the auxiliary electrode and the reference electrode are connected with the ZF-9 potentiostat, a power switch of the potentiostat is turned on, and the nickel-phosphorus alloy is electrodeposited on the surface of the nickel phosphide-carbon cloth chip in a constant current control mode, wherein the current density is 5mAcm-2The electrodeposition temperature is room temperature, and the electrodeposition time is 180 s;
and step ten, after the electrodeposition in the step nine is finished, taking out the nickel phosphide-carbon cloth chips loaded with nickel and phosphorus on the surfaces from the nickel-phosphorus alloy electroplating solution, respectively cleaning the nickel phosphide-carbon cloth chips with deionized water and absolute ethyl alcohol, and then placing the cleaned samples in a vacuum drying oven for drying treatment at the drying temperature of 60 ℃ for 12h under the vacuum degree of-0.1 MPa to obtain the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material.
The prepared nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode is used as a working electrode, a graphite rod is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode, a testing instrument is a Shanghai Chenghua CHI650C type electrochemical workstation, and a cathode linear voltammetry scanning test is carried out at room temperature to detect the electrochemical hydrogen evolution performance of the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode; introducing nitrogen into the electrolyte for 30min before electrochemical test, and calibrating the measured Ag/AgCl potential value to be the potential relative to the reversible hydrogen electrode in all tests; the potential window of linear volt-ampere scanning is-0.3-0V, and the scanning rate is 2mVs-1(ii) a The tafel curve graph is obtained by drawing a logarithmic relation curve of overpotential and current density, and the linear part of the tafel curve meets the tafel formula:η=blog(j)+awhereinηThe indication of the over-potential is,jit is shown that the current density is,bwhich represents the slope of the tafel slope,arepresenting intercept, the overpotential window of a Tafel plot is 0-0.4V, and the scanning rate is 2mVs-1。
The crystal plane structure and the morphology of the nickel-phosphorus/nickel phosphide-carbon cloth electrode material prepared in the embodiment are not significantly different from those of the sample prepared in the embodiment 1, and therefore, the description is omitted.
Fig. 5 is a graph showing cathode linear scanning polarization curves of the prepared nickel-carbon phosphide cloth and the nickel-phosphorus/nickel-carbon phosphide-hydrogen evolution electrodes prepared in examples 1, 2 and 3, respectively, and it can be seen from fig. 5 that curves 1, 2, 3 and 4 are respectively the cathode linear scanning polarization curves of the nickel-carbon phosphide cloth prepared in example 1, the nickel-phosphorus/nickel-carbon phosphide prepared in example 2 and the nickel-phosphorus/nickel-carbon phosphide-hydrogen evolution electrode prepared in example 3, and from the test results, it can be seen that the electrochemical hydrogen evolution activity of the prepared nickel-phosphorus/nickel-carbon phosphide-hydrogen evolution cloth is superior to that of the prepared nickel-carbon phosphide. When the current density is 10mAcm-2In this case, the nickel phosphide-carbon cloth test prepared in example 1The overpotentials of the hydrogen evolution electrodes of the sample, the nickel-phosphorus/nickel-phosphorus-carbon cloth sample prepared in example 1, the nickel-phosphorus/nickel-phosphorus-carbon cloth sample prepared in example 2, and the nickel-phosphorus/nickel-phosphorus-carbon cloth sample prepared in example 3 were 120mV, 95mV, 112mV, and 114mV, respectively; the hydrogen evolution overpotential of the samples of nickel-phosphorus/nickel-phosphorus-carbon cloth prepared in example 1 was the smallest compared to the other samples prepared, which indicates that the three-dimensional self-supporting electrode material prepared in example 1 has the best hydrogen evolution performance and the better preparation conditions in the samples of nickel-phosphorus/nickel-phosphorus-carbon cloth and nickel-phosphorus-carbon cloth prepared.
FIG. 6 is Tafel slope curves of three-dimensional self-supporting electrodes manufactured in examples 1, 2 and 3 of the present invention, and it can be seen from FIG. 6 that curves a, b, c and d are Tafel slope curves of the nickel-carbon cloth manufactured in example 1, the nickel-phosphorus/nickel-carbon cloth manufactured in example 2 and the nickel-phosphorus/nickel-carbon-hydrogen-evolution electrode manufactured in example 3, respectively, and from the test results, the Tafel slopes of the nickel-carbon cloth specimen manufactured in example 1, the nickel-phosphorus/nickel-carbon cloth specimen manufactured in example 2 and the nickel-phosphorus ec/nickel-carbon cloth specimen manufactured in example 3 are 91.9 mVdVd slope curves of the nickel-carbon cloth specimen manufactured in example 1, the nickel-phosphorus/nickel-carbon cloth specimen manufactured in example 2 and the nickel-phosphorus ec/nickel-carbon cloth specimen manufactured in-1、80.4mVdec-1、87.2mVdec-1And 88.5mVdec-1It is proved that the nickel-phosphorus/nickel phosphide-carbon cloth electrode has faster hydrogen evolution reaction kinetics than the nickel phosphide-carbon cloth electrode. The tafel slope is 40-120 mVdec-1The interval indicates that the mechanism of the hydrogen evolution reaction is Volmer-Heyrovsky, that is, the Heyrovsky process is the rate control step of the process. The tafel slope of the nickel-phosphorus/nickel-phosphorus-carbon cloth sample prepared in example 1 was the smallest, further demonstrating that the three-dimensional self-supporting electrode material prepared in example 1 has the best hydrogen evolution performance among the three electrode materials. The existence of the nickel-phosphorus alloy coating can not be fully proved by an XRD diffraction pattern and a scanning electron microscope topography, but the electrochemical hydrogen evolution activity of the prepared nickel-phosphorus/nickel-phosphide-carbon cloth is obviously superior to that of the prepared nickel-phosphide-carbon cloth, and the nickel-phosphorus alloy coating is further explained to be loaded on the surface nickel phosphide vacant part.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape, principle and the like of the invention are covered by the protection scope of the invention.
Alternative materials for the various components are listed in the description of the invention, but it will be understood by those skilled in the art that: the above list of component materials is not intended to be limiting and non exhaustive, and the various components may be replaced by other equivalent materials not mentioned in the present description, while still achieving the objects of the present invention. The specific embodiments mentioned in the description are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
In addition, the range of the amount of each component of the present invention includes any combination of any lower limit and any upper limit mentioned in the specification, and also includes any range where the specific content of the component in each specific example is made up as a combination of the upper limit or the lower limit: all such ranges are intended to be included within the scope of the present invention for brevity and clarity only and are not intended to be exhaustive or to limit the scope of the invention to the precise forms disclosed. Each feature of the invention described in this specification may be combined with any other feature of the invention which combination is not specifically disclosed in the specification for the sake of brevity.
Claims (2)
1. The preparation method of the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material is characterized by comprising the following steps of:
step one, adding nickel nitrate and hexamethylenetetramine into a beaker filled with deionized water in sequence, placing the beaker on a magnetic stirrer, and stirring at room temperature to dissolve the nickel nitrate and the hexamethylenetetramine;
step two, transferring the solution stirred in the step one to a stainless steel reaction kettle with a polytetrafluoroethylene lining, simultaneously putting the carbon cloth subjected to acid soaking treatment into the stainless steel reaction kettle, screwing a sealing cover of the stainless steel reaction kettle, transferring the stainless steel reaction kettle to an electric furnace, and reacting for a period of time; after the reaction is finished, turning off the power supply of the electric furnace, taking out the stainless steel reaction kettle from the electric furnace after the temperature of the hearth is cooled to room temperature, opening a sealing cover of the reaction kettle, taking out the carbon cloth from the reaction kettle, washing the carbon cloth by using the additionally moved deionized water, and then washing the carbon cloth by using absolute ethyl alcohol; the temperature of a hearth of the electric furnace is 100-110 ℃, and the hydrothermal reaction is carried out for 10-12 h at the temperature;
thirdly, placing the carbon cloth washed cleanly in the second step into a vacuum drying oven for drying treatment for a period of time to obtain a nickel hydroxide-carbon cloth precursor material; the drying temperature of the vacuum drying oven is 60-80 ℃, the drying time is 10-12 h, and the vacuum degree is-0.1 Mpa;
step four, respectively putting the nickel hydroxide-carbon cloth precursor material prepared in the step three and sodium hypophosphite powder into two porcelain boats, then putting the two porcelain boats filled with the samples into the center of a tube furnace, and connecting a nitrogen inlet pipe to the sample placing inlet end of the tube furnace; placing the porcelain boat filled with the sodium hypophosphite at one side close to a nitrogen gas inlet of the tubular furnace, and placing the porcelain boat filled with the nickel hydroxide/carbon cloth precursor at one side of a gas outlet;
connecting a working gas path, connecting a gas outlet end of the tube furnace with a mechanical pump, vacuumizing to negative pressure, evacuating a corundum tube and a gas pipeline of the tube furnace, then opening a nitrogen cylinder switch knob, opening an air inlet valve of the tube furnace, slowly introducing nitrogen into the tube furnace, and opening an air outlet valve of the tube furnace when a pressure gauge of the tube furnace gas is stabilized at 0 MPa; simultaneously, starting a heating switch of the tubular furnace, raising the temperature of the hearth from room temperature to a certain temperature at a constant heating rate under the protection of nitrogen, and preserving the heat for a period of time at the temperature to ensure that the nickel hydroxide loaded on the surface of the carbon cloth is phosphated to generate nickel phosphide; vacuumizing to make the vacuum surface to-0.1 MPa; raising the temperature of the hearth from room temperature to 280-300 ℃ at a temperature raising rate of 2-3 ℃/min, and preserving the heat for 2-3 h at the temperature;
step six, after the phosphating reaction in the step five is finished, closing the power supply of the tubular furnace and still keeping nitrogen gas introduction, naturally cooling the temperature in the tubular furnace to room temperature under the protection of the nitrogen gas, and then taking out the nickel hydroxide/carbon cloth after phosphating treatment from the tubular furnace to obtain the nickel phosphide-carbon cloth self-supporting material;
carbon cloth in the first step to the sixth step: nickel nitrate: hexamethylenetetramine: sodium hypophosphite: the mass proportion relation of the deionized water = 0.055-0.06: 0.7-0.75: 0.7-0.75: 0.25-0.3: 15-20;
step seven, adding nickel chloride, trisodium citrate, ammonium sulfate and sodium hypophosphite into a beaker filled with deionized water in sequence, placing the beaker on a magnetic stirrer, starting a stirring control knob switch, stirring the solution to completely dissolve all the added reagents, and obtaining nickel-phosphorus alloy electroplating solution after the reagents are dissolved and the solution is uniformly stirred; the mass ratio of the raw materials is as follows: trisodium citrate: ammonium sulfate: sodium hypophosphite: deionized water = 1.0-1.25: 2.75-3.0: 3.0-3.25: 2.75-3.0: 45-55, wherein the deionized water is 50 mL;
step eight, constructing a three-electrode system by using the nickel phosphide-carbon cloth self-supporting material prepared in the step six as a working electrode, a clean graphite rod as an auxiliary electrode, an Ag/AgCl electrode as a reference electrode and the nickel phosphorus alloy electroplating solution prepared in the step seven as an electrolyte; the working electrode, the auxiliary electrode and the reference electrode need to be fully soaked in the nickel-phosphorus alloy electroplating solution;
step nine, after the working electrode, the auxiliary electrode and the reference electrode in the step eight are connected with a constant potential rectifier, a power switch of the constant potential rectifier is turned on, and a constant current control mode is adopted to electrodeposit nickel-phosphorus alloy on the surface of the nickel phosphide-carbon cloth small piece; the current density of the constant potential rectifier is 1-5 mAcm-2The electrodeposition temperature is room temperature, and the electrodeposition time is 60-180 s;
step ten, after the electrodeposition in the step nine is finished, taking out the nickel phosphide-carbon cloth loaded with nickel and phosphorus on the surface from the nickel-phosphorus alloy electroplating solution, respectively cleaning the nickel phosphide-carbon cloth with deionized water and absolute ethyl alcohol, and then placing the cleaned sample in a vacuum drying oven for drying treatment to obtain the nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material; the drying temperature of the vacuum drying oven is 60-80 ℃, the drying time is 10-12 h, and the vacuum degree is-0.1 MPa.
2. The method for preparing the nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material according to claim 1, which is characterized in that: the carbon cloth in the second step is prepared through the following steps;
step I, adding concentrated nitric acid with the volume of 100mL and the mass concentration of 65-68% into a 250mL beaker, then cutting eight carbon cloths into 2cm multiplied by 2cm, adding the carbon cloths into the beaker containing the concentrated nitric acid, sealing the opening of the beaker by using a preservative film, and standing at room temperature for 45-48 h to carry out acid-soaking hydrophilic modification on the carbon cloths;
step II, after standing, placing the beaker in an ultrasonic cleaner for ultrasonic treatment, wherein deionized water with the temperature of 20-30 ℃ is filled in the ultrasonic cleaner, the power of the cleaner is 450W, and the ultrasonic treatment time is 1-2 h;
step III, taking the carbon cloth subjected to ultrasonic treatment out of the beaker, and washing the carbon cloth by using deionized water until the pH value of the washing water is neutral; then, soaking and washing the carbon cloth twice by using absolute ethyl alcohol at room temperature, wherein the soaking time is 10-15 min each time, so as to ensure that the surface of the carbon cloth is clean, and washing the carbon cloth by using the absolute ethyl alcohol and then washing the carbon cloth by using deionized water for three times;
and step IV, after the carbon cloth is washed clean, placing the carbon cloth in a vacuum drying oven for drying at the temperature of 60-80 ℃, wherein the vacuum degree is-0.1 MPa, and the drying time is 10-12 h, so that the carbon cloth subjected to acid dipping treatment is obtained.
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| CN111957329B (en) * | 2020-07-20 | 2023-09-19 | 中科润谷智慧能源科技(佛山)有限公司 | Preparation method of self-supporting Ni2P-WOx hydrogen evolution electrocatalyst |
| CN113130905A (en) * | 2021-04-16 | 2021-07-16 | 陕西科技大学 | Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof |
| CN113725426B (en) * | 2021-08-27 | 2022-11-11 | 北京理工大学 | Ni (OH) 2 -Ni 2 P @ carbon cloth composite material, preparation and application thereof |
| CN114134529B (en) * | 2021-11-30 | 2023-03-31 | 燕山大学 | Hydrogen evolution electrode and preparation method and application thereof |
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