CN110644016A - Preparation method of nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution by water and electricity dissociation - Google Patents
Preparation method of nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution by water and electricity dissociation Download PDFInfo
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a self-supporting catalytic material, in particular to a preparation method of a nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution by water-electricity dissociation, which is used for the technical field of non-noble metal-based cathode catalyst preparation and comprises the steps of activating and sensitizing a substrate after substrate pretreatment, carrying out electrodeposition of a zinc layer by taking the activated and sensitized substrate as an anode, carrying out negative chemical nickel-phosphorus plating on the surface of the substrate subjected to the electrodeposition of the zinc layer, and then preparing the nickel phosphide-carbon cloth self-supporting electrode by a phosphating reaction.
Description
Technical Field
The invention relates to a self-supporting catalytic material, in particular to a preparation method of a nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution through water and electricity dissociation, belonging to or being used in the technical field of preparation of non-noble metal-based cathode catalysts.
Background
The energy is the main line of human development and is the 'blood vessel' of the world economy, the problem of environmental pollution caused by the imminent exhaustion of traditional fossil energy and the combustion thereof forces countries in the world to develop the hot tide of green clean energy, and hydrogen is taken as green energy which has high energy density, is clean, pollution-free and renewable, and is hopeful in coping with the problems of energy and environment. Compared with the hydrogen production method relying on primary energy in industry, the hydrogen production by water electrolysis has the characteristics of simple device, high hydrogen production purity, high energy conversion rate and the like, and is concerned; however, the hydrogen production by water electrolysis needs higher reaction overpotential to overcome the reaction energy barrier of hydrogen bond breakage in water molecules, so that the energy loss in the reaction process can be greatly increased, and the performance of the catalyst for the electrochemical cathode hydrogen evolution reaction is the key for restricting the hydrogen production efficiency by water and electricity dissociation. Therefore, the research and development of the efficient and stable cathode hydrogen evolution catalyst for accelerating the hydrogen evolution reaction kinetics and reducing the hydrogen production energy consumption is an important measure for promoting the application of electrochemical cathode hydrogen evolution. At present, materials with excellent electrochemical catalytic hydrogen evolution performance are mainly noble metals such as Pt, the materials have low overpotential and excellent hydrogen evolution performance, but the noble metals such as Pt are low in storage capacity on the earth and expensive in price and cannot meet the requirements of engineering application, so that the research and development of non-noble metal catalysts with wide sources, convenience in use and high hydrogen evolution efficiency are urgent. In addition, in the process of producing hydrogen, different electrolysis devices are suitable for different pH values, for example, an acid-resistant catalyst must be used for a proton exchange membrane fuel cell, a catalyst with excellent catalytic activity and stability under an alkaline condition is required for an alkaline electrolysis process, and an electrocatalyst with excellent catalytic performance under a neutral pH value is generally required for a microbial fuel cell hydrogen production system. Therefore, the non-noble metal-based electrochemical cathode hydrogen evolution catalytic material has the characteristics of high efficiency, stability, low price, easy obtainment and the like of hydrogen evolution performance, and also needs to have a wide pH application range, which is the key of green hydrogen production measures.
In non-noble metal-based cathode catalytic materials, transition metal phosphide represented by nickel phosphide is widely concerned as a hydrogen evolution material due to special morphological structure and physicochemical properties, and domestic and foreign scholars conduct a lot of researches in the field, and the research on the preparation way of nickel phosphide and the evaluation of the hydrogen evolution performance of water and electricity dissociation of the nickel phosphide are the key points of the research in the field. At present, the solution phase reaction such as hydrothermal synthesis for preparing nickel phosphide mainly uses white phosphorus or tri-n-octylphosphine as a phosphorus source, but the reaction temperature range is limited to a certain extent, and the toxicity of intermediate products in the reaction process is high. Therefore, the researchers improve the above process, and in patent CN107142488A, firstly, nickel hydroxide precursor powder is synthesized by hydrothermal method, and then nickel phosphide hollow microsphere powder is synthesized by solid phase method, the nickel phosphide powder has excellent performance of catalytic hydrogen evolution, but the prepared nickel phosphide powder needs to be bonded and fixed on the material used as current collector by using binders such as polytetrafluoroethylene emulsion, perfluorosulfonic acid solution and the like, the binders can block active sites and reduce the electrical conductivity of the material, and the catalyst powder is easy to fall off in the process of electrolytic hydrogen production; the patent CN 109267095A provides a preparation method of a novel nickel phosphide catalytic material, which comprises the steps of firstly synthesizing a metal organic framework precursor containing nitrogen and phosphorus atoms by a micro-droplet method, then sintering and thermally treating the precursor at the high temperature of 900-1100 ℃, and then preparing a nickel phosphide catalytic hydrogen evolution material; patent CN107502919A mentions the preparation of nickel phosphide catalyst by solvothermal method, but the technology involves high temperature and high pressure procedures which are not favorable for industrial production application. Based on the technical defects of the existing nickel phosphide preparation, the preparation technology of the nickel phosphide, which has the advantages of wide material source, convenient preparation process, no pollution, easy industrial popularization, high and stable hydrogen evolution performance and wide pH application range, is sought, and is an important measure for promoting the hydrogen production by cathode water and electricity dissociation.
Disclosure of Invention
The invention aims to provide a preparation method of a nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution through water and electricity dissociation.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution by water and electricity dissociation comprises the following steps:
(1) pre-treating a substrate, cutting the substrate into rectangular sheets with a specified size, carrying out acid-soaking hydrophilic modification treatment on the substrate, carrying out ultrasonic treatment on the substrate after the acid-soaking hydrophilic modification, cleaning the substrate by using a detergent until the pH value of the detergent is neutral, and drying the substrate;
(2) activating and sensitizing a matrix, wherein the activating treatment is to immerse the matrix in stannous chloride solution, taking out the matrix for cleaning after ultrasonic treatment, the sensitizing treatment is to immerse the matrix after the activating treatment in palladium chloride solution, taking out the matrix for cleaning after ultrasonic treatment, and drying the matrix;
(3) performing electrodeposition zinc layer treatment on the matrix, namely plating by using the activated and sensitized matrix as an anode and a carbon rod as a cathode by using a galvanizing electrolyte solution, electrodepositing a loaded thin zinc layer on the surface of the matrix, and taking out the matrix for cleaning after plating;
(4) carrying a chemical nickel-phosphorus plating layer on the surface of a substrate, heating a chemical nickel-phosphorus plating solution to a certain temperature, immersing the substrate carrying a thin zinc layer on the surface in the chemical nickel-phosphorus plating solution, chemically plating and depositing the nickel-phosphorus plating layer on the surface of the substrate, keeping a certain temperature in the plating process, taking out the substrate after the plating is finished, cleaning the substrate, drying the substrate, recording the mass difference of the substrate before and after the substrate is dried, and determining the carrying capacity of the nickel-phosphorus plating layer on the surface of the substrate;
(5) and (3) preparing a nickel phosphide-carbon cloth self-supporting electrode, and calculating the mass of the phosphorus source according to the load of the nickel-phosphorus coating on the surface of the matrix. And respectively placing the substrate and the phosphorus source into two corundum porcelain boats, placing the two corundum porcelain boats into the center of a hearth of a tubular furnace, placing the corundum porcelain boats with the phosphorus source at one side close to an inert gas inlet of the tubular furnace, slowly introducing the inert gas into the tubular furnace, heating the tubular furnace to a set temperature, carrying out phosphating reaction on the substrate, cooling the tubular furnace to room temperature, and taking out the substrate after phosphating treatment to obtain the nickel phosphide self-supporting electrode.
The technical scheme of the invention is further improved as follows: in the step (1), the substrate is carbon cloth with the length and the width of 2cm, the substrate is subjected to acid-soaking hydrophilic modification by using 65% concentrated nitric acid in percentage by mass, ultrasonic treatment is performed on a sealed opening of the container for 48 hours, deionized water is used as a detergent to clean the substrate, the substrate is placed in a vacuum drying oven to be dried at the temperature of 60 ℃, and the vacuum degree of the vacuum drying oven is-0.1 MPa.
The technical scheme of the invention is further improved as follows: and (3) carrying out activation treatment on the stannous chloride solution in the step (2), taking out the substrate after ultrasonic treatment for 10-20 min, washing the substrate with deionized water for 5 times, carrying out sensitization treatment on the palladium chloride solution in the step (0.2 g/L), taking out the substrate after ultrasonic treatment for 20-30 min, washing the substrate with deionized water for 5 times, placing the substrate in a vacuum drying oven, and drying the substrate at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa.
The technical scheme of the invention is further improved as follows: the zinc plating electrolyte solution in the step (3) is a mixed water solution of zinc sulfate and potassium chloride of 1.0 mol/L and the plating current density is 3-5 mA/cm2And the plating time is 60-100 s, and the substrate is cleaned for 5 times by using deionized water after the plating is finished.
The technical scheme of the invention is further improved as follows: in the step (4), the temperature of the chemical nickel-phosphorus plating solution is 80-85 ℃, the temperature of the plating solution is kept at 80-85 ℃ in the plating process, the plating time is 40-60 min, the substrate is taken out and washed with deionized water for 5 times after the plating is finished, the substrate is placed in a vacuum drying oven to be dried at the temperature of 60 ℃, and the vacuum degree of the vacuum drying oven is-0.1 MPa.
The technical scheme of the invention is further improved as follows: in the step (5), the mass of the phosphorus source is calculated according to the ratio of the phosphorus source to the loading amount of the nickel-phosphorus coating on the surface of the substrate being 1:5, the phosphorus source is sodium hypophosphite, the inert gas is nitrogen, the introduction amount of the nitrogen is 10-30 mL/min, the tubular furnace is heated to 300 ℃, and the time for carrying out the phosphating reaction on the substrate is 2 hours.
The technical scheme adopted by the invention is as follows: (1) firstly, sequentially adding nickel sulfate serving as soluble nickel salt, citric acid and succinic acid serving as composite complexing agents, sodium acetate serving as a buffering agent and ammonium bifluoride serving as a corrosion inhibitor into a container filled with distilled water, wherein the mass proportion relationship is that the nickel sulfate: sodium hypophosphite: citric acid: succinic acid: sodium acetate: 25-30% of ammonium bifluoride: 15-30: 10-15: 3-5: 3-5: 3-5; placing the container on a magnetic stirrer, starting a stirring control knob and a heating control switch, controlling the temperature of the solution to be 40-50 ℃, and stirring the solution to completely dissolve all the added reagents;
(2) after the reagents in the step (1) are completely dissolved, adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of a magnetic stirrer to naturally cool the solution from 40-50 ℃ to room temperature;
(3) adding an ammonia water solution with the mass percentage concentration of 25% into the solution to adjust the pH value of the solution to 4.6-5.0, simultaneously placing a pH meter probe into the solution to monitor the change of the pH value, and magnetically stirring the solution for 10-20 min after the pH value is adjusted, thus preparing the chemical nickel-phosphorus plating solution.
Due to the adoption of the technical scheme, the invention has the technical progress that:
the acid-dipping hydrophilic modification is carried out on the matrix, so that the effect of the matrix in the subsequent treatment step is improved; activating and sensitizing a non-metal substrate such as a conductive cross substrate, and attaching palladium on the surface of the substrate to make the substrate conductive; the activated and sensitized substrate is subjected to electro-deposition loading of a thin zinc layer on the surface of the substrate before chemical plating, so that the bonding strength between the substrate and a chemical nickel-phosphorus plating layer can be enhanced, and the bonding force of the nickel-phosphorus plating layer is improved; chemical nickel and phosphorus plating is carried out on the substrate treated by the electro-deposition zinc layer, so that the bonding strength is high; and heating the substrate in a tubular furnace to perform a phosphating reaction to prepare the nickel phosphide-carbon cloth self-supporting electrode. The substrate is carbon cloth with the length and the width of 2cm, acid dipping hydrophilic modification is carried out through concentrated nitric acid for ultrasonic treatment, the modification effect is improved, the deionized water washing effect is good, and vacuum is carried outThe drying oven is set to have the vacuum degree of-0.1 MPa, and the drying effect at 60 ℃ is optimal; the activating effect is better after the substrate is immersed in stannous chloride solution and is subjected to ultrasonic treatment, the sensitizing effect is better after the substrate is immersed in palladium chloride solution and is subjected to ultrasonic treatment, and the plating current density for electrodepositing a zinc layer is 3-5 mA/cm2The plating time is 60-100 s, which is beneficial to forming a better deposition layer, the zinc is selected for electro-deposition on the surface of the substrate to form a thin zinc layer, the bonding strength between the substrate and the chemical nickel and phosphorus plating layer can be enhanced, the corundum porcelain boat is used for carrying out phosphating reaction in the tubular furnace, the chemical nickel and phosphorus plating layer on the surface of the substrate can be phosphated, and the catalytic efficiency is improved. The chemical nickel-phosphorus plating solution uses nickel sulfate as a nickel source to improve the effect of chemical nickel-phosphorus plating, and the ratio of the components of the chemical nickel-phosphorus plating solution improves the effect of chemical nickel-phosphorus plating.
Drawings
FIG. 1 is a 10 μm scanning electron micrograph of a hydrophilically treated carbon cloth;
FIG. 2 scanning electron micrograph of 1 μmm of hydrophilically treated carbon cloth sheet
FIG. 3 is a 10 μm scanning electron micrograph of a nickel-phosphorus-carbon cloth;
FIG. 4 is a 1 μm scanning electron micrograph of a nickel-phosphorus-carbon cloth;
FIG. 5 is a 6 μm scanning electron micrograph of a nickel-phosphorus-carbon cloth sheet after heat treatment;
FIG. 6 is a 1 μm scanning electron micrograph of a nickel-phosphorus-carbon cloth sheet after heat treatment;
FIG. 7 scanning electron micrograph of 6 μm nickel phosphide-carbon cloth;
FIG. 8 scanning electron micrograph of nickel phosphide-carbon cloth at 800 nm;
fig. 9 is an X-ray diffraction (XRD) pattern (relating to nickel-phosphorus-carbon cloth sheet, nickel-phosphorus-carbon cloth sheet after heat treatment, nickel-carbon cloth phosphide);
FIG. 10 is a polarization curve in a 0.5 mol/L sulfuric acid solution with a scan rate of 2 mV/s; (related to carbon cloth, nickel phosphorus-carbon cloth sheet after heat treatment, nickel phosphide-carbon cloth sheet, commercial platinum carbon electrode);
FIG. 11 is a polarization curve in 1.0 mol/L phosphate buffer solution with a scan rate of 2 mV/s; (related to carbon cloth, nickel phosphorus-carbon cloth sheet after heat treatment, nickel phosphide-carbon cloth sheet, commercial platinum carbon electrode);
FIG. 12 is a polarization curve in a 1.0 mol/L potassium hydroxide solution with a scan rate of 2 mV/s; (related to carbon cloth, nickel phosphorus-carbon cloth sheet after heat treatment, nickel phosphide-carbon cloth sheet, commercial platinum carbon electrode).
Detailed Description
The present invention will be described in further detail with reference to the following examples:
the working principle is as follows: the preparation method of the nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution by water and electricity dissociation comprises the following steps:
(1) pre-treating a substrate, cutting the substrate into rectangular sheets with a specified size, carrying out acid-soaking hydrophilic modification treatment on the substrate, carrying out ultrasonic treatment on the substrate after hydrophilic modification, cleaning the substrate until the pH value of a detergent is neutral, and drying the substrate; the matrix can be carbon cloth, a carbon fiber tube, a carbon sheet or other metal matrixes and non-metal matrixes, the matrix is subjected to acid-soaking hydrophilic modification by using 65% concentrated nitric acid in percentage by mass, ultrasonic treatment is performed on a sealed opening of the container for 48 hours, deionized water is used as a detergent to clean the matrix, the matrix is washed for multiple times until the pH value of the detergent for cleaning the matrix is neutral, the matrix is dried in a vacuum drying oven at the temperature of 60 ℃, and the vacuum degree of the vacuum drying oven is-0.1 MPa.
(2) Activating and sensitizing a substrate, wherein the activating treatment is to immerse the substrate in 10g/L stannous chloride solution, the substrate is taken out and washed by deionized water for 5 times after ultrasonic treatment is carried out for 10-20 min, the sensitizing treatment is to immerse the activated substrate in 0.2g/L palladium chloride solution, the substrate is taken out and washed by deionized water for 5 times after ultrasonic treatment is carried out for 20-30 min, the substrate is placed in a vacuum drying oven to be dried at the temperature of 60 ℃, and the vacuum degree of the vacuum drying oven is-0.1 MPa;
(3) treating an electrodeposited zinc layer of the matrix, namely plating by using a zinc plating electrolyte solution by taking the activated and sensitized matrix as an anode and a carbon rod as a cathode, electrodepositing a loaded thin zinc layer on the surface of the matrix, and taking out and cleaning the matrix after plating is finished; the zinc plating electrolyte solution is a mixed aqueous solution of 1.0 mol/L zinc sulfate and 3.0 mol/L potassium chloride, and the plating current densityIs 3 to 5mA/cm2The plating time is 60-100 s.
(4) Carrying a chemical nickel-phosphorus plating layer on the surface of a substrate, heating the chemical nickel-phosphorus plating solution to 80-85 ℃, immersing the substrate carrying a thin zinc layer on the surface in the chemical nickel-phosphorus plating solution, chemically plating and depositing a nickel-phosphorus plating layer on the surface of the substrate, keeping the temperature of the plating solution at 80-85 ℃ in the plating process, carrying out plating for 40-60 min, taking out the substrate after the plating is finished, cleaning the substrate with deionized water for 5 times, drying the substrate in a vacuum drying oven at the temperature of 60 ℃, keeping the vacuum degree of the vacuum drying oven at-0.1 MPa, recording the mass difference of the substrate before and after the substrate, and determining the carrying capacity of the nickel-phosphorus plating layer on the surface of the substrate;
(5) the preparation of the nickel phosphide-carbon cloth self-supporting electrode calculates the mass of the phosphorus source according to the load of the nickel-phosphorus coating on the surface of the substrate, and the ratio of the load of the phosphorus source to the load of the nickel-phosphorus coating on the surface of the substrate is 1: 5. The method comprises the following steps of respectively placing a base body and a phosphorus source into two corundum porcelain boats, placing the two corundum porcelain boats into the center of a hearth of a tubular furnace, placing the corundum porcelain boats with the phosphorus source at one side close to an inert gas inlet of the tubular furnace, slowly introducing inert gas into the tubular furnace, heating the tubular furnace to 300 ℃, and carrying out a phosphating reaction on the base body for 2 hours, wherein the corundum porcelain boats are placed with the phosphorus source and placed at the side close to the inert gas inlet of the tubular furnace, the inert gas is slowly introduced into the tubular furnace, the. And (4) after the phosphating reaction is finished, cooling the tubular furnace to room temperature, and taking out the matrix after phosphating treatment to obtain the nickel phosphide self-supporting electrode.
Preparing a chemical nickel-phosphorus plating solution:
the chemical raw materials used are as follows: soluble nickel salt, reducing agent, buffering agent, composite complexing agent and corrosion inhibitor. Soluble nickel salt: nickel sulfate; reducing agent: sodium hypophosphite; a composite complexing agent: citric acid, succinic acid; buffering agent: sodium acetate; corrosion inhibitor: ammonium bifluoride; the dosage of each reagent has the following mass proportion relation: nickel sulfate: sodium hypophosphite: citric acid: succinic acid: sodium acetate: 25-30% of ammonium bifluoride: 15-30: 10-15: 3-5: 3-5: 3-5;
the preparation process of the chemical nickel-phosphorus plating solution comprises the following steps:
(1) firstly, sequentially adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a beaker filled with 1L of distilled water, placing the beaker on a magnetic stirrer, starting a stirring control knob and a heating control switch, controlling the temperature of a solution to be 40-50 ℃, and stirring the solution to completely dissolve all added reagents;
(2) after the reagents are completely dissolved, adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of a magnetic stirrer to naturally cool the solution from 40-50 ℃ to room temperature;
(3) dropwise adding an ammonia water solution with the mass percentage concentration of 25% into the solution by using a dropper to adjust the pH value of the solution to 4.6-5.0, simultaneously placing a pH meter probe into the solution to monitor the change of the pH value, and magnetically stirring the solution for 10-20 min after the pH value is adjusted, thus preparing the chemical nickel-phosphorus plating solution.
Example 1
(1) Pretreatment of a carbon cloth current collector:
cutting and acid dipping treatment of carbon cloth:
firstly, cutting a commercially available carbon cloth into small pieces with the length and the width of 2cm, then placing the cut carbon cloth pieces into a beaker filled with concentrated nitric acid with the volume of 50 mL and the mass percentage concentration of 65%, carrying out acid soaking hydrophilic modification on the carbon cloth pieces at room temperature, sealing the mouth of a container with a preservative film, then placing the beaker into an ultrasonic cleaner for ultrasonic treatment, wherein the power of the ultrasonic cleaner is 90W, and the ultrasonic treatment time is 48 h; then taking the carbon cloth piece after ultrasonic treatment out of the beaker, washing the carbon cloth piece for multiple times by using deionized water until the pH value of the residual deionized water is neutral, and finally drying the carbon cloth piece which is washed clean in a vacuum drying oven at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa;
activation and sensitization treatment of the carbon cloth piece:
the activation process of the carbon cloth piece is as follows: immersing the carbon cloth piece subjected to acid dipping treatment in a 10g/L stannous chloride solution prepared in advance, performing ultrasonic treatment for 10-20 min at room temperature, wherein the power of an ultrasonic cleaner is 90W, taking out the carbon cloth piece from the stannous chloride solution, and cleaning the carbon cloth piece for 5 times by using deionized water;
the sensitization treatment process of the carbon cloth sheet comprises the following steps: immersing the activated carbon cloth piece into a palladium chloride solution which is prepared in advance and is 0.2g/L again, performing ultrasonic treatment for 20-30 min at room temperature, wherein the power of an ultrasonic cleaner is 90W, and then taking out the carbon cloth piece from the palladium chloride solution and cleaning the carbon cloth piece for 5 times by using deionized water; finally, drying the cleaned carbon cloth piece in a vacuum drying oven at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa;
processing the electro-deposition zinc layer of the carbon cloth sheet:
in order to enhance the bonding strength between the carbon cloth sheet and the chemical nickel-phosphorus plating layer and improve the bonding force of the nickel-phosphorus plating layer, before the activated and sensitized carbon cloth sheet is plated with the nickel-phosphorus plating layer, a thin zinc layer is firstly carried on the surface of the activated and sensitized carbon cloth sheet through electrodeposition, and the implementation process is as follows: the activated and sensitized carbon cloth piece is taken as an anode, a carbon rod is taken as a cathode, the electrolyte is a mixed aqueous solution of zinc sulfate of 1.0 mol/L and potassium chloride of 3.0 mol/L, and the plating current density is controlled to be 3 mA/cm by using a ZF-9 constant potential rectifier2The plating time is 60 s; after plating, taking out the carbon cloth piece from the zinc plating electrolyte solution and cleaning the carbon cloth piece for 5 times by using deionized water;
preparing a chemical nickel-phosphorus plating solution:
chemical raw materials used are as follows:
the nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate and ammonium bifluoride are used in the following mass proportion relationship: nickel sulfate: sodium hypophosphite: citric acid: succinic acid: sodium acetate: ammonium bifluoride 25: 15: 10: 3: 3: 3;
preparing the chemical nickel-phosphorus plating solution:
firstly, sequentially adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a beaker filled with 1L of distilled water, placing the beaker on a magnetic stirrer, starting a stirring control knob and a heating control switch, controlling the temperature of a solution to be 40-50 ℃, and stirring the solution to completely dissolve all added reagents;
after the reagents are completely dissolved, adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of a magnetic stirrer to naturally cool the solution from 40-50 ℃ to room temperature;
dropwise adding an ammonia water solution with the mass percentage concentration of 25% into the solution by using a dropper to adjust the pH value of the solution to 4.6, simultaneously placing a pH meter probe into the solution to monitor the change of the pH value, and magnetically stirring the solution for 10-20 min after the pH value is adjusted, thus preparing the chemical nickel-phosphorus plating solution;
(3) loading a chemical nickel-phosphorus plating layer on the surface of the carbon cloth sheet:
placing a beaker filled with electroless plating solution in a constant-temperature magnetic stirring water bath filled with deionized water, and heating to ensure that the temperature of the plating solution is 80 ℃;
immersing the carbon cloth sheet loaded with the thin electro-galvanized layer on the surface in the step (1) in the chemical plating solution after the temperature of the chemical plating solution rises to 80 ℃, and chemically plating and depositing a nickel-phosphorus coating on the surface of the carbon cloth sheet, wherein the temperature of the plating solution is kept at 80 ℃ in the plating process, and the plating time is 40 min;
thirdly, after the plating is finished, taking out the carbon cloth from the plating solution, cleaning the carbon cloth for 5 times by using deionized water, and then placing the carbon cloth in a vacuum drying oven to be dried at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa;
fourthly, calculating the loading capacity of the nickel-phosphorus coating on the surface of the carbon cloth piece, wherein the mass difference of the carbon cloth piece before and after chemical plating is the loading capacity of the nickel-phosphorus coating;
(4) preparing a nickel phosphide-carbon cloth self-supporting electrode:
preparing materials:
the materials used for preparing the nickel phosphide-carbon cloth self-supporting electrode comprise analytically pure sodium hypophosphite and a carbon cloth sheet with a nickel-phosphorus coating loaded on the surface, wherein the molar ratio of the sodium hypophosphite to the carbon cloth sheet with the nickel-phosphorus coating loaded on the surface is measured by the ratio of the loading amount of the sodium hypophosphite to the loading amount of the nickel-phosphorus coating on the carbon cloth sheet; the loading capacity of nickel phosphorus on the carbon cloth piece is as follows: sodium hypophosphite = 1: 5;
preparing the nickel phosphide-carbon cloth self-supporting electrode:
a. firstly, respectively placing a carbon cloth sheet with a chemical nickel-phosphorus plating coating loaded on the surface and sodium hypophosphite powder into two corundum porcelain boats, then placing the two porcelain boats into the center of a hearth of a tubular furnace, wherein the porcelain boat with the sodium hypophosphite placed is placed at one side close to a nitrogen gas inlet of the tubular furnace, so as to ensure that phosphine gas decomposed by the sodium hypophosphite can be fully contacted with the nickel-phosphorus plating coating on the carbon cloth sheet to be phosphorized;
b. after the two corundum porcelain boats are placed in the center of the hearth of the tubular furnace, a switch knob of a nitrogen cylinder is turned on, so that nitrogen slowly enters the tubular furnace, and the introduction amount of the nitrogen is 10 mL/min; simultaneously, a heating switch of the tubular furnace is opened, so that the temperature of the hearth is increased from room temperature to 300 ℃ at the heating rate of 1 ℃/min, and the chemical nickel-phosphorus plating layer is subjected to a phosphating reaction for 2 hours at the temperature of 300 ℃;
c. after the phosphorization reaction is finished, closing the power supply of the tubular furnace, naturally cooling the hearth to room temperature, and taking out the carbon cloth sheet after the phosphorization treatment after the hearth of the tubular furnace is cooled to room temperature to obtain the nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution through water and electricity dissociation;
(5) electrochemical cathode hydrogen evolution performance test of nickel phosphide-carbon cloth self-supporting electrode
Adopting an electrochemical three-electrode system, respectively taking carbon cloth, the prepared nickel-phosphorus coating/carbon cloth, thermally treated nickel-phosphorus-carbon cloth, a commercial platinum-carbon electrode and the prepared nickel-carbon phosphide self-supporting electrode as working electrodes, a saturated Ag/AgCl electrode as a reference electrode and a carbon rod as a counter electrode, and respectively connecting the three electrodes with an electrochemical workstation CHI660E in Shanghai province; the electrolyte solution used in the test is 1.0 mol/L sulfuric acid solution, and the electrochemical hydrogen evolution performance of the electrolyte solution under the acidic condition is tested by adopting a linear scanning voltammetry method, wherein the potential scanning speed is 2 mV/s.
FIGS. 1 to 8 are SEM images, and FIGS. 1 and 2 are scanning electron microscope images of a hydrophilically treated carbon cloth, from which it can be seen that the hydrophilically treated carbon cloth has a smooth surface, fibrous texture, and no protrusions; FIGS. 3 and 4 are scanning electron micrographs of the carbon cloth after chemical nickel-phosphorus plating, the surface of the carbon cloth is uniformly covered by the nickel-phosphorus plating layer, the fiber texture of the carbon cloth is no longer significant, and a small amount of protruding nickel-phosphorus particles can be observed; FIGS. 5 and 6 are scanning electron micrographs of a nickel-phosphorus-carbon cloth sheet after heat treatment at 300 ℃ alone without addition of a phosphorus source for phosphating, in which cauliflower-like small protrusions are clearly visible, which are caused by nickel-phosphorus heat treatment crystallization; FIGS. 7 and 8 are scanning electron micrographs of a nickel phosphide-carbon cloth obtained by phosphating at 300 ℃ for 2 hours, and the nickel phosphorus plated layer after phosphating is converted into irregular snow-cake-like nickel phosphide, unlike the morphology obtained by simple heat treatment.
Fig. 9 is an XRD chart, in each sample pattern, the peak of the amorphous steamed bun appearing around 2 θ =25 ° is a (002) diffraction peak of the carbon cloth, which is an amorphous graphite carbon layer structure of the carbon cloth, indicating that the carbon fiber of the carbon cloth is composed of anisotropically dispersed graphite-like crystallites; after heat treatment of the nickel-phosphorus-carbon cloth, Ni is present3P metastable phase generation, but Ni3The diffraction peak intensity of the P phase is weak, and the crystallinity is poor; the phosphorized nickel-carbon cloth obtained after the phosphorization treatment of the nickel-phosphorus-carbon cloth is of an obvious crystalline structure, the crystallinity is good, and the crystalline diffraction peak of the phosphorized nickel-carbon cloth is consistent with the diffraction peak of a standard nickel phosphide card, which indicates that the nickel-phosphorus coating is converted into a nickel phosphide metastable phase after the phosphorization treatment.
FIG. 10 is a linear sweep voltammetry curve in a 0.5 mol/L sulfuric acid medium; according to experimental results, except for a commercial platinum-carbon electrode, the electrochemical hydrogen evolution performance of a nickel phosphide-carbon cloth sample is optimal; when the current density is-10 mA/cm2In the meantime, the hydrogen evolution potential of the nickel phosphide-carbon cloth sample is-119 mV, and referring to the research result of electrochemical hydrogen evolution of the currently disclosed phosphide catalytic material, the nickel phosphide-carbon cloth prepared in example 1 has excellent electrochemical hydrogen evolution performance.
Example 2
(1) Pretreatment of a carbon cloth current collector:
cutting and acid dipping treatment of carbon cloth: same as example 1;
activation and sensitization treatment of the carbon cloth piece: same as example 1;
processing the electro-deposition zinc layer of the carbon cloth sheet:
in order to enhance the bonding strength between the carbon cloth sheet and the chemical nickel-phosphorus plating layer and improve the bonding force of the nickel-phosphorus plating layer, before the activated and sensitized carbon cloth sheet is plated with the nickel-phosphorus plating layer, a thin zinc layer is firstly carried on the surface of the activated and sensitized carbon cloth sheet through electrodeposition, and the implementation process is as follows: the activated and sensitized carbon cloth is used asThe anode and the carbon rod are the cathode, the electrolyte is a mixed water solution of zinc sulfate of 1.0 mol/L and potassium chloride of 3.0 mol/L, and the plating current density is controlled to be 4 mA/cm by using a ZF-9 constant potential rectifier2The plating time is 80 s; after plating, taking out the carbon cloth piece from the zinc plating electrolyte solution and cleaning the carbon cloth piece for 5 times by using deionized water;
preparing a chemical nickel-phosphorus plating solution:
chemical raw materials used are as follows:
the nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate and ammonium bifluoride are used in the following mass proportion relationship: nickel sulfate: sodium hypophosphite: citric acid: succinic acid: sodium acetate: ammonium acid fluoride ═ 28: 23: 13: 4: 4: 4;
preparing the chemical nickel-phosphorus plating solution:
firstly, sequentially adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a beaker filled with 1L of distilled water, placing the beaker on a magnetic stirrer, starting a stirring control knob and a heating control switch, controlling the temperature of a solution to be 40-50 ℃, and stirring the solution to completely dissolve all added reagents;
after the reagents are completely dissolved, adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of a magnetic stirrer to naturally cool the solution from 40-50 ℃ to room temperature;
dropwise adding an ammonia water solution with the mass percentage concentration of 25% into the solution by using a dropper to adjust the pH value of the solution to 4.8, simultaneously placing a pH meter probe into the solution to monitor the change of the pH value, and magnetically stirring the solution for 10-20 min after the pH value is adjusted, thus preparing the chemical nickel-phosphorus plating solution;
(3) loading a chemical nickel-phosphorus plating layer on the surface of the carbon cloth sheet:
placing a beaker filled with electroless plating solution in a constant-temperature magnetic stirring water bath filled with deionized water, and heating to ensure that the temperature of the plating solution is 83 ℃;
immersing the carbon cloth sheet loaded with the thin electro-galvanized layer on the surface in the step (1) in the chemical plating solution after the temperature of the chemical plating solution rises to 83 ℃, and chemically plating and depositing a nickel-phosphorus coating on the surface of the carbon cloth sheet, wherein the temperature of the plating solution is kept at 83 ℃ in the plating process, and the plating time is 50 min;
thirdly, after the plating is finished, taking out the carbon cloth from the plating solution, cleaning the carbon cloth for 5 times by using deionized water, and then placing the carbon cloth in a vacuum drying oven to be dried at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa;
fourthly, calculating the loading capacity of the nickel-phosphorus coating on the surface of the carbon cloth piece, wherein the mass difference of the carbon cloth piece before and after chemical plating is the loading capacity of the nickel-phosphorus coating;
(4) preparing a nickel phosphide-carbon cloth self-supporting electrode:
preparing materials: same as example 1;
preparing the nickel phosphide-carbon cloth self-supporting electrode:
a. same as example 1;
b. after the two corundum porcelain boats are placed in the center of the hearth of the tubular furnace, a switch knob of a nitrogen cylinder is turned on, so that nitrogen slowly enters the tubular furnace, and the introduction amount of the nitrogen is 20 mL/min; simultaneously, a heating switch of the tubular furnace is opened, so that the temperature of the hearth is increased from room temperature to 300 ℃ at the heating rate of 3 ℃/min, and the chemical nickel-phosphorus plating layer is subjected to a phosphating reaction for 2 hours at the temperature of 300 ℃;
c. after the phosphorization reaction is finished, closing the power supply of the tubular furnace, naturally cooling the hearth to room temperature, and taking out the carbon cloth sheet after the phosphorization treatment after the hearth of the tubular furnace is cooled to room temperature to obtain the nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution through water and electricity dissociation;
(5) electrochemical cathode hydrogen evolution performance test of nickel phosphide-carbon cloth self-supporting electrode
Adopting an electrochemical three-electrode system, respectively taking carbon cloth, the prepared nickel-phosphorus coating/carbon cloth, thermally treated nickel-phosphorus-carbon cloth, a commercial platinum-carbon electrode and the prepared nickel-carbon phosphide self-supporting electrode as working electrodes, a saturated Ag/AgCl electrode as a reference electrode and a carbon rod as a counter electrode, and respectively connecting the three electrodes with an electrochemical workstation CHI660E in Shanghai province; the electrolyte solution used in the test is 1.0 mol/L phosphate buffer solution, and the electrochemical hydrogen evolution performance of the electrolyte solution under the neutral condition is tested by adopting a linear sweep voltammetry method, wherein the potential sweep speed is 2 mV/s.
FIG. 11 is a linear sweep voltammetry curve in 1.0 mol/L phosphate buffer solution, and from experimental results, it can be seen that the electrochemical hydrogen evolution performance of the nickel phosphide-carbon cloth sample is the best except for the commercial platinum-carbon electrode; when the current density is-10 mA/cm2In the meantime, the hydrogen evolution potential of the nickel phosphide-carbon cloth sample is-160 mV, and referring to the research result of electrochemical hydrogen evolution of the currently disclosed phosphide catalytic material, the nickel phosphide-carbon cloth prepared in example 2 has excellent electrochemical hydrogen evolution performance. The SEM image and XRD image are not significantly different from those of the sample prepared in example 1, and thus the details are not described.
Example 3
(1) Pretreatment of a carbon cloth current collector:
cutting and acid dipping treatment of carbon cloth: same as example 1;
activation and sensitization treatment of the carbon cloth piece: same as in example 1:
processing the electro-deposition zinc layer of the carbon cloth sheet:
in order to enhance the bonding strength between the carbon cloth sheet and the chemical nickel-phosphorus plating layer and improve the bonding force of the nickel-phosphorus plating layer, before the activated and sensitized carbon cloth sheet is plated with the nickel-phosphorus plating layer, a thin zinc layer is firstly carried on the surface of the activated and sensitized carbon cloth sheet through electrodeposition, and the implementation process is as follows: the activated and sensitized carbon cloth piece is taken as an anode, a carbon rod is taken as a cathode, the electrolyte is a mixed aqueous solution of zinc sulfate of 1.0 mol/L and potassium chloride of 3.0 mol/L, and the plating current density is controlled to be 5mA/cm by using a ZF-9 constant potential rectifier2The plating time is 100 s; after plating, taking out the carbon cloth piece from the zinc plating electrolyte solution and cleaning the carbon cloth piece for 5 times by using deionized water;
preparing a chemical nickel-phosphorus plating solution:
chemical raw materials used are as follows:
the nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate and ammonium bifluoride are used in the following mass proportion relationship: nickel sulfate: sodium hypophosphite: citric acid: succinic acid: sodium acetate: ammonium bifluoride 30: 30: 15: 5: 5: 5;
preparing the chemical nickel-phosphorus plating solution:
firstly, sequentially adding nickel sulfate, citric acid, succinic acid, sodium acetate and ammonium bifluoride into a beaker filled with 1L of distilled water, placing the beaker on a magnetic stirrer, starting a stirring control knob and a heating control switch, controlling the temperature of a solution to be 40-50 ℃, and stirring the solution to completely dissolve all added reagents;
after the reagents are completely dissolved, adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of a magnetic stirrer to naturally cool the solution from 40-50 ℃ to room temperature;
dropwise adding an ammonia water solution with the mass percentage concentration of 25% into the solution by using a dropper to adjust the pH value of the solution to 5.0, simultaneously placing a pH meter probe into the solution to monitor the change of the pH value, and magnetically stirring the solution for 10-20 min after the pH value is adjusted, thus preparing the chemical nickel-phosphorus plating solution;
(3) loading a chemical nickel-phosphorus plating layer on the surface of the carbon cloth sheet:
placing a beaker filled with electroless plating solution in a constant-temperature magnetic stirring water bath filled with deionized water, and heating to ensure that the temperature of the plating solution is 85 ℃;
immersing the carbon cloth sheet loaded with the thin electro-galvanized layer on the surface in the step (1) in the chemical plating solution after the temperature of the chemical plating solution rises to 85 ℃, and chemically plating and depositing a nickel-phosphorus coating on the surface of the carbon cloth sheet, wherein the temperature of the plating solution is kept at 85 ℃ in the plating process, and the plating time is 60 min;
③ same as example 1;
fourthly, calculating the loading capacity of the nickel-phosphorus coating on the surface of the carbon cloth piece, wherein the mass difference of the carbon cloth piece before and after chemical plating is the loading capacity of the nickel-phosphorus coating;
(4) preparing a nickel phosphide-carbon cloth self-supporting electrode:
preparing materials: same as example 1;
preparing the nickel phosphide-carbon cloth self-supporting electrode:
a. same as example 1;
b. after the two corundum porcelain boats are placed in the center of the hearth of the tubular furnace, a switch knob of a nitrogen cylinder is turned on, so that nitrogen slowly enters the tubular furnace, and the introduction amount of the nitrogen is 30 mL/min; simultaneously, a heating switch of the tubular furnace is opened, so that the temperature of the hearth is increased from room temperature to 300 ℃ at the temperature rise rate of 5 ℃/min, and the chemical nickel-phosphorus plating layer is subjected to a phosphating reaction for 2 hours at the temperature of 300 ℃;
c. after the phosphorization reaction is finished, closing the power supply of the tubular furnace, naturally cooling the hearth to room temperature, and taking out the carbon cloth sheet after the phosphorization treatment after the hearth of the tubular furnace is cooled to room temperature to obtain the nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution through water and electricity dissociation;
(5) electrochemical cathode hydrogen evolution performance test of nickel phosphide-carbon cloth self-supporting electrode
Adopting an electrochemical three-electrode system, respectively taking carbon cloth, the prepared nickel-phosphorus coating/carbon cloth, thermally treated nickel-phosphorus-carbon cloth, a commercial platinum-carbon electrode and the prepared nickel-carbon phosphide self-supporting electrode as working electrodes, a saturated Ag/AgCl electrode as a reference electrode and a carbon rod as a counter electrode, and respectively connecting the three electrodes with an electrochemical workstation CHI660E in Shanghai province; the electrolyte solution used in the test is 1.0 mol/L potassium hydroxide solution, and the electrochemical hydrogen evolution performance of the electrolyte solution under the alkaline condition is tested by adopting a linear scanning voltammetry method, wherein the potential scanning speed is 2 mV/s.
FIG. 12 is a linear sweep voltammetry curve in a 1.0 mol/L KOH solution, and it can be seen from the experimental results that the electrochemical hydrogen evolution performance of the nickel phosphide-carbon cloth sample is the best except for the commercial platinum-carbon electrode; when the current density is-10 mA/cm2In the meantime, the hydrogen evolution potential of the nickel phosphide-carbon cloth sample is-148 mV, and referring to the research result of electrochemical hydrogen evolution of the currently disclosed phosphide catalytic material, the nickel phosphide-carbon cloth prepared in example 3 has excellent electrochemical hydrogen evolution performance. The SEM image and XRD image are not significantly different from those of the sample prepared in example 1, and thus the details are not described.
Claims (7)
1. The preparation method of the nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution by water and electricity dissociation is characterized by comprising the following steps:
(1) pre-treating a substrate, cutting the substrate into rectangular sheets with a specified size, carrying out acid-soaking hydrophilic modification treatment on the substrate, carrying out ultrasonic treatment on the substrate after the acid-soaking hydrophilic modification treatment, cleaning the substrate by using a detergent until the pH value of the detergent is neutral, and drying the substrate;
(2) activating and sensitizing a matrix, wherein the activating treatment is to immerse the matrix in stannous chloride solution, taking out the matrix for cleaning after ultrasonic treatment, the sensitizing treatment is to immerse the matrix after the activating treatment in palladium chloride solution, taking out the matrix for cleaning after ultrasonic treatment, and drying the matrix;
(3) performing electrodeposition zinc layer treatment on the matrix, namely plating by using the activated and sensitized matrix as an anode and a carbon rod as a cathode by using a galvanizing electrolyte solution, electrodepositing a loaded thin zinc layer on the surface of the matrix, and taking out the matrix for cleaning after plating;
(4) carrying a chemical nickel-phosphorus plating layer on the surface of a substrate, heating a chemical nickel-phosphorus plating solution to a certain temperature, immersing the substrate carrying a thin zinc layer on the surface in the chemical nickel-phosphorus plating solution, chemically plating and depositing the nickel-phosphorus plating layer on the surface of the substrate, keeping a certain temperature in the plating process, taking out the substrate after the plating is finished, cleaning the substrate, drying the substrate, recording the mass difference of the substrate before and after the substrate is dried, and determining the carrying capacity of the nickel-phosphorus plating layer on the surface of the substrate;
(5) the preparation of the nickel phosphide-carbon cloth self-supporting electrode comprises the steps of calculating the quality of a phosphorus source through the load of a nickel phosphorus coating on the surface of a substrate, respectively placing the substrate and the phosphorus source into two corundum porcelain boats, placing the two corundum porcelain boats into the center of a hearth of a tubular furnace, placing the corundum porcelain boat in which the phosphorus source is placed on one side close to an inert gas inlet of the tubular furnace, slowly introducing the inert gas into the tubular furnace, heating the tubular furnace to a set temperature, carrying out a phosphating reaction on the substrate, cooling the tubular furnace to room temperature, taking out the substrate after the phosphating treatment, and thus obtaining the nickel phosphide self-supporting electrode.
2. The method for preparing a nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution from hydroelectric dissociation as claimed in claim 1, which is characterized in that: in the step (1), the substrate is carbon cloth with the length and the width of 2cm, the substrate is subjected to acid-soaking hydrophilic modification by using 65% concentrated nitric acid in percentage by mass, ultrasonic treatment is performed on a sealed opening of the container for 48 hours, deionized water is used as a detergent to clean the substrate, the substrate is placed in a vacuum drying oven to be dried at the temperature of 60 ℃, and the vacuum degree of the vacuum drying oven is-0.1 MPa.
3. The method for preparing a nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution from hydroelectric dissociation as claimed in claim 1, which is characterized in that: and (3) carrying out activation treatment on the stannous chloride solution in the step (2), taking out the substrate after ultrasonic treatment for 10-20 min, washing the substrate with deionized water for 5 times, carrying out sensitization treatment on the palladium chloride solution in the step (0.2 g/L), taking out the substrate after ultrasonic treatment for 20-30 min, washing the substrate with deionized water for 5 times, placing the substrate in a vacuum drying oven, and drying the substrate at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa.
4. The method for preparing a nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution from hydroelectric dissociation as claimed in claim 1, which is characterized in that: the zinc plating electrolyte solution in the step (3) is a mixed water solution of zinc sulfate and potassium chloride of 1.0 mol/L and the plating current density is 3-5 mA/cm2And the plating time is 60-100 s, and the substrate is cleaned for 5 times by using deionized water after the plating is finished.
5. The method for preparing a nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution from hydroelectric dissociation as claimed in claim 1, which is characterized in that: and (4) keeping the temperature of the chemical nickel-phosphorus plating solution at 80-85 ℃ in the plating process, keeping the temperature of the plating solution at 80-85 ℃ for 40-60 min, taking out the substrate after plating, washing the substrate with deionized water for 5 times, drying the substrate in a vacuum drying oven at the temperature of 60 ℃, wherein the vacuum degree of the vacuum drying oven is-0.1 MPa.
6. The method for preparing a nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution from hydroelectric dissociation as claimed in claim 1, which is characterized in that: in the step (5), the mass of the phosphorus source is calculated according to the ratio of the phosphorus source to the loading amount of the nickel-phosphorus coating on the surface of the substrate being 1:5, the phosphorus source is sodium hypophosphite, the inert gas is nitrogen, the introduction amount of the nitrogen is 10-30 mL/min, the tubular furnace is heated to 300 ℃, and the time for carrying out the phosphating reaction on the substrate is 2 hours.
7. The method for preparing an electroless nickel-phosphorus plating solution according to claim 1, comprising the steps of:
(1) firstly, sequentially adding nickel sulfate serving as soluble nickel salt, citric acid and succinic acid serving as composite complexing agents, sodium acetate serving as a buffering agent and ammonium bifluoride serving as a corrosion inhibitor into a container filled with distilled water, wherein the mass proportion relationship is that the nickel sulfate: sodium hypophosphite: citric acid: succinic acid: sodium acetate: 25-30% of ammonium bifluoride: 15-30: 10-15: 3-5: 3-5: 3-5; placing the container on a magnetic stirrer, starting a stirring control knob and a heating control switch, controlling the temperature of the solution to be 40-50 ℃, and stirring the solution to completely dissolve all the added reagents;
(2) after the reagents in the step (1) are completely dissolved, adding sodium hypophosphite into the solution, stirring to dissolve the sodium hypophosphite, and after the sodium hypophosphite is completely dissolved, closing a heating control switch of a magnetic stirrer to naturally cool the solution from 40-50 ℃ to room temperature;
(3) adding an ammonia water solution with the mass percentage concentration of 25% into the solution to adjust the pH value of the solution to 4.6-5.0, simultaneously placing a pH meter probe into the solution to monitor the change of the pH value, and magnetically stirring the solution for 10-20 min after the pH value is adjusted, thus preparing the chemical nickel-phosphorus plating solution.
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