A zirconium-doped nickel sulfide self-supporting electrode material and its preparation method and application

Abstract

The invention discloses a zirconium-doped nickel sulfide self-supporting electrode material, a preparation method thereof, and an application thereof. The method comprises the following steps: step 1, adding 0.5-3 mmol of zirconium nitrate pentahydrate and 1.5-9 mmol of thioacetamide to a beaker containing 20 mL of anhydrous ethanol, and stirring evenly to obtain a mixed solution A; step 2, firstly transferring the mixed solution A dropwise to a polytetrafluoroethylene liner, then placing 1.5 cm×4 cm×0.2 cm of pure nickel foam into the polytetrafluoroethylene liner containing the mixed solution A, then sealing the polytetrafluoroethylene liner and placing it in an autoclave, finally placing the autoclave in an oven, heating the temperature from room temperature to 120-180° C. at a heating rate of 5° C. / min, and keeping the temperature until the reaction is fully completed; step 3, after the heat preservation is completed, allowing the autoclave to cool naturally to room temperature, taking out the product, cleaning it, and standing it at room temperature. After the product is completely dried, Zr-Ni 0.96 S / NF has excellent catalytic performance for water electrolysis.

Description

Technical Field

[0001] The invention relates to a composite material, in particular to a zirconium-doped nickel sulfide self-supporting electrode material and a preparation method and application thereof. Background Art

[0002] Hydrogen energy, as a new, clean, and renewable energy source, is an ideal energy source to replace fossil fuels in the future. Water electrolysis offers hope for sustainable hydrogen production and is the most promising method for obtaining hydrogen on a large scale. Water electrolysis is the process of using abundant electricity generated by new and renewable energy sources, such as solar energy, wind energy, and tides, to electrolyze water, generating hydrogen and oxygen at the cathode and anode, respectively. However, due to the high energy consumption and low conversion efficiency of the electrolysis process, it has become a common consensus to use efficient catalysts to reduce the overpotential of the hydrogen and oxygen evolution reactions to achieve energy reduction. In the field of electrocatalysis, precious metal-based materials (Pt, Ru, or Ir oxides) are currently the most efficient electrocatalysts for hydrogen production. However, their low reserves and high costs make them difficult to be widely used. Therefore, the development of non-precious metal HER catalysts with high reserves, high catalytic activity, and stability has become the research focus of many scientific researchers.

[0003] Transition metal nickel and its compounds are not only low-cost and readily available, but nickel sulfide also exhibits excellent electrocatalytic hydrogen evolution performance. Furthermore, nickel and its derived compounds exhibit particularly good electrochemical properties, effectively reducing the overpotential during electrocatalytic reactions and effectively replacing the original precious metals for use as electrode materials in electrocatalytic reaction systems. At the same time, element doping, a common method for enhancing intrinsic activity, can be achieved by adjusting the electronic structure of nickel sulfide catalysts through the addition of exogenous elements. Using methods to dope exogenous elements into nickel sulfide to enhance its catalytic performance in water electrolysis is of great research interest. Summary of the Invention

[0004] The purpose of the present invention is to provide a zirconium-doped nickel sulfide self-supporting electrode material and its preparation method and application. Not only is the preparation method simple, but the prepared zirconium-doped nickel sulfide also has excellent electrolytic water catalytic performance.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A method for preparing a zirconium-doped nickel sulfide self-supporting electrode material comprises the following steps:

[0007] Step 1: add 0.5-3 mmol of zirconium nitrate pentahydrate and 1.5-9 mmol of thioacetamide into a beaker containing 20 mL of anhydrous ethanol and stir to obtain a mixed solution A;

[0008] Step 2: First, the mixed solution A is transferred dropwise into a polytetrafluoroethylene liner, and then a 1.5 cm × 4 cm × 0.2 cm pure nickel foam is placed into the polytetrafluoroethylene liner containing the mixed solution A. The polytetrafluoroethylene liner is then sealed and placed in an autoclave. Finally, the autoclave is placed in an oven and heated from room temperature to 120-180°C at a heating rate of 5°C / min, and kept warm until the reaction is fully completed.

[0009] Step 3: After the heat preservation is completed, the autoclave is cooled naturally to room temperature, the product is taken out, cleaned, and allowed to stand at room temperature until the product is completely dried to obtain Zr-Ni 0.96 S / NF.

[0010] Furthermore, the purity of zirconium nitrate pentahydrate in step 1 is 99.9%.

[0011] Furthermore, the stirring in step 1 is carried out using a magnetic stirrer at 500-700 r / min and at a temperature of 50-60° C. for 30-45 min.

[0012] Furthermore, the pure nickel foam in step 2 is prepared by the following method:

[0013] Step 2.1, placing commercial nickel foam in acetone, 3 mol / L HCl solution, and deionized water, respectively, for ultrasonic cleaning;

[0014] Step 2.2: Rinse the nickel foam after ultrasonic cleaning alternately with deionized water and anhydrous ethanol, and obtain pure nickel foam after drying.

[0015] Furthermore, the ultrasonic cleaning in step 2.1 is performed at a power of 70 to 80 W for 5 to 10 minutes.

[0016] Furthermore, the drying in step 2.2 is carried out in a forced air drying oven at 60° C. for 2 h.

[0017] Furthermore, the insulation time of step 2 is 10 to 16 hours.

[0018] Furthermore, the washing in step 3 is performed by alternately rinsing with deionized water and anhydrous ethanol until the washing is clean.

[0019] A zirconium-doped nickel sulfide self-supporting electrode material Zr-Ni 0.96 S / NF.

[0020] A zirconium-doped nickel sulfide self-supporting electrode material Zr-Ni 0.96 Application of S / NF as electrocatalyst for hydrogen evolution reaction.

[0021] The present invention has the following beneficial effects:

[0022] (1) The present invention uses zirconium Zr atoms as doping elements. Since the ionic radius of Zr is large, Zr doped into the transition metal layer can expand the ion diffusion channel, thereby increasing the ion migration rate of the material, thereby improving the electrocatalytic performance, so that the final product Zr-Ni 0.96 Under the coordination of Zr, the electronegativity of S in S / NF becomes stronger, while that of Ni becomes weaker. S has a stronger proton adsorption ability during the HER reaction, which is conducive to the occurrence of the HER reaction. The weakening of Ni's electronegativity will reduce Ni's adsorption capacity for hydrides, which makes the generated products easier to be released, which is more conducive to the improvement of electrocatalytic performance.

[0023] (2) The final product Zr-Ni prepared by the present invention 0.96 Compared with the product Ni3S2 / NF without Zr doping, S / NF presents a dispersed nanoparticle structure with a relatively uniform appearance. This structure provides the electrode material with a larger specific surface area, thereby increasing the contact area between the material and the electrolyte during the reaction, enabling it to expose more active sites, which is conducive to the occurrence of water electrolysis reaction and has good water electrolysis catalytic performance.

[0024] (3) The present invention adopts a simple one-step solvent thermal method to synthesize Zr-doped electrode materials with excellent electrocatalytic performance. This method mainly adopts medium and low temperature liquid phase control, which makes the process simpler and easier to control. No high temperature treatment is required to obtain products with complete crystal form, uniform particle size distribution and good dispersion, thereby relatively reducing energy consumption and being environmentally friendly. In addition, the preparation time is short, there is no large-scale reaction equipment and harsh conditions, the raw materials are relatively cheap and easy to obtain, the yield is high, and the product morphology and size are controllable.

[0025] (4) The present invention utilizes nickel sulfide to have a catalytic activity for hydrogen evolution reaction similar to that of platinum, and prepares a hydrogen evolution reaction electrocatalyst Zr-Ni by rationally regulating the composition and structure of nickel sulfide. 0.96 S / NF has high activity and good stability, and has important significance and application prospects in reducing the cost of hydrogen evolution catalysts in water electrolysis and improving hydrogen production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 : Zr-Ni prepared in Example 1 of the present invention 0.96 XRD patterns of S / NF and Ni3S2 / NF prepared in Comparative Example 1;

[0027] Figure 2 : Zr-Ni prepared in Example 1 of the present invention 0.96 Morphology images of S / NF at different magnifications (ab) and morphology images of Ni3S2 / NF prepared in Comparative Example 1 at different magnifications (cd);

[0028] Figure 3 : Zr-Ni prepared in Example 1 of the present invention 0.96 Transmission diagram of S / NF (ab);

[0029] Figure 4 : Zr-Ni prepared in Example 1 of the present invention 0.96 Element distribution of S / NF Figure 1 (c);

[0030] Figure 5 : Zr-Ni prepared in Example 1 of the present invention 0.96 Element distribution of S / NF Figure 2 (dg)

[0031] Figure 6 : Zr-Ni prepared in Example 1 of the present invention 0.96 LSV curves of hydrogen production of S / NF, Ni3S2 / NF prepared in Comparative Example 1, NF prepared in Comparative Example 2, and 20% Pt / C / NF prepared in Comparative Example 3;

[0032] Figure 7 : Zr-Ni prepared in Example 1 of the present invention 0.96 Comparison of oxygen production LSV curves of S / NF, Ni3S2 / NF prepared in Comparative Example 1, NF prepared in Comparative Example 2, and IrO2 / NF prepared in Comparative Example 4. DETAILED DESCRIPTION

[0033] The specific contents of the present invention are further explained in detail below with reference to the embodiments, but are not intended to limit the present invention.

[0034] The present invention uses a fixed volume (length 1.5cm, width 4cm, thickness 0.2cm) of commercial nickel foam as a carrier, and uses it as a substrate and nickel source to prepare zirconium-doped nickel sulfide Zr-Ni 0.96 S / NF, Zr-Ni 0.96 S / NF can be directly used as a working electrode with a working area of ​​∼0.25 cm 2 The loading amount of nickel sulfide on nickel foam is ~0.8mg / cm 2 .

[0035] Example 1

[0036] Step 1: 1 mmol of zirconium nitrate pentahydrate and 3 mmol of thioacetamide were added to a beaker containing 20 mL of ethanol, and stirred at 60° C. for 40 min using a magnetic stirrer at 500 rpm to obtain a mixed solution A.

[0037] Step 2: First, a commercial nickel foam NF with a size of 1.5 cm × 4 cm × 0.2 cm was placed in acetone, a 3 mol / L HCl solution, and deionized water, and ultrasonically cleaned at 70 W for 10 minutes, then rinsed alternately with deionized water and anhydrous ethanol, and then dried in a 60°C forced air drying oven for 2 hours to obtain pure nickel foam;

[0038] Step 3: First, transfer the mixed solution A dropwise to a polytetrafluoroethylene liner, then add pure nickel foam, then seal the polytetrafluoroethylene liner and place it in an autoclave. Finally, place the autoclave in an oven, heat it from room temperature to 160°C at a heating rate of 5°C / min, and keep it warm for 12 hours.

[0039] Step 4: After the heat preservation is completed, the autoclave is cooled naturally to room temperature, the product is taken out, and it is rinsed alternately with deionized water and anhydrous ethanol, and then allowed to stand at room temperature until the product is completely dried to obtain Zr-Ni 0.96 S / NF.

[0040] The electrode material Zr-Ni prepared in Example 1 0.96 S / NF was tested for hydrogen evolution reaction in potassium hydroxide solution with pH=14: when the current density was 10 mA / cm 2 When the current density is 100mA / cm 2 When , the sample overpotential is 202mV.

[0041] The electrode material Zr-Ni prepared in Example 1 0.96 S / NF was tested for oxygen evolution reaction in potassium hydroxide solution with pH=14: when the current density was 10 mA / cm 2 When the current density is 100mA / cm 2 When , the sample overpotential is 646mV.

[0042] Example 2

[0043] Step 1: 0.5 mmol of zirconium nitrate pentahydrate and 1.5 mmol of thioacetamide were added to a beaker containing 20 mL of ethanol, and stirred at 55° C. for 45 min using a magnetic stirrer at 550 rpm to obtain a mixed solution A.

[0044] Step 2: First, a commercial nickel foam NF with a size of 1.5 cm × 4 cm × 0.2 cm was placed in acetone, a 3 mol / L HCl solution, and deionized water, and ultrasonically cleaned at 75 W for 8 minutes, then rinsed alternately with deionized water and anhydrous ethanol, and then dried in a 60°C forced air drying oven for 2 hours to obtain pure nickel foam;

[0045] Step 3: First, transfer the mixed solution A dropwise to a polytetrafluoroethylene liner, then add pure nickel foam, then seal the polytetrafluoroethylene liner and place it in an autoclave. Finally, place the autoclave in an oven, heat it from room temperature to 120°C at a heating rate of 5°C / min, and keep it warm for 16 hours.

[0046] Step 4: After the heat preservation is completed, the autoclave is cooled naturally to room temperature, the product is taken out, and it is rinsed alternately with deionized water and anhydrous ethanol, and then allowed to stand at room temperature until the product is completely dried to obtain Zr-Ni 0.96 S / NF.

[0047] Example 3

[0048] Step 1: 1.75 mmol of zirconium nitrate pentahydrate and 4 mmol of thioacetamide were added to a beaker containing 20 mL of ethanol, and stirred at 50° C. for 35 min using a magnetic stirrer at 600 rpm to obtain a mixed solution A.

[0049] Step 2: First, a commercial nickel foam NF with a size of 1.5 cm × 4 cm × 0.2 cm was placed in acetone, a 3 mol / L HCl solution, and deionized water, and ultrasonically cleaned at 80 W for 6 minutes, then rinsed alternately with deionized water and anhydrous ethanol, and then dried in a 60°C forced air drying oven for 2 hours to obtain pure nickel foam;

[0050] Step 3: First, transfer the mixed solution A dropwise to a polytetrafluoroethylene liner, then add pure nickel foam, then seal the polytetrafluoroethylene liner and place it in an autoclave. Finally, place the autoclave in an oven, heat it from room temperature to 140°C at a heating rate of 5°C / min, and keep it warm for 14 hours.

[0051] Step 4: After the heat preservation is completed, the autoclave is cooled naturally to room temperature, the product is taken out, and it is rinsed alternately with deionized water and anhydrous ethanol, and then allowed to stand at room temperature until the product is completely dried to obtain Zr-Ni 0.96 S / NF.

[0052] Example 4

[0053] Step 1: 2.3 mmol of zirconium nitrate pentahydrate and 5.25 mmol of thioacetamide were added to a beaker containing 20 mL of ethanol, and stirred at 60° C. for 30 min using a magnetic stirrer at 650 rpm to obtain a mixed solution A.

[0054] Step 2: First, a commercial nickel foam NF with a size of 1.5 cm × 4 cm × 0.2 cm was placed in acetone, a 3 mol / L HCl solution, and deionized water, and ultrasonically cleaned at 80 W for 5 minutes, then rinsed alternately with deionized water and anhydrous ethanol, and then dried in a 60°C forced air drying oven for 2 hours to obtain pure nickel foam;

[0055] Step 3: First, transfer the mixed solution A dropwise to a polytetrafluoroethylene liner, then add pure nickel foam, then seal the polytetrafluoroethylene liner and place it in an autoclave. Finally, place the autoclave in an oven, heat it from room temperature to 150°C at a heating rate of 5°C / min, and keep it warm for 13 hours.

[0056] Step 4: After the heat preservation is completed, the autoclave is cooled naturally to room temperature, the product is taken out, and it is rinsed alternately with deionized water and anhydrous ethanol, and then allowed to stand at room temperature until the product is completely dried to obtain Zr-Ni 0.96 S / NF.

[0057] Example 5

[0058] Step 1: 3 mmol of zirconium nitrate pentahydrate and 7 mmol of thioacetamide were added to a beaker containing 20 mL of ethanol, and stirred at 55° C. for 30 min using a magnetic stirrer at 700 rpm to obtain a mixed solution A.

[0059] Step 2: First, a commercial nickel foam NF with a size of 1.5 cm × 4 cm × 0.2 cm was placed in acetone, a 3 mol / L HCl solution, and deionized water, and ultrasonically cleaned at 70 W for 9 minutes, then rinsed alternately with deionized water and anhydrous ethanol, and then dried in a 60°C forced air drying oven for 2 hours to obtain pure nickel foam;

[0060] Step 3: First, transfer the mixed solution A dropwise into a polytetrafluoroethylene liner, then add pure nickel foam, then seal the polytetrafluoroethylene liner and place it in an autoclave. Finally, place the autoclave in an oven, heat it from room temperature to 180°C at a heating rate of 5°C / min, and keep it warm for 10 hours.

[0061] Step 4: After the heat preservation is completed, the autoclave is cooled naturally to room temperature, the product is taken out, and it is rinsed alternately with deionized water and anhydrous ethanol, and then allowed to stand at room temperature until the product is completely dried to obtain Zr-Ni 0.96 S / NF.

[0062] Example 6

[0063] Step 1: 3 mmol of zirconium nitrate pentahydrate and 9 mmol of thioacetamide were added to a beaker containing 20 mL of ethanol, and stirred at 50° C. for 45 min using a magnetic stirrer at 700 rpm to obtain a mixed solution A.

[0064] Step 2: First, a commercial nickel foam NF with a size of 1.5 cm × 4 cm × 0.2 cm was placed in acetone, a 3 mol / L HCl solution, and deionized water, and ultrasonically cleaned at 75 W for 7 minutes, then rinsed alternately with deionized water and anhydrous ethanol, and then dried in a 60°C forced air drying oven for 2 hours to obtain pure nickel foam;

[0065] Step 3: First, transfer the mixed solution A dropwise into a polytetrafluoroethylene liner, then add pure nickel foam, then seal the polytetrafluoroethylene liner and place it in an autoclave. Finally, place the autoclave in an oven, heat it from room temperature to 170°C at a heating rate of 5°C / min, and keep it warm for 11 hours.

[0066] Step 4: After the heat preservation is completed, the autoclave is cooled naturally to room temperature, the product is taken out, and it is rinsed alternately with deionized water and anhydrous ethanol, and then allowed to stand at room temperature until the product is completely dried to obtain Zr-Ni 0.96 S / NF.

[0067] Comparative Example 1

[0068] Step 1: 3 mmol of thioacetamide was added to a beaker containing 20 mL of ethanol, and the mixture was stirred at 60° C. for 40 min using a magnetic stirrer at 500 rpm to obtain a mixed solution A.

[0069] Step 2: First, a commercial nickel foam NF with a size of 1.5 cm × 4 cm × 0.2 cm was placed in acetone, a 3 mol / L HCl solution, and deionized water, and ultrasonically cleaned at 70 W for 10 minutes, then rinsed alternately with deionized water and anhydrous ethanol, and then dried in a 60°C forced air drying oven for 2 hours to obtain pure nickel foam;

[0070] Step 3: First, transfer the mixed solution A dropwise to a polytetrafluoroethylene liner, then add pure nickel foam, then seal the polytetrafluoroethylene liner and place it in an autoclave. Finally, place the autoclave in an oven, heat it from room temperature to 160°C at a heating rate of 5°C / min, and keep it warm for 12 hours.

[0071] Step 4: After the insulation is completed, the autoclave is allowed to cool naturally to room temperature, the product is taken out, and it is rinsed alternately with deionized water and anhydrous ethanol. The product is allowed to stand at room temperature until it is completely dried to obtain Ni3S2 / NF.

[0072] The electrode material Ni3S2 / NF prepared in Comparative Example 1 was subjected to a hydrogen evolution reaction test in a potassium hydroxide solution with a pH of 14: when the current density was 10 mA / cm 2 When the current density is 100mA / cm 2 When , the sample overpotential is 353mV.

[0073] The electrode material Ni3S2 / NF prepared in Comparative Example 1 was subjected to an oxygen evolution reaction test in a potassium hydroxide solution with a pH of 14: when the current density was 10 mA / cm 2 When the current density is 100mA / cm 2 When the sample overpotential is 415mV.

[0074] Comparative Example 2

[0075] A commercial nickel foam NF with a size of 1.5 cm × 4 cm × 0.2 cm was placed in acetone, 3 mol / L HCl solution and deionized water in sequence and ultrasonically cleaned at a power of 70 W for 10 min respectively. It was then rinsed alternately with deionized water and anhydrous ethanol and then dried in a forced air drying oven at 60°C for 2 h to obtain pure nickel foam NF.

[0076] The electrode material nickel foam NF prepared in Comparative Example 2 was subjected to hydrogen evolution reaction test in potassium hydroxide solution with pH=14: when the current density was 10 mA / cm 2 When the current density is 100mA / cm 2 When , the sample overpotential is 392mV.

[0077] The electrode material Ni3S2 / NF prepared in Comparative Example 2 was subjected to an oxygen evolution reaction test in a potassium hydroxide solution with a pH of 14: when the current density was 10 mA / cm 2 When the current density is 100mA / cm 2 When , the sample overpotential is 484mV.

[0078] Comparative Example 3

[0079] Step 1. A commercial nickel foam NF (1.5 cm × 4 cm × 0.2 cm) was sequentially placed in acetone, a 3 mol / L HCl solution, and deionized water, and ultrasonically cleaned at 70 W for 10 min, then rinsed alternately with deionized water and anhydrous ethanol, and then dried in a 60°C forced air drying oven for 2 h to obtain a pure nickel foam NF.

[0080] Step 2: Add 5 mg of 20 wt% noble metal electrocatalyst Pt / C to 50 μL of isopropanol and 4 μL of 5% mass concentration Nafion solution, stir evenly to prepare mixed solution B, and use a pipette to take 7 μL of mixed solution B and drop it on the working area of ​​0.25 cm. 2 The pure nickel foam NF surface was dried to obtain 20% Pt / C / NF electrode material.

[0081] The 20% Pt / C / NF electrode material prepared in Comparative Example 3 was subjected to a hydrogen evolution reaction test in a potassium hydroxide solution with a pH of 14: when the current density was 10 mA / cm 2 When the current density is 100mA / cm 2 When , the sample overpotential is 283mV.

[0082] Comparative Example 4

[0083] Step 1. A commercial nickel foam NF (1.5 cm × 4 cm × 0.2 cm) was sequentially placed in acetone, a 3 mol / L HCl solution, and deionized water, and ultrasonically cleaned at 70 W for 10 min, then rinsed alternately with deionized water and anhydrous ethanol, and then dried in a 60°C forced air drying oven for 2 h to obtain a pure nickel foam NF.

[0084] Step 2: Prepare IrO2 into a solution and then drop it onto the surface of pure nickel foam NF to obtain IrO2 / NF electrode material.

[0085] The electrode material IrO2 / NF prepared in Comparative Example 4 was subjected to an oxygen evolution reaction test in a potassium hydroxide solution with a pH of 14: when the current density was 10 mA / cm 2 When the current density is 100mA / cm 2 When the sample overpotential is 455mV.

[0086] from Figure 1 From the XRD pattern, it can be seen that for the Ni3S2 / NF without zirconium doping prepared in Comparative Example 1, all diffraction peaks except the peak assigned to the nickel foam substrate can be assigned to Ni3S2 (PDF#44-1418), and there is no second phase. 0.96 In S / NF, with the introduction of zirconium Zr, the Ni3S2 peak of nickel sulfide disappears and a new diffraction peak appears, which can be corresponding to Ni 0.96S (PDF#50-1791), compared with Ni3S2 / NF without Zr doping, the strongest peak Ni peak has a low angle shift from its original position, indicating that the introduction of Zr doping expands the interlayer spacing of the product, which is attributed to the incorporation of Zr ions. The addition of doping Z element causes the nickel sulfide phase to change.

[0087] Figure 2 Figures a and b are Zr-Ni 0.96 The morphology of the S / NF sample shows a nano-granular structure with a relatively uniform appearance; Figure 2 Figures c and d in the figure are the morphologies of Ni3S2 / NF prepared in comparative example 1, and they show a network-like structure with alternating distribution of lines and sheets, and the overall morphology is relatively mixed. 0.96 Under the influence of Zr, the synergistic effect between electrons in S / NF changes, making the morphology closer to the whole, and forming a nano-granular structure connected together. This structure makes Zr-Ni 0.96 S / NF has a larger surface area, which increases its contact area with the solution during the reaction, allowing it to expose more active sites, which is conducive to the occurrence of water electrolysis reaction; it also shows that the presence of Zr can have a certain impact on the morphology and structure of the sample.

[0088] Figure 3 a in the equation is Zr-Ni 0.96 Microscopic morphology of S / NF, Figure 3 b in the equation is Zr-Ni 0.96 From the TEM image of S / NF, it can be seen that the interplanar spacing of the nanoparticles is 0.296 nm, which corresponds to Ni 0.96 (100) crystal plane of S (PDF#50-1791).

[0089] from Figure 4 and Figure 5 The element distribution diagram (dg) shows that Ni, S, and Zr are evenly distributed, which also confirms that Zr appears in the sample in the form of doping.

[0090] from Figure 6 It can be seen that Zr-Ni 0.96 The S / NF ratios were 10, 100, and 500 mA cm -2 When the current density is 10 mA cm, the corresponding overpotentials are 95 mV, 202 mV and 338 mV respectively. -2 When the corresponding overpotentials are 205mV, 94mV and 268mV respectively. 0.96S / NF exhibits excellent electrocatalytic performance comparable to that of 20% Pt / C / NF, which indicates that zirconium-doped nickel sulfide does have advantages in HER performance. -2 When the current density is 500 mA cm -2 and 800mA cm -2 When Zr-Ni 0.96 The overpotentials of S / NF are 338mV and 402mV respectively. It can be seen that Zr-Ni 0.96 S / NF also has excellent catalytic performance at high current density, so it has certain prospects in practical industrial applications.

[0091] Depend on Figure 7 It can be seen that Zr-Ni 0.96 The S / NF current density was 10 mA cm -2 , 100mA cm -2 and 200mAcm -2 When the current density is 10 mA cm, the corresponding overpotentials are 143 mV, 351 mV and 403 mV respectively. In comparison, Ni3S2 / NF, IrO2 / NF and NF have the highest overpotentials at 10 mA cm -2 When the circuit density is 100 mA cm, the corresponding overpotentials are 130 mV, 104 mV and 314 mV respectively; Ni3S2 / NF, IrO2 / NF and NF -2 When the overpotential is 427mV, 455mV and 484mV respectively. 0.96 S / NF also has relatively excellent catalytic performance, which has certain advantages for OER with four-electron transfer in the process.

Claims

1. A method for preparing a zirconium-doped nickel sulfide self-supporting electrode material, characterized in that: The steps include: Step 1: 1 mmol of zirconium nitrate pentahydrate and 1.5-9 mmol of thioacetamide were added to a beaker containing 20 mL of anhydrous ethanol and stirred to obtain a mixed solution A. Step 2: First, the mixed solution A is transferred dropwise into a polytetrafluoroethylene liner. Then, a 1.5 cm × 4 cm × 0.2 cm area of ​​pure nickel foam is placed into the polytetrafluoroethylene liner containing the mixed solution A. The polytetrafluoroethylene liner is then sealed and placed in an autoclave. Finally, the autoclave is placed in an oven and heated from room temperature to 120-180°C at a heating rate of 5°C / min, and kept warm until the reaction is fully completed. Step 3: After the heat preservation is completed, the autoclave is cooled naturally to room temperature, the product is taken out, cleaned, and allowed to stand at room temperature until the product is completely dried to obtain Zr-Ni 0.96 S / NF.

2. The method for preparing a zirconium-doped nickel sulfide self-supporting electrode material according to claim 1, characterized in that: The purity of zirconium nitrate pentahydrate in step 1 is 99.9%.

3. The method for preparing the zirconium-doped nickel sulfide self-supporting electrode material according to claim 1, characterized in that: The stirring in step 1 is carried out using a magnetic stirrer at 500-700 r / min and at a temperature of 50-60° C. for 30-45 min.

4. The method for preparing a zirconium-doped nickel sulfide self-supporting electrode material according to claim 1, characterized in that: The pure nickel foam in step 2 is prepared by the following method: Step 2.1, placing commercial nickel foam in acetone, 3 mol / L HCl solution, and deionized water, respectively, for ultrasonic cleaning; Step 2.2: Rinse the nickel foam after ultrasonic cleaning alternately with deionized water and anhydrous ethanol, and obtain pure nickel foam after drying.

5. The method for preparing a zirconium-doped nickel sulfide self-supporting electrode material according to claim 4, characterized in that: The ultrasonic cleaning in step 2.1 is performed at a power of 70 to 80 W for 5 to 10 minutes.

6. The method for preparing a zirconium-doped nickel sulfide self-supporting electrode material according to claim 4, characterized in that: The drying in step 2.2 is carried out in a forced air drying oven at 60° C. for 2 h.

7. The method for preparing a zirconium-doped nickel sulfide self-supporting electrode material according to claim 1, characterized in that: The holding time of step 2 is 10 to 16 hours.

8. The method for preparing a zirconium-doped nickel sulfide self-supporting electrode material according to claim 1, characterized in that: The washing in step 3 is performed by alternately rinsing with deionized water and anhydrous ethanol until the washing is clean.

9. A zirconium-doped nickel sulfide self-supporting electrode material Zr-Ni prepared by the method according to any one of claims 1 to 8 0.96 S / NF.

10. The zirconium-doped nickel sulfide self-supporting electrode material Zr-Ni according to claim 9 0.96 Application of S / NF as electrocatalyst for hydrogen evolution reaction.

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