Ni-se-hree hydrogen evolution electrode and preparation method thereof

Abstract

The application relates to the field of electrocatalysis, and particularly relates to a high-catalytic-activity Ni-Se-HREE hydrogen evolution electrode and a preparation method thereof.The atomic content percentage of the surface of the nickel-based hydrogen evolution electrode coating layer is as follows: Se: 6-10%; Gd: 0.1-1.0%, and the rest is Ni; or the atomic content percentage of the surface of the nickel-based hydrogen evolution electrode coating layer is as follows: Se: 5-20%; Lu: 1-5%, and the rest is Ni.After optimization, the hydrogen evolution overpotential of the prepared Ni-Se-HREE hydrogen evolution electrode material is less than or equal to 43 mV; after long-time electrolysis of the electrode for 1200 h, the stability is good, the requirements of low hydrogen evolution overpotential, high catalytic activity and high stability are met, and the electrode can be widely applied to the water electrolysis hydrogen production industry.

Description

Technical Field

[0001] This invention relates to the field of electrocatalysis technology, specifically to a highly catalytically active Ni-Se-HREE hydrogen evolution electrode and its preparation method. Background Technology

[0002] As global environmental pollution worsens, the mineral energy sources upon which humanity depends for survival, such as oil, coal, and natural gas, are dwindling. Energy consumption and environmental pressures pose enormous challenges to humankind, making a sustainable and clean energy source urgently needed. Among various energy sources, hydrogen has garnered significant attention due to its zero-pollution, high energy density, and high calorific value, making it an ideal alternative to fossil fuels.

[0003] However, since hydrogen rarely exists in its elemental form in nature, it must be produced industrially. The main sources of hydrogen can be categorized as byproducts from industrial production; hydrogen production from fossil fuels, such as coal; biomass; solar energy; and water electrolysis. The differences between these methods lie in the cleanliness of the process, the renewability of the raw materials, and the cost of hydrogen production. Statistics show that currently, over 95% of the world's hydrogen production comes from fossil fuel reforming, a process that inevitably emits carbon dioxide. The remaining hydrogen primarily comes from water electrolysis, a process that does not emit carbon dioxide. Furthermore, among all hydrogen production methods, the electrochemical water separation hydrogen reaction (HER) offers advantages such as stable operation, clean production, and high purity. Considering the continuously improving efficiency of renewable energy sources (such as hydrogen, wind, and solar power) and the high cost of precious metal catalysts, water electrolysis is expected to become the mainstream hydrogen production method.

[0004] However, electrode materials are a key factor affecting the efficiency of hydrogen production through water electrolysis. Metals and their oxides are recognized as the most effective catalysts for reducing overpotential in hydrogen evolution and oxygen evolution reactions. Among them, the noble metal platinum has excellent electrocatalytic activity and a moderate bond energy with hydrogen atoms, making it the best electrode material for hydrogen evolution. However, platinum is scarce, resource-limited, and very expensive, severely restricting its large-scale application in hydrogen evolution through water electrolysis. Therefore, developing an electrocatalyst with high cost-effectiveness and high catalytic activity using non-noble metals for hydrogen production through water electrolysis is of great significance. Currently, researchers have attempted to develop catalysts with high catalytic activity using Ni and Se. For example, patent CN202211499307.1 discloses a Ni-Se-C hydrogen evolution electrode and its preparation method; as shown in Table 1, the obtained product exhibits high activity at 10 mA·cm⁻¹. -2The overpotential at the current density is greater than 62 mV. In the same year, the inventors' research group published "One-step galvanostatic electrodeposition of Ni-Se-Dy film on Ni foam for hydrogenevolution reaction in alkaline solution," in which the obtained product was measured at 10 mA·cm⁻¹. -2 The overpotential at the given current density is approximately 72 mV. To further enhance electrode activity and reduce the hydrogen evolution overpotential, this invention was developed based on the published paper, resulting in this invention. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a Ni-Se-HREE composite hydrogen evolution electrode that enables efficient hydrogen production through water electrolysis. This method is mainly due to the fact that the prepared Ni-Se-HREE composite hydrogen evolution electrode has a low hydrogen evolution overpotential and good stability.

[0006] The present invention provides a Ni-Se-HREE hydrogen evolution electrode, comprising a nickel foam substrate and a Ni-Se-HREE coating electroplated on the surface of the substrate, wherein the HREE is Gd or Lu;

[0007] When the HREE is Gd, the coating comprises the following components by atomic percentage: Ni: 89-93.9%; Se: 6.0-10%; Gd: 0.1-1.0%;

[0008] When the HREE is Lu, the coating comprises the following components by atomic percentage: Ni: 80-95%; Se: 5-20%; Lu: 1-5%.

[0009] Preferably, the present invention provides a Ni-Se-HREE hydrogen evolution electrode, wherein when the HREE is Gd, the coating comprises the following components in atomic percentage: Ni: 89.71-92.1%; Se: 6.9-9.57%; Gd: 0.71-1.0%;

[0010] When the HREE is Lu, the resulting electrode coating, in atomic percentage, is: Ni: 84.5–85%; Se: 13.5–14%; Lu: 1.5–2%.

[0011] As a further preferred embodiment, the present invention provides a Ni-Se-HREE hydrogen evolution electrode; when HREE is Gd, the coating comprises the following components in atomic percentage: Ni: 89.71%; Se: 9.57%; Gd: 0.71%, with the balance being impurities.

[0012] As a further preferred embodiment, the present invention provides a Ni-Se-HREE hydrogen evolution electrode, wherein when HREE is Lu, the coating of the resulting electrode, in atomic percentage terms, is: Ni: 84.71%; Se: 13.73%; Lu: 1.56%; with the balance being impurities.

[0013] This invention discloses a method for preparing a Ni-Se-HREE hydrogen evolution electrode. When the HREE is Gd, the preparation method is as follows:

[0014] Clean and dry nickel foam is used as the working electrode. The working electrode is immersed in the electroplating solution and electroplated at 15-30°C for at least 20 minutes. After electroplating, it is cleaned and dried to obtain the product. During electroplating, the current density is controlled at 30-50 mA and the pH of the electroplating solution is controlled at 4-5. The electroplating solution is composed of the following components:

[0015] Nickel sulfate 100-160 g / L, selenium oxide 1-10 g / L, sodium chloride 30 g / L, boric acid 13.33 g / L, sulfosalicylic acid 14 g / L, triammonium citrate 20 g / L, gadolinium chloride 1-5 g / L.

[0016] In industrial applications, clean and dry nickel foam can be obtained by rinsing with hydrochloric acid, rinsing with anhydrous ethanol, or ultrasonic treatment followed by drying.

[0017] Preferably, when the HREE is Gd, the electroplating temperature is controlled at 18-22℃.

[0018] Preferably, when HREE is Gd, the current density is controlled to be 38-42 mA during electroplating.

[0019] Preferably, when the HREE is Gd, the electroplating solution consists of the following components:

[0020] Nickel sulfate 140 g / L, selenium oxide 5 g / L, sodium chloride 30 g / L, boric acid 13.33 g / L, sulfosalicylic acid 14 g / L, triammonium citrate 20 g / L, gadolinium chloride 3 g / L.

[0021] Through experiments, this invention found that when HREE is Gd, the hydrogen evolution electrode prepared under the following conditions has the best effect: concentration of sodium chloride 30 g / L, boric acid 13.33 g / L, sulfosalicylic acid 14 g / L, and triammonium citrate 20 g / L. Both low and high concentrations affect the electrode performance.

[0022] When the HREE is Gd, the electroplating time is 20 to 60 minutes, preferably 40 minutes.

[0023] This invention discloses a method for preparing a Ni-Se-HREE hydrogen evolution electrode. When the HREE is Lu, the preparation method is as follows:

[0024] Clean and dry nickel foam is used as the working electrode. The working electrode is immersed in the electroplating solution and electroplated at 15-30°C for at least 10 minutes. After electroplating, it is cleaned and dried to obtain the product. During electroplating, the current density is controlled at 40-100 mA and the pH of the electroplating solution is controlled at 3-5. The electroplating solution is composed of the following components:

[0025] Nickel sulfate 100-180 g / L, selenium oxide 2-10 g / L, sodium chloride 30 g / L, boric acid 13-14 g / L, sulfosalicylic acid 10-12 g / L, triammonium citrate 20-30 g / L, lutetium chloride 2-10 g / L.

[0026] In industrial applications, clean and dry nickel foam can be obtained by rinsing with hydrochloric acid, rinsing with anhydrous ethanol, or ultrasonic treatment followed by drying.

[0027] Preferably, when the HREE is Lu, the electroplating temperature is controlled at 24-26℃.

[0028] Preferably, when the HREE is Lu, the current density is controlled at 49–51 mA during electroplating.

[0029] Preferably, when the HREE is Lu, the electroplating solution is composed of the following components:

[0030] Nickel sulfate 150g / L, selenium oxide 5g / L, sodium chloride 30g / L, boric acid 14g / L, sulfosalicylic acid 10g / L, triammonium citrate 25g / L, lutetium chloride 5g / L.

[0031] Preferably, when the HREE is Lu, the electroplating time is controlled to be 60 min.

[0032] This invention discloses a method for preparing a highly catalytically active Ni-Se-Gd hydrogen evolution electrode. The counter electrode is preferably a graphite plate, with the surface A of the graphite plate facing the working electrode having an area larger than the surface B of the working electrode facing the counter electrode. Preferably, the area of ​​A is 4-6 times the area of ​​B. For example, if the length × width × thickness of the working electrode is 1cm × 1cm × A1cm, then the dimensions of the matching counter electrode graphite plate are 2cm × 2cm × A2cm.

[0033] During the research and development process, it was also discovered that different heavy rare earth elements have a very important influence on the content and rate of Se electrodeposition.

[0034] The advantages of this invention are:

[0035] (1) The method of the present invention is simple, can be carried out at lower temperatures and lower current densities, is easy to operate and execute, and reduces the cost of precious metals;

[0036] (2) The prepared Ni-Se-heavy rare earth composite electrode has a low hydrogen evolution overpotential, high hydrogen evolution catalytic activity and good stability, and can be widely used in the field of alkaline water electrolysis for hydrogen production.

[0037] (3) This invention achieves for the first time at 10 mA·cm -2 The overpotential at the current density was less than 60mV, the optimized product was less than or equal to 43mV, and the further optimized product was less than 35mV, which greatly exceeded the initial expectations. This invention also discovered that different heavy rare earth elements have a very important influence on the electrodeposition content and rate of Se. Attached Figure Description

[0038] Figure 1 Linear current-amperometry (LSV) plots of the Ni-Se-Gd electrodes obtained in Examples 1-3;

[0039] Figure 2 The surface morphology of the Ni-Se-Gd electrode electroplating layer obtained in Example 1;

[0040] Figure 3 The EDS energy spectrum of the Ni-Se-Gd electrode electroplated layer obtained in Example 1;

[0041] Figure 4 This is an overpotential diagram of the Ni-Se-Gd electrode electroplating layer obtained in Example 1 after 5000 CV cycles at the product current density;

[0042] Figure 5 LSV diagrams of Ni-Se, Ni-Gd, and Se-Gd electrodes prepared under the same conditions as in Example 1.

[0043] Figure 6 LSV curves of the products obtained in Example 4 and Comparative Series 2;

[0044] Figure 7 The surface morphology diagram of the product obtained in Example 4;

[0045] Figure 8 The EDS spectrum of the product obtained in Example 4;

[0046] Figure 9 The LSV curves of the products obtained in Examples 5 and 6;

[0047] Figure 10 Long-time electrolysis diagram of the Ni-Se-Gd electrode obtained in Example 1;

[0048] Figure 11 This is a long-time electrolysis diagram of the Ni-Se-Lu electrode obtained in Example 4.

[0049] from Figure 1As can be seen from the results, when the products obtained in Examples 1-3 were tested at 25°C in a 1 mol / L KOH solution, the resulting electrodes operated at 10–50 mA·cm⁻¹. -2 The overpotential distribution under current density, wherein the product obtained in Example 1 at 10 mA·cm⁻¹. -2 The overpotential at the current density is 33 mV, and the product obtained in Example 2 has an overpotential of 10 mA·cm⁻¹. -2 The overpotential at the current density is 59 mV, and the product obtained in Example 3 has an overpotential of 10 mA·cm⁻¹. -2 The overpotential at the current density is 71 mV.

[0050] from Figure 2 The surface morphology of the Ni-Se-Gd electrode electroplating layer obtained in Example 1 can be seen in the figure.

[0051] from Figure 3 The results show the types of elements in the Ni-Se-Gd electrode plating layer obtained in Example 1, and the content of each element can be calculated.

[0052] from Figure 4 The image shows the overpotential distribution of the Ni-Se-Gd electrode electroplating layer obtained in Example 1 after 5000 CV cycles at the product current density. The overpotential distribution of the product at 10 mA·cm⁻¹ is shown in the image. -2 At a current density of [value missing], after 5000 cycles, the product's overpotential rise is less than 2%. The product operates at 30 mA·cm [value missing]. -2 At a current density of [value missing], after 5000 cycles, the product's overpotential rise is less than 1%. The product operates at 50 mA·cm [value missing]. -2 At the specified current density, after 5000 cycles, the product overpotential rise was less than 0.5%. This is significantly different from the hydrogen evolution performance of existing electrodes.

[0053] from Figure 5 As can be seen from the results, the Ni-Se-Gd electrode obtained in Example 1 is far superior to other electrodes. Combined with Examples 1, 2, and 3, this proves that the component content design of Example 1 of the present invention has a significant effect.

[0054] from Figure 6 It can be seen that the electrodes obtained in Example 4 and Comparative Example Series 2 were tested at 25°C in a 1 mol / L KOH solution, and the overpotential distribution of the electrodes under different current densities was observed.

[0055] from Figure 7 The surface morphology of the electrode obtained in Example 4 can be seen.

[0056] from Figure 8 The EDS energy spectrum distribution of the electrode obtained in Example 4 can be seen.

[0057] from Figure 9 It can be seen that the electrodes obtained in Examples 5 and 6 were tested at 25°C in a 1 mol / L KOH solution, and the overpotential distribution of the electrodes under different current densities was observed.

[0058] from Figure 10 It can be seen that the potential distribution of the electrodes changes with different electrolysis durations, and the changes are basically consistent with the changes in the corresponding LSV curves. During long-term electrolysis, the overpotential decreases, indicating that the hydrogen evolution performance improves.

[0059] from Figure 11 It can be seen that the potential distribution of the electrodes changes with different electrolysis durations, and the changes are basically consistent with the changes in the corresponding LSV curves. During long-term electrolysis, the overpotential decreases, indicating that the hydrogen evolution performance improves. Detailed Implementation

[0060] The present invention will be further described below with reference to examples and accompanying drawings. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention, nor should they be used to limit the scope of protection of the present invention.

[0061] Example 1:

[0062] (1) Pretreatment of the nickel foam substrate

[0063] Cut the purchased sheet of nickel foam into 1cm x 1cm pieces. First, wash the nickel foam three times with deionized water, then rinse it three times with anhydrous ethanol, and immerse it in a beaker containing anhydrous ethanol for sonication for 6 minutes. After sonication, remove the beaker and wash it three times with deionized water, then rinse it three times with 1mol / L hydrochloric acid, and immerse it in a beaker containing 1mol / L hydrochloric acid for sonication for 6 minutes. After sonication, wash it again with deionized water. Finally, pour in a certain amount of anhydrous ethanol and store it for later use.

[0064] (2) Preparation of electroplating solution and electrodeposition of Ni-Se-Gd electrode

[0065] A Ni-Se-Gd electrode was prepared by electrodeposition on a CHI660E electrochemical workstation using a three-electrode system. The reference electrode was a saturated calomel electrode (SCE), the working electrode was the prepared nickel foam NF (1cm×1cm×0.03cm) from step (1), and the counter electrode was a graphite plate (2cm×2cm×0.5cm). The electroplating solution was prepared with the following components: nickel sulfate 140g / L, selenium oxide 5g / L, sodium chloride 30g / L, boric acid 13.33g / L, sulfosalicylic acid 14g / L, triammonium citrate 20g / L, and gadolinium chloride 3g / L. The electroplating time was 40min, the electroplating temperature was 20℃, and the current density was 40mA. After the electroplating process, the electroplated sheet was rinsed with deionized water, then removed and placed on paper to air dry for further testing.

[0066] The resulting electrode coating, by atomic percentage, is: Ni: 89.71%; Se: 9.57%; Gd: 0.71%, with the balance being impurities.

[0067] (3) Hydrogen evolution performance testing and structural characterization of Ni-Se-Gd electrode

[0068] The Ni-Se-Gd electrode prepared by electrodeposition was tested using a three-electrode system on a CHI660E electrochemical workstation. The reference electrode was a saturated calomel electrode (SCE), the working electrode was Ni-Se-Gd, and the counter electrode was a graphite plate. The hydrogen evolution performance of the Ni-Se-Gd electrode was tested using 1 mol / L KOH solution as the electrolyte and under water bath heating at 25°C. The linear voltammogram (LSV curve) is shown below. Figure 1 As shown, the surface morphology is as follows Figure 2 As shown, the EDS energy spectrum is as follows Figure 3 As shown, the overpotential at the product current density after 5000 CV cycles is as follows: Figure 4 As shown,

[0069] Ni-Se, Ni-Gd, and Se-Gd electrodes were prepared under the same conditions, and LSVs were used as follows. Figure 5 As shown.

[0070] The obtained product was tested at 25°C in a 1 mol / L KOH solution, and the obtained electrode was tested at 10 mA·cm⁻¹. -2 The overpotential at the current density is 33mV.

[0071] At 10mA·cm -2 At a current density of 5000 cycles, the overpotential rise of the product is less than 2%.

[0072] At 30mA·cm -2 At a current density of 1, after 5000 cycles, the overpotential rise of the product is less than 1%.

[0073] At 50mA·cm -2 At the specified current density, after 5000 cycles, the product overpotential rise was less than 0.5%. This is significantly different from the hydrogen evolution performance of existing electrodes.

[0074] Example 2:

[0075] (1) Pretreatment of the nickel foam substrate

[0076] Cut the purchased sheet of nickel foam into 1cm x 1cm pieces. First, wash the nickel foam three times with deionized water, then rinse it three times with anhydrous ethanol, and then immerse it in a beaker containing anhydrous ethanol and sonicate for 6 minutes. After sonication, remove the beaker and wash it three times with deionized water, then rinse it three times with 1.5mol / L hydrochloric acid, and then immerse it in a beaker containing 1.5mol / L hydrochloric acid and sonicate for 6 minutes. After sonication, wash it again with deionized water. Finally, pour in a certain amount of anhydrous ethanol and store it for later use.

[0077] (2) Preparation of electroplating solution and electrodeposition of Ni-Se-Gd electrode

[0078] A Ni-Se-Gd electrode was prepared by electrodeposition on a CHI660E electrochemical workstation using a three-electrode system. The reference electrode was a saturated calomel electrode (SCE), the working electrode was the treated nickel foam NF (1cm×1cm×0.03cm) prepared in step (1), and the counter electrode was a graphite plate (2cm×2cm×0.5cm). The electroplating solution was prepared with the following components: nickel sulfate 100g / L, selenium oxide 10g / L, sodium chloride 30g / L, boric acid 13.33g / L, sulfosalicylic acid 14g / L, triammonium citrate 20g / L, and gadolinium chloride 3g / L. The electroplating time was 50min, the electroplating temperature was 22℃, and the current density was 40mA. After the electroplating process, the electroplated sheet was rinsed with deionized water, then removed and placed on paper to air dry for further testing. The resulting electrode coating, in atomic percentage terms, is as follows: Ni: 92.1%; Se: 6.9%; Gd: 1.0%.

[0079] (3) Hydrogen evolution performance testing and structural characterization of Ni-Se-Gd electrode

[0080] The Ni-Se-Gd electrode prepared by electrodeposition was tested using a three-electrode system on a CHI660E electrochemical workstation. The reference electrode was a saturated calomel electrode (SCE), the working electrode was Ni-Se-Gd, and the counter electrode was a graphite plate. The hydrogen evolution performance of the Ni-Se-Gd electrode was tested using 1 mol / L KOH solution as the electrolyte and under water bath heating at 25°C. The linear voltammogram (LSV curve) is shown below. Figure 1 As shown.

[0081] The obtained product was tested at 25°C in a 1 mol / L KOH solution, and the obtained electrode was tested at 10 mA·cm⁻¹. -2 The overpotential at the current density is 59mV.

[0082] Example 3:

[0083] (1) Pretreatment of the nickel foam substrate

[0084] Cut the purchased sheet of nickel foam into 1cm x 1cm pieces. First, wash the nickel foam three times with deionized water, then rinse it three times with anhydrous ethanol, and immerse it in a beaker containing anhydrous ethanol for sonication for 6 minutes. After sonication, remove the beaker and wash it three times with deionized water, then rinse it three times with 2mol / L hydrochloric acid, and immerse it in a beaker containing 2mol / L hydrochloric acid for sonication for 10 minutes. After sonication, wash it again with deionized water. Finally, pour in a certain amount of anhydrous ethanol and store it for later use.

[0085] (2) Preparation of electroplating solution and electrodeposition of Ni-Se-Gd electrode

[0086] A Ni-Se-Gd electrode was prepared by electrodeposition on a CHI660E electrochemical workstation using a three-electrode system. The reference electrode was a saturated calomel electrode (SCE), the working electrode was the treated nickel foam NF (1cm×1cm×0.03cm) prepared in step (1), and the counter electrode was a graphite plate (2cm×2cm×0.5cm). The electroplating solution was prepared with the following components: nickel sulfate 160g / L, selenium oxide 1g / L, sodium chloride 30g / L, boric acid 13.33g / L, sulfosalicylic acid 14g / L, triammonium citrate 20g / L, and gadolinium chloride 1g / L. The electroplating time was 40min, the electroplating temperature was 20℃, and the current density was 40mA. After the electroplating process, the electroplated sheet was rinsed with deionized water, then removed and placed on paper to air dry for further testing.

[0087] The resulting electrode coating, by atomic percentage, is as follows: Ni: 93.5%; Se: 6.1%; Gd: 0.4%.

[0088] (3) Hydrogen evolution performance testing and structural characterization of Ni-Se-Gd electrode

[0089] The Ni-Se-Gd electrode prepared by electrodeposition was tested using a three-electrode system on a CHI660E electrochemical workstation. The reference electrode was a saturated calomel electrode (SCE), the working electrode was Ni-Se-Gd, and the counter electrode was a graphite plate. The hydrogen evolution performance of the Ni-Se-Gd electrode was tested using 1 mol / L KOH solution as the electrolyte and under water bath heating at 25°C. The linear voltammogram (LSV curve) is shown below. Figure 1 As shown.

[0090] The obtained product was tested at 25°C in a 1 mol / L KOH solution, and the obtained electrode was tested at 10 mA·cm⁻¹. -2 The overpotential at the current density is 71mV.

[0091] Comparative Example 1

[0092] Other conditions were the same as in Example 1, except that the electroplating solution was prepared with the following components: nickel sulfate 140 g / L, selenium oxide 5 g / L, sodium chloride 3 g / L, boric acid 1.33 g / L, sulfosalicylic acid 1.33 g / L, triammonium citrate 2 g / L, and gadolinium chloride 3 g / L. The resulting product was tested at 25°C in a 1 mol / L KOH solution, and the electrode was tested at 10 mA·cm⁻¹. -2 The overpotential at the current density is 65mV.

[0093] Example 4 (Design and fabrication of a nickel-selenium-lutetium electrode)

[0094] (1) Pretreatment of the nickel foam substrate

[0095] Cut the purchased sheet of nickel foam into 1cm x 1cm pieces. First, wash the nickel foam three times with deionized water, then rinse it three times with anhydrous ethanol, and immerse it in a beaker containing anhydrous ethanol for sonication for 6 minutes. After sonication, remove the beaker and wash it three times with deionized water, then rinse it three times with 1mol / L hydrochloric acid, and immerse it in a beaker containing 1mol / L hydrochloric acid for sonication for 6 minutes. After sonication, wash it again with deionized water. Finally, pour in a certain amount of anhydrous ethanol and store it for later use.

[0096] (2) Preparation of electroplating solution and electrodeposition of Ni-Se-Lu electrode

[0097] A Ni-Se-Lu electrode was prepared by electrodeposition on a CHI660E electrochemical workstation using a three-electrode system. The reference electrode was a saturated calomel electrode (SCE), the working electrode was the prepared nickel foam NF (1cm×1cm×0.03cm) from step (1), and the counter electrode was a graphite plate (2cm×2cm×0.3cm). The electroplating solution was prepared with the following components: nickel sulfate 150g / L, selenium dioxide 5g / L, lutetium chloride 5g / L, sodium chloride 30g / L, boric acid 14g / L, sulfosalicylic acid 10g / L, and triammonium citrate 25g / L. The electroplating time was 60min, the electroplating temperature was 25℃, and the current density was 50mA. After the electroplating process, the electroplated sheet was rinsed with deionized water, then removed and placed on paper to air dry for further testing. The resulting electrode coating, in atomic percentage, is as follows: Ni: 84.71%; Se: 13.73%; Lu: 1.56%.

[0098] (3) Hydrogen evolution performance testing and structural characterization of Ni-Se-Lu electrode

[0099] The Ni-Se-Lu electrode prepared by electrodeposition experiments was tested using a three-electrode system on a CHI660E electrochemical workstation. The reference electrode was a saturated calomel electrode (SCE), the working electrode was Ni-Se-Lu, and the counter electrode was a graphite plate. The hydrogen evolution performance of the Ni-Se-Lu electrode was tested under the conditions of 1 mol / L KOH solution as the electrolyte and water bath heating at 25℃. Simultaneously, Ni-Se, Ni-Lu, and Se-Lu electrodes were prepared under the same conditions, and their linear voltammograms (LSV curves) are shown below. Figure 6 As shown, the surface morphology is as follows Figure 7 As shown, the EDS energy spectrum is as follows Figure 8 As shown.

[0100] from Figure 6 It can be seen from the results that: the obtained electrode was tested at 25℃ in a 1mol / L KOH solution, and the obtained electrode was tested at 10mA·cm. -2 The overpotential at the current density is 43mV.

[0101] The resulting products,

[0102] At 10mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 1.5%.

[0103] At 30mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 2.1%.

[0104] At 50mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 3.1%.

[0105] Comparison Series 2

[0106] All other conditions are the same as in Example 4, except that:

[0107] When preparing Ni-Se, lutetium chloride is not added to the electroplating solution;

[0108] Selenium dioxide is not added to the electroplating solution when preparing Ni-Lu;

[0109] Nickel sulfate is not added to the electroplating solution when preparing Se-Lu;

[0110] The performance of the obtained product is shown in the figure. Figure 6 .

[0111] Example 5:

[0112] (1) Pretreatment of the nickel foam substrate

[0113] Cut the purchased sheet of nickel foam into 1cm x 1cm pieces. First, wash the nickel foam three times with deionized water, then rinse it three times with anhydrous ethanol, and immerse it in a beaker containing anhydrous ethanol for sonication for 12 minutes. After sonication, remove the beaker and wash it three times with deionized water, then rinse it three times with 2mol / L hydrochloric acid, and immerse it in a beaker containing 1mol / L hydrochloric acid for sonication for 10 minutes. After sonication, wash it again with deionized water. Finally, pour in a certain amount of anhydrous ethanol and store it for later use.

[0114] (2) Preparation of electroplating solution and electrodeposition of Ni-Se-Lu electrode

[0115] A Ni-Se-Lu electrode was prepared by electrodeposition on a CHI660E electrochemical workstation using a three-electrode system. The reference electrode was a saturated calomel electrode (SCE), the working electrode was the prepared nickel foam NF (1cm×1cm×0.03cm) from step (1), and the counter electrode was a graphite plate (2cm×2cm×0.3cm). The electroplating solution was prepared with the following components: nickel sulfate 100g / L, selenium dioxide 10g / L, lutetium chloride 10g / L, sodium chloride 30g / L, boric acid 14g / L, sulfosalicylic acid 10g / L, and triammonium citrate 25g / L. The electroplating time was 10min, the electroplating temperature was 10℃, and the current density was 40mA. After the electroplating process, the electroplated sheet was rinsed with deionized water, then removed and placed on paper to air dry for further testing. The resulting electrode coating, by atomic percentage, is as follows: Ni: 82.11%; Se: 15.32%; Lu: 2.57%.

[0116] (3) Hydrogen evolution performance testing and structural characterization of Ni-Se-Lu electrode

[0117] The Ni-Se-Lu electrode prepared by electrodeposition was tested using a three-electrode system on a CHI660E electrochemical workstation. The reference electrode was a saturated calomel electrode (SCE), the working electrode was Ni-Se-Lu, and the counter electrode was a graphite plate. The hydrogen evolution performance of the Ni-Se-Lu electrode was tested under the conditions of 1 mol / L KOH solution as the electrolyte and water bath heating at 25℃. Its linear voltammogram (LSV curve) is shown below. Figure 9 As shown.

[0118] from Figure 9 It can be seen from the results that: the obtained electrode was tested at 25℃ in a 1mol / L KOH solution, and the obtained electrode was tested at 10mA·cm. -2 The overpotential at the current density is 60mV.

[0119] The resulting products,

[0120] At 10mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 2.1%.

[0121] At 30mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 3.5%.

[0122] At 50mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 4.2%.

[0123] Example 6:

[0124] (1) Pretreatment of the nickel foam substrate

[0125] Cut the purchased sheet of nickel foam into 1cm x 1cm pieces. First, wash the nickel foam three times with deionized water, then rinse it three times with anhydrous ethanol, and immerse it in a beaker containing anhydrous ethanol for sonication for 12 minutes. After sonication, remove the beaker and wash it three times with deionized water, then rinse it three times with 2mol / L hydrochloric acid, and immerse it in a beaker containing 1mol / L hydrochloric acid for sonication for 10 minutes. After sonication, wash it again with deionized water. Finally, pour in a certain amount of anhydrous ethanol and store it for later use.

[0126] (2) Preparation of electroplating solution and electrodeposition of Ni-Se-Lu electrode

[0127] A Ni-Se-Lu electrode was prepared by electrodeposition on a CHI660E electrochemical workstation using a three-electrode system. The reference electrode was a saturated calomel electrode (SCE), the working electrode was the prepared nickel foam NF (1cm×1cm×0.03cm) from step (1), and the counter electrode was a graphite plate (2cm×2cm×0.3cm). The electroplating solution was prepared with the following components: nickel sulfate 180g / L, selenium dioxide 2g / L, lutetium chloride 1g / L, sodium chloride 30g / L, boric acid 14g / L, sulfosalicylic acid 10g / L, and triammonium citrate 25g / L. The electroplating time was 80min, the electroplating temperature was 30℃, and the current density was 100mA. After the electroplating process, the electroplated sheet was rinsed with deionized water, then removed and placed on paper to air dry for further testing. The resulting electrode coating, by atomic percentage, is as follows: Ni: 93.21%; Se: 5.29%; Lu: 1.50%.

[0128] (3) Hydrogen evolution performance testing and structural characterization of Ni-Se-Lu electrode

[0129] The Ni-Se-Lu electrode prepared by electrodeposition was tested using a three-electrode system on a CHI660E electrochemical workstation. The reference electrode was a saturated calomel electrode (SCE), the working electrode was Ni-Se-Lu, and the counter electrode was a graphite plate. The hydrogen evolution performance of the Ni-Se-Lu electrode was tested under the conditions of 1 mol / L KOH solution as the electrolyte and water bath heating at 25℃. Its linear voltammogram (LSV curve) is shown below. Figure 9 As shown.

[0130] from Figure 9 It can be seen from the results that: the obtained electrode was tested at 25℃ in a 1mol / L KOH solution, and the obtained electrode was tested at 10mA·cm. -2 The overpotential at the current density is 51mV.

[0131] The resulting products,

[0132] At 10mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 3.5%.

[0133] At 30mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 4.1%.

[0134] At 50mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 5.5%.

[0135] Example 7

[0136] All other conditions are the same as in Example 4, except that:

[0137] The electroplating parameters are: nickel sulfate 140 g / L, selenium oxide 5 g / L, sodium chloride 30 g / L, boric acid 13.33 g / L, sulfosalicylic acid 14 g / L, triammonium citrate 20 g / L, and lutetium chloride 3 g / L. The electroplating time is 40 min, the electroplating temperature is 20℃, and the current density is 40 mA.

[0138] The obtained electrode was tested at 25℃ in a 1 mol / L KOH solution, and the obtained electrode was tested at 10 mA·cm. -2 The overpotential at the current density is 58mV.

[0139] The resulting products,

[0140] At 10mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 2.1%.

[0141] At 30mA·cm -2At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 4.2%.

[0142] At 50mA·cm -2 At the specified current density, after 5000 cycles, the overpotential rise of the product is less than 5.2%.

[0143] Comparative Example 3

[0144] All other conditions are the same as in Example 4, except that:

[0145] The electroplating parameters are: nickel sulfate 140 g / L, selenium dioxide 5 g / L, sodium chloride 3 g / L, boric acid 1.33 g / L, sulfosalicylic acid 1.33 g / L, trisodium citrate 2 g / L, and lutetium chloride 3 g / L. The electroplating time is 40 min, the electroplating temperature is 30℃, and the current density is 30 mA / cm². 2 .

[0146] The obtained electrode was tested at 25℃ in a 1 mol / L KOH solution, and the obtained electrode was tested at 10 mA·cm. -2 The overpotential at the current density is 65mV.

Claims

1. A Ni-Se-HREE hydrogen evolution electrode, characterized in that: The Ni-Se-HREE hydrogen evolution electrode includes a nickel foam substrate and a Ni-Se-HREE coating electroplated on the surface of the substrate, wherein the HREE is Gd or Lu; When HREE is Gd, the coating comprises the following components by atomic percentage: Ni: 89~93.9%; Se: 6.0~10%; Gd: 0.1~1.0%; When HREE is Gd, its preparation method is as follows: Clean and dry nickel foam is used as the working electrode. The working electrode is immersed in the electroplating solution and electroplated at 15~30℃ for at least 20 minutes. After electroplating, it is cleaned and dried to obtain the product. During electroplating, the current density is controlled at 38~42mA and the pH of the electroplating solution is controlled at 4~5. The electroplating solution is composed of the following components: Nickel sulfate 140 g / L, selenium oxide 5 g / L, sodium chloride 30 g / L, boric acid 13.33 g / L, sulfosalicylic acid 14 g / L, triammonium citrate 20 g / L, gadolinium chloride 3 g / L; The electroplating time is 20-60 minutes; the temperature during electroplating is controlled at 18-22℃. When the HREE is Lu, the coating comprises the following components by atomic percentage: Ni: 80~95%; Se: 5~20%; Lu: 1~5%; and the preparation method is as follows: Clean and dry nickel foam is used as the working electrode. The working electrode is immersed in the electroplating solution and electroplated at 15~30℃ for at least 10 minutes. After electroplating, it is cleaned and dried to obtain the product. During electroplating, the current density is controlled at 40~100mA and the pH of the electroplating solution is controlled at 3~5. The electroplating solution is composed of the following components: Nickel sulfate 100~180g / L, selenium oxide 2~10g / L, sodium chloride 30g / L, boric acid 13~14g / L, sulfosalicylic acid 10~12g / L, triammonium citrate 20~30g / L, lutetium chloride 2~10g / L.

2. The Ni-Se-HREE hydrogen evolution electrode according to claim 1, characterized in that: When the HREE is Gd, the coating comprises the following components by atomic percentage: Ni: 89.71~92.1%; Se: 6.9~9.57%; Gd: 0.71~1.0%; When the HREE is Lu, the resulting electrode coating, in atomic percentage, is: Ni: 84.5~85%; Se: 13.5~14%; Lu: 1.5~2%.

3. The Ni-Se-HREE hydrogen evolution electrode according to claim 2, characterized in that: When the HREE is Gd, the coating comprises the following components by atomic percentage: Ni: 89.71%; Se: 9.57%; Gd: 0.71%, with the balance being impurities; When the HREE is Lu, the resulting electrode coating, in atomic percentage, is: Ni: 84.71%; Se: 13.73%; Lu: 1.56%; with the balance being impurities.

4. A Ni-Se-HREE hydrogen evolution electrode as described in claim 1, characterized in that: When the HREE is Lu, the temperature is controlled at 24-26℃ during electroplating; when the HREE is Lu, the current density is controlled at 49~51mA during electroplating.

5. A Ni-Se-HREE hydrogen evolution electrode as described in claim 1, characterized in that: When HREE is Lu, the electroplating solution consists of the following components: Nickel sulfate 150 g / L, selenium oxide 5 g / L, sodium chloride 30 g / L, boric acid 14 g / L, sulfosalicylic acid 10 g / L, triammonium citrate 25 g / L, lutetium chloride 5 g / L; The electroplating time is controlled to be 60 minutes.

6. The Ni-Se-HREE hydrogen evolution electrode according to claim 1, characterized in that: The counter electrode is a graphite plate, and the area of ​​the graphite plate facing the working electrode (A) is larger than the area of ​​the working electrode facing the counter electrode (B).

7. The Ni-Se-HREE hydrogen evolution electrode according to claim 6, characterized in that: The area of ​​A is 4-6 times the area of ​​B.

8. The Ni-Se-HREE hydrogen evolution electrode according to claim 1, characterized in that: The resulting electrode is at 10 mA·cm -2 The overpotential at the current density is less than 60mV.

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