阅读说明：本技术 一种泡沫镍表面电沉积Ni-Fe-Sn-P合金的方法 (Method for electrodepositing Ni-Fe-Sn-P alloy on surface of foamed nickel ) 是由 寇昕莉 周延科 魏恒 张�林 于 2021-01-07 设计创作，主要内容包括：一种泡沫镍表面电沉积Ni-Fe-Sn-P合金的方法,其具体工艺如下：(1)选取泡沫镍基底；(2)泡沫镍基底预处理；(3)电镀液配置；(4)施镀：将电镀液在水浴锅中加热至45-65℃,将处理好的泡沫镍基底放入作为阴极,将含碳量>99.99%高纯度石墨片作为阳极,在40-120mA/cm～2条件下进行电镀,电镀时长30-50min,电镀完后将工作电极取出,用去离子水冲洗,在45-50℃下烘干得到Ni-Fe-Sn-P合金。本发明Ni-Fe-Sn-P合金借助泡沫镍的多孔、高比表面的特性,大大增加了析氢反应过程中的活性位点数量,降低了阴极过电位,减少能源损耗,在电解水制氢方面,是一种性能高效、成本低廉的阴极材料。(A method for electrodepositing Ni-Fe-Sn-P alloy on the surface of foamed nickel comprises the following specific processes: (1) selecting a foam nickel substrate; (2) pretreating a foamed nickel substrate; (3) preparing electroplating solution; (4) plating: heating the electroplating solution to 45-65 deg.C in water bath, placing the treated foamed nickel substrate as cathode, and adding carbon>99.99% high-purity graphite flake as anode at 40-120mA/cm 2 Electroplating for 30-50min, taking out the working electrode after electroplating, washing with deionized water, and drying at 45-50 deg.C to obtain Ni-Fe-Sn-P alloy. The Ni-Fe-Sn-P alloy greatly increases the hydrogen evolution reaction by virtue of the characteristics of porous and high specific surface of the foamed nickelThe number of active sites in the process reduces the overpotential of the cathode and reduces the energy consumption, and the cathode material is a cathode material with high efficiency and low cost in the aspect of hydrogen production by water electrolysis.)

1. A method for electrodepositing Ni-Fe-Sn-P alloy on the surface of foamed nickel is characterized by comprising the following specific processes:

(1) selecting a foamed nickel substrate

Selecting the product with the purity of 98%;

(2) foam nickel pretreatment

Sequentially carrying out steps of removing an oxidation film, washing, deoiling, washing with absolute ethyl alcohol, washing with water and drying on the bubble foam nickel substrate, and finally sealing the obtained sample for later use;

(3) electroplating solution preparation

Adding nickel chloride hexahydrate, stannous chloride, ferrous sulfate hexahydrate, sodium hypophosphite, sodium gluconate, boric acid, sodium chloride, ascorbic acid, saccharin and peptone into deionized water, and fully stirring until the materials are completely dissolved to obtain the product;

(4) plating of

Heating the electroplating solution to 45-65 deg.C in water bath, placing the treated foamed nickel substrate as cathode, and adding carbon>99.99% high-purity graphite flake as anode at 40-120mA/cm²Electroplating for 30-50min, taking out the working electrode after electroplating, washing with deionized water, and drying at 45-50 deg.C to obtain Ni-Fe-Sn-P alloy.

2. The method for electrodepositing the Ni-Fe-Sn-P alloy on the surface of the foamed nickel as claimed in claim 1, wherein: in the step (1), the aperture of the foamed nickel is 100-110ppi, and the thickness is 0.3-0.5 mm.

3. The method of producing the Sn-P alloy according to claim 1 or 2, wherein the plating solution in the step (3) is prepared by: firstly, adding 40 mL of deionized water, stannous chloride, ferrous sulfate hexahydrate, sodium hypophosphite, sodium gluconate, boric acid, sodium chloride, ascorbic acid, saccharin and peptone, stirring for 1-2 hours at room temperature until the components are completely dissolved, adjusting the pH value to 4-6, then adding deionized water to constant volume to 50mL to prepare the electroplating solution, wherein the nickel chloride hexahydrate is 83-90g/L, the stannous chloride is 6-8g/L, and the ferrous sulfate hexahydrate is FeSO₄·6H₂12-24g/L of O, 60-100g/L of sodium hypophosphite, 120g/L of sodium gluconate, 2g/L of ascorbic acid, 15-56g/L of boric acid, 17.5g/L of sodium chloride, 2g/L of saccharin and 0.1g/L of peptone.

4. The method for electrodepositing the Ni-Fe-Sn-P alloy on the surface of the foamed nickel as claimed in claim 3, wherein: and (3) adjusting the pH value of the electroplating solution to 4-6 by using 2M sodium hydroxide solution and 1M sulfuric acid solution.

5. The method for electrodepositing the Ni-Fe-Sn-P alloy on the surface of the foamed nickel as claimed in claim 1 or 4, wherein: the method for pretreating the foamed nickel substrate in the step (2) comprises the following steps: firstly, putting the foamed nickel substrate into 2.8-3.2 mol/L hydrochloric acid solution for ultrasonic treatment for 10-20 min to remove an oxide layer on the surface, washing with deionized water, then respectively removing oil stains and other impurities on the surface by ultrasonic treatment for 10-20 min, washing with deionized water again, drying at 60-65 ℃ and sealing for later use.

6. The method for electrodepositing the Ni-Fe-Sn-P alloy on the surface of the foamed nickel as claimed in claim 5, wherein: in the step (4), the processed foamed nickel is cut into 1 × 3cm to be used as a cathode, and a high-purity graphite sheet of 2 × 2cm is used as an anode.

Technical Field

The invention belongs to the technical field of electrodeposition alloy, and particularly relates to a method for electrodepositing Ni-Fe-Sn-P alloy on the surface of foamed nickel.

Background

With the rapid development of modern science and technology, energy problems and environmental problems are increasingly prominent. Hydrogen energy is regarded as an ideal future energy carrier as clean and efficient renewable energy. Among the numerous methods for producing hydrogen, the method for producing hydrogen by electrolyzing water is an important method for simply and efficiently obtaining hydrogen. At present, the platinum group noble metal is the best electro-catalytic hydrogen evolution material, but cannot be applied in large scale in production due to the small reserves thereof. The nickel-based electrode material prepared based on the electrodeposition technology is widely researched by scientific researchers as a cathode material in the process of hydrogen production by electrolyzing water due to the simple preparation method, large raw material reserves and low cost. For example: nickel-iron alloy electrodes, nickel-phosphorus alloy electrodes, and the like. At present, researchers at home and abroad research nickel-based catalysts in binary and ternary systems, and the activity of the prepared nickel-based catalysts cannot meet the requirements of commercial application, mainly because the hydrogen evolution potential of cathode materials is too high, the energy consumption is too high, and industrial production cannot be realized. In order to continuously optimize the electrocatalytic cathode material, a Ni-Fe-Sn-P quaternary alloy deposited on the surface of the foamed nickel is developed, namely, a tin element and an iron element are sequentially introduced on the Ni-P binary system.

Disclosure of Invention

The invention aims to solve the technical problem of providing a method for electrodepositing Sn-P alloy on the surface of foamed nickel aiming at the defects in the prior art, and the invention ensures that the Ni-Fe-Sn-P quaternary alloy prepared by electrodeposition on the surface of the foamed nickel has more hydrogen evolution active sites by virtue of the characteristic of larger specific surface area of the foamed nickel, thereby promoting the hydrogen evolution reaction; the prepared Ni-Fe-Sn-P alloy can be used as a very excellent cathode material in an electrocatalytic reaction.

The technical scheme is adopted to solve the technical problem of the invention.

A method for electrodepositing Ni-Fe-Sn-P alloy on the surface of foamed nickel comprises the following specific processes:

(1) selecting a foamed nickel substrate

Selecting foamed nickel with the purity of 98 percent;

(2) foam nickel substrate pretreatment

Sequentially carrying out steps of removing an oxidation film, washing, deoiling, washing with absolute ethyl alcohol, washing with water and drying on the bubble foam nickel substrate, and finally sealing the obtained sample for later use;

(3) electroplating solution preparation

Adding nickel chloride hexahydrate, stannous chloride, ferrous sulfate hexahydrate, sodium hypophosphite, sodium gluconate, boric acid, sodium chloride, ascorbic acid, saccharin and peptone into deionized water, and fully stirring until the materials are completely dissolved to prepare an electroplating solution;

(4) plating of

Heating the electroplating solution to 45-65 deg.C in water bath, placing the treated foamed nickel substrate as cathode, and adding carbon>99.99% high-purity graphite flake as anode at 40-120mA/cm²Electroplating for 30-50min, taking out the working electrode after electroplating, washing with deionized water, and drying at 45-50 deg.C to obtain Ni-Fe-Sn-P alloy.

In the step (1), the aperture of the foamed nickel is 100-110ppi, and the thickness is 0.3-0.5 mm.

The preparation method of the electroplating solution in the step (3) comprises the following steps: firstly, adding nickel chloride hexahydrate, stannous chloride, ferrous sulfate hexahydrate, sodium hypophosphite, sodium gluconate, boric acid, sodium chloride, ascorbic acid, saccharin and peptone into 40 mL of deionized water, then stirring for 1-2 hours at room temperature until the sodium chloride, the stannous chloride, the ferrous sulfate hexahydrate, the sodium hypophosphite, the sodium gluconate, the boric acid, the sodium chloride, the saccharin, the peptone and the saccharin are completely dissolved, adjusting the pH to 4-6, then adding the deionized water to the constant volume of 50mL to prepare the electroplating solution, wherein the nickel chloride hexahydrate is 83-90g/L, the stannous chloride is 6-8g/L, and the ferrous sulfate hexahydrate₄·6H₂12-24g/L of O, 60-100g/L of sodium hypophosphite, 120g/L of sodium gluconate, 2g/L of ascorbic acid, 15-56g/L of boric acid, 17.5g/L of sodium chloride, 2g/L of saccharin and 0.1g/L of peptone.

And (3) adjusting the pH value of the electroplating solution to 4-6 by using 2M sodium hydroxide solution and 1M sulfuric acid solution.

The method for pretreating the foamed nickel substrate in the step (2) comprises the following steps: firstly, putting a foamed nickel substrate into 2.8-3.2 mol/L hydrochloric acid solution for ultrasonic treatment for 10-20 min to remove an oxide layer on the surface, washing with deionized water, then respectively carrying out ultrasonic treatment with acetone and absolute ethyl alcohol for 10-20 min to remove oil stains and other impurities on the surface, washing with deionized water again, drying at 60-65 ℃ and sealing for later use.

In the step (4), the processed foamed nickel is cut into 1 × 3cm to be used as a cathode, and a high-purity graphite sheet of 2 × 2cm is used as an anode.

d. Electrochemical testing

Cutting the dried sample to 1cm²The method comprises the steps of performing linear voltammetry scan test, in a three-electrode system, taking Ni-Fe-Sn-P/NF as a working electrode, a 1 x 1cm platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, performing the test in a 1mol/L sodium hydroxide solution at 25 ℃, performing open-circuit potential stabilization before the test for 30min, and performing the linear voltammetry scan test at a scan speed of 2mV/s within a range of-1.5-1V.

The invention prepares the Ni-Fe-Sn-P quaternary alloy on the foam nickel substrate by electrodeposition for the first time, wherein the atomic proportion of Ni is 40-60%, the atomic proportion of Fe is 10-20%, the atomic proportion of Sn is 5-15%, and the balance is P. The electroplating layer has good binding force with the foamed nickel substrate, the used electroplating solution has little corrosivity and does not contain heavy metal, the whole electroplating process has no pollution to the environment, and the requirements of environmental protection and sustainable production are met. The Ni-Fe-Sn-P quaternary alloy prepared by the invention can have an electrocatalytic hydrogen evolution effect of more than 60h in 1M sodium hydroxide solution, has good catalytic stability, and simultaneously greatly increases the number of active sites in the hydrogen evolution reaction process and the synergistic effect among the elements of the quaternary alloy by virtue of the characteristics of porosity and high specific surface of the foamed nickel, reduces the overpotential of the cathode, reduces the energy consumption, and is a cathode material with high efficiency and low cost in the aspect of hydrogen production by water electrolysis.

Drawings

FIG. 1a is an SEM image of a Ni-Fe-Sn-P quaternary alloy at pH4 of example 1 of the present invention; FIG. 1b is an SEM image of a Ni-Fe-Sn-P quaternary alloy at pH6 for example 2 in accordance with the present invention;

FIG. 2 is XPS diagram of Ni-Fe-Sn-P quaternary alloy prepared by 2;

FIG. 3 is an EDAX diagram of a Ni-Fe-Sn-P quaternary alloy prepared in example 2 of the present invention;

FIG. 4 is a graph comparing the linear voltammetry scans of examples 1, 2, 3, and 4 of the present invention.

Detailed Description

The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

Example 1

A method for electrodepositing Ni-Fe-Sn-P alloy on the surface of foamed nickel comprises the following specific processes:

(1) selecting a foamed nickel substrate

Selecting foamed nickel with the pore diameter of 110ppi, the thickness of 0.3mm and the purity of 98 percent;

(2) foam nickel substrate pretreatment

Firstly, putting a foamed nickel substrate into 2.8 mol/L hydrochloric acid solution for ultrasonic treatment for 20min to remove an oxide layer on the surface, washing with deionized water, respectively carrying out ultrasonic treatment for 20min with acetone and absolute ethyl alcohol to remove surface oil stains and other impurities, washing with deionized water again, drying at 60 ℃ and sealing for later use;

(3) electroplating solution preparation

Firstly, adding 4.16g of nickel chloride hexahydrate, 0.3g of stannous chloride, 0.6g of ferrous sulfate hexahydrate, 3g of sodium hypophosphite, 6g of sodium gluconate, 2.78g of boric acid, 0.877g of sodium chloride, 0.1g of ascorbic acid, 0.1g of saccharin and 0.005g of peptone into 40 mL of deionized water, stirring for 2 hours at room temperature until the materials are completely dissolved, adjusting the pH value to 4 by using 2M sodium hydroxide solution and 1M sulfuric acid solution, and then adding deionized water to fix the volume to 50mL to prepare the electroplating solution, wherein the nickel chloride hexahydrate is 83g/L, the stannous chloride is 6g/L, and the ferrous sulfate hexahydrate is FeSO₄·6H₂12g/L of O, 60g/L of sodium hypophosphite, 120g/L of sodium gluconate, 2g/L of ascorbic acid, 56g/L of boric acid, 17.5g/L of sodium chloride, 2g/L of saccharin and 0.1g/L of peptone;

(4) plating of

Cutting the processed foamed nickel into 1 x 3cm as cathode, 2 x 2cm high-purity graphite flake as anode, heating the electroplating solution to 45 deg.C in water bath, placing the processed foamed nickel substrate as cathode, and adding carbon>99.99% high purity graphite flake asAnode at 120mA/cm²Electroplating for 50min, taking out the working electrode after electroplating, washing with deionized water, and drying at 50 ℃ to obtain Ni-Fe-Sn-P alloy;

(5) electrochemical testing

Cutting the dried sample to 1cm²The method comprises the steps of performing linear voltammetry scan test, in a three-electrode system, taking Ni-Fe-Sn-P/NF as a working electrode, a 1 x 1cm platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, performing the test in a 1mol/L sodium hydroxide solution at 25 ℃, performing open-circuit potential stabilization before the test for 30min, and performing the linear voltammetry scan test at a scan speed of 2mV/s within a range of-1.5-1V.

Example 2

A method for electrodepositing Ni-Fe-Sn-P alloy on the surface of foamed nickel comprises the following specific processes:

(1) selecting a foamed nickel substrate

Selecting foamed nickel with the pore diameter of 100ppi, the thickness of 0.5mm and the purity of 98 percent;

(2) foam nickel substrate pretreatment

Firstly, placing a foamed nickel substrate in 3.2 mol/L hydrochloric acid solution for ultrasonic treatment for 10 min to remove an oxide layer on the surface, washing with deionized water, then respectively using acetone and absolute ethyl alcohol for ultrasonic treatment for 10 min to remove surface oil stains and other impurities, washing with deionized water again, drying at 65 ℃ and sealing for later use;

(3) electroplating solution preparation

Firstly, adding 4.16g of nickel chloride hexahydrate, 0.3g of stannous chloride, 0.6g of ferrous sulfate hexahydrate, 4g of sodium hypophosphite, 6g of sodium gluconate, 2.78g of boric acid, 0.877g of sodium chloride, 0.1g of ascorbic acid, 0.1g of saccharin and 0.005g of peptone into 40 mL of deionized water, stirring for 2 hours at room temperature until the materials are completely dissolved, adjusting the pH value to 4 by using 2M sodium hydroxide solution and 1M sulfuric acid solution, and then adding deionized water to fix the volume to 50mL to prepare the electroplating solution, wherein the nickel chloride hexahydrate is 83g/L, the stannous chloride is 6g/L, and the ferrous sulfate hexahydrate is FeSO₄·6H₂12g/L of O, 80g/L of sodium hypophosphite, 120g/L of sodium gluconate, 2g/L of ascorbic acid, 56g/L of boric acid and chloridizationSodium 17.5g/L, saccharin 2g/L, peptone 0.1 g/L;

(4) plating of

Cutting the processed foamed nickel into 1 x 3cm as cathode, 2 x 2cm high-purity graphite flake as anode, heating the electroplating solution to 65 deg.C in water bath, placing the processed foamed nickel substrate as cathode, and adding carbon>99.99% high-purity graphite flake is used as anode at 40mA/cm²Electroplating for 30min, taking out the working electrode after electroplating, washing with deionized water, and drying at 45 deg.C to obtain Ni-Fe-Sn-P alloy;

(5) electrochemical testing was the same as in example 1.

Example 3

A method for electrodepositing Ni-Fe-Sn-P alloy on the surface of foamed nickel comprises the following specific processes:

(1) selecting a foamed nickel substrate

Selecting foamed nickel with the pore diameter of 110ppi, the thickness of 0.4mm and the purity of 98 percent;

(2) foam nickel substrate pretreatment

Firstly, placing a foamed nickel substrate in 3.0mol/L hydrochloric acid solution for ultrasonic treatment for 15min to remove an oxide layer on the surface, washing with deionized water, then respectively carrying out ultrasonic treatment with acetone and absolute ethyl alcohol for 20min to remove surface oil stains and other impurities, washing with deionized water again, drying at 65 ℃ and sealing for later use;

(3) electroplating solution preparation

Firstly, adding 4.16g of nickel chloride hexahydrate, 0.3g of stannous chloride, 0.9g of ferrous sulfate hexahydrate, 5g of sodium hypophosphite, 6g of sodium gluconate, 0.75g of boric acid, 0.877g of sodium chloride, 0.1g of ascorbic acid, 0.1g of saccharin and 0.005g of peptone into 40 mL of deionized water, stirring for 2 hours at room temperature until the materials are completely dissolved, adjusting the pH value to 4 by using 2M sodium hydroxide solution and 1M sulfuric acid solution, and then adding deionized water to fix the volume to 50mL to prepare the electroplating solution, wherein the nickel chloride hexahydrate is 83g/L, the stannous chloride is 6g/L, and the ferrous sulfate hexahydrate is FeSO₄·6H₂18g/L of O, 100g/L of sodium hypophosphite, 120g/L of sodium gluconate, 2g/L of ascorbic acid, 15g/L of boric acid, 17.5g/L of sodium chloride, 2g/L of saccharin and 0.1g/L of peptone;

(4) plating of

The treated nickel foam was cut to 1 × 3cm as the cathode and 2 × 2cm of high purity graphite sheet as the anode. Heating the electroplating solution to 50 deg.C in water bath, placing the treated foamed nickel substrate as cathode, and adding carbon>99.99% high-purity graphite flake is used as anode at 40mA/cm²Electroplating for 40min, taking out the working electrode, washing with deionized water, and drying at 50 deg.C;

(5) electrochemical testing was the same as in example 1.

Example 4

A method for electrodepositing Ni-Fe-Sn-P alloy on the surface of foamed nickel comprises the following specific processes:

(1) selecting a foamed nickel substrate

Selecting foamed nickel with the pore diameter of 110ppi, the thickness of 0.4mm and the purity of 98 percent;

(2) foam nickel substrate pretreatment

Firstly, placing a foamed nickel substrate in 3.0mol/L hydrochloric acid solution for ultrasonic treatment for 20min to remove an oxide layer on the surface, washing with deionized water, then respectively using acetone and absolute ethyl alcohol for ultrasonic treatment for 15min to remove surface oil stains and other impurities, washing with deionized water again, drying at 60 ℃ and sealing for later use;

(3) electroplating solution preparation

Firstly, adding 4.5g of nickel chloride hexahydrate, 0.4g of stannous chloride, 1.2g of ferrous sulfate hexahydrate, 4g of sodium hypophosphite, 6g of sodium gluconate, 2.78g of boric acid, 0.877g of sodium chloride, 0.1g of ascorbic acid, 0.1g of saccharin and 0.005g of peptone into 40 mL of deionized water, stirring for 2 hours at room temperature until the materials are completely dissolved, adjusting the pH value to 4 by using 2M sodium hydroxide solution and 1M sulfuric acid solution, and then adding deionized water to fix the volume to 50mL to prepare the electroplating solution, wherein the nickel chloride hexahydrate is 90g/L, the stannous chloride is 8g/L, and the ferrous sulfate hexahydrate is FeSO₄·6H₂24g/L of O, 80g/L of sodium hypophosphite, 120g/L of sodium gluconate, 2g/L of ascorbic acid, 56g/L of boric acid, 17.5g/L of sodium chloride, 2g/L of saccharin and 0.1g/L of peptone;

(4) plating of

Cutting the processed foam nickel1 x 3cm was used as the cathode and 2 x 2cm of high purity graphite sheet was used as the anode. Heating the electroplating solution to 55 deg.C in water bath, placing the treated foamed nickel substrate as cathode, and adding carbon>99.99% high-purity graphite flake is used as anode at 40mA/cm²Electroplating for 35min, taking out the working electrode after electroplating, washing with deionized water, and drying at 50 deg.C;

(5) electrochemical testing was the same as in example 1.

The invention discovers that the microscopic morphologies of the prepared Ni-Fe-Sn-P quaternary alloy are cauliflower-shaped under different pH values, as shown in figure 1a (example 1) and figure 1b (example 2), the Ni-Fe-Sn-P quaternary alloy is composed of small particles with the size of 60-150nm, the small particles are tightly packed into larger particles with the size of 1-3 mu m, the size is uniform, the surface is rough, and the catalytic surface area is further improved on the basis of the structure of the foamed nickel. FIG. 2 is an X-ray photoelectron spectroscopy (XPS) of a Ni-Fe-Sn-P quaternary alloy of example 2, from which we can see that it contains a part of oxygen elements in addition to four elements of Ni, Fe, Sn, P, and carbon elements for calibration, which shows that there are a part of oxides in addition to the formation of the Ni-Fe-Sn-P quaternary alloy. In addition, the peak position comparison of each element on XPS shows that the element is not in a zero valence state, which also indicates that the Ni-Fe-Sn-P quaternary alloy is not purely physically mixed, and electron transfer occurs, so that a certain degree of synergistic effect exists. FIG. 3 is an EDAX diagram of the Ni-Fe-Sn-P quaternary alloy of example 2, from which we have determined the contents of the elements, Ni being 61%, Fe 23%, Sn 8%, P8%. FIG. 4 is a graph of (examples 1, 2, 3 and 4) the electrocatalytic hydrogen evolution performance measured by an electrochemical workstation on a linear voltammetric sweep versus 10mA/cm²The overpotential of the time shows that the performance of the Ni-Fe-Sn-P quaternary alloy with the pH value of 6 is better than that of the Ni-Fe-Sn quaternary alloy with the pH value of 4, and simultaneously, the performance is better than that of the Ni-Fe-Sn ternary alloy prepared under the same condition.