Preparation method of foamy copper-based seawater electrolysis oxygen desorption material

Abstract

The invention provides a preparation method of a foamy copper-based seawater electrolysis oxygen desorption material, which comprises the following steps: immersing a foamy copper matrix in an activating treatment solution composed of stannous mono-sulphate, citric acid, ammonium sulfate, sulfamic acid and deionized water for surface activating treatment to obtain activated foamy copper; the activated foamy copper is immersed in the electro-deposition liquid, electro-deposition is carried out under water bath heating at trapezoidal / semi-cycle sine anisotropic potential, and a tin-nickel-manganese-chromium multi-element electro-deposition layer is formed on the surface of a foamy copper matrix; and carrying out Er modification and oxygen atom introduction surface treatment on the tin-nickel-manganese-chromium multi-element electro-deposition layer to finally obtain the oxygen evolution material. The seawater electrolysis oxygen desorption material prepared by the method has excellent reaction activity and excellent corrosion resistance.

Description

Technical Field

[0001] This invention relates to the field of seawater electrolytic oxygen materials, and in particular to a method for preparing a foamed copper-based seawater electrolytic oxygen material. Background Technology

[0002] Compared with fossil fuel hydrogen production technologies that use coal, natural gas, and oil as raw materials, seawater electrolysis hydrogen production technology can not only produce high-purity hydrogen, but also achieve zero emissions and no polluting byproducts. Furthermore, it does not rely on limited non-renewable resources—especially since it can use abundant seawater as a production raw material. Therefore, it has become the most promising technological approach for large-scale production of clean hydrogen energy.

[0003] However, in the process of hydrogen evolution through seawater electrolysis, the oxygen evolution reaction at the anolyte requires a four-electron transfer, resulting in a high activation energy and a slow reaction rate. This problem severely restricts the overall efficiency of hydrogen evolution through seawater electrolysis. Furthermore, chloride ions in seawater not only easily corrode the materials used in seawater electrolysis for oxygen evolution but also occupy the reactive sites of the materials, further affecting the reaction process.

[0004] To date, materials possessing ideal oxygen evolution activity in seawater electrolysis remain limited to precious metals iridium, ruthenium, and their oxides. These materials are not only expensive but also extremely scarce in the Earth's crust, making it difficult to meet the demands of large-scale production and widespread application. In the field of seawater electrolysis oxygen evolution materials, existing materials have significant shortcomings: unsatisfactory oxygen evolution reactivity and poor corrosion resistance. These problems have become the core bottlenecks restricting the further development of seawater electrolysis hydrogen production technology. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, the present invention provides a method for preparing a foamed copper-based seawater electrolytic oxygen desorption material. The seawater electrolytic oxygen desorption material prepared by this method has excellent reactivity and superior corrosion resistance.

[0006] The technical solution adopted by this invention to solve its technical problem is:

[0007] This invention first provides a method for preparing a foamed copper-based seawater electrolytic oxygen desorption material, comprising the following steps performed in sequence:

[0008] Step [1] Add a certain amount of stannous sulfate, citric acid, ammonium sulfate and aminosulfonic acid to deionized water and mix to form an activation treatment solution; immerse the copper foam substrate in the activation treatment solution for surface activation treatment to obtain activated copper foam.

[0009] Step [2] Add a certain amount of stannous sulfate, nickel methanesulfonate, manganese dihydrogen phosphate, chromium acetate, disodium DL-hydroxysuccinate, and acetic acid solution with a mass fraction of 36% to deionized water and mix to form an electrodeposition solution; immerse activated foam copper in the electrodeposition solution and use it as the working electrode, and stainless steel as the counter electrode, and perform electrodeposition under water bath heating with a trapezoidal / half-cycle sinusoidal anisotropic potential to obtain electrodeposited foam copper with an electrodeposition layer formed on the surface;

[0010] Step [3] Add a certain amount of erbium chloride, erbium hydroxide, ammonium persulfate, and acetic acid solution with a mass fraction of 36% to deionized water and mix to form a modification solution; immerse the electrodeposited copper foam in this modification solution and react at 110-140℃ for 6-8 hours, and obtain the copper foam-based seawater electrolytic oxygen material after drying.

[0011] Preferably, the components of the activation treatment solution are in the following weight proportions: 25-65 parts stannous sulfate, 20-50 parts citric acid, 50-90 parts ammonium sulfate, 0.5-4 parts aminosulfonic acid, and 800-900 parts deionized water.

[0012] Preferably, the mass ratio between the activation treatment liquid and the foamed copper in step [1] is 100:11 to 18; the surface activation treatment time is 3 to 5 hours.

[0013] Preferably, the weight proportions of each component in the electrodeposition solution are as follows: 20-40 parts stannous sulfate, 60-100 parts nickel methanesulfonate, 40-60 parts manganese dihydrogen phosphate, 40-70 parts chromium acetate, 10-30 parts disodium DL-hydroxysuccinate, 15-30 parts acetic acid solution, and 700-850 parts deionized water.

[0014] Preferably, the mass ratio between the activation treatment solution and the activated copper foam in step [2] is 100:6 to 9; the water bath heating temperature is 50 to 70°C; and the electrodeposition time is 20 to 35 minutes.

[0015] Preferably, the specific operation of electrodeposition with trapezoidal / half-cycle sinusoidal anisotropic potential in step [2] is as follows: the electrodeposition voltage is linearly reduced from 0V at a rate of 0.6V / s-4.5V / s, reaching -0.15 to -1.8V after 0.25 to 0.5s and then held for 0.5 to 1.5s; then the electrodeposition voltage is linearly increased at a rate of 0.8V / s-4.5V / s, reaching 0V after 0.18 to 0.5s; then a positive half-cycle sinusoidal electrodeposition voltage with an amplitude of 0.25 to 0.8V and a period of 0.8 to 2s is applied, and finally held at 0V for 0.5 to 1.3s, thus completing one trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition cycle.

[0016] Preferably, the components of the modifying solution are in the following weight proportions: 20-50 parts of erbium chloride, 10-25 parts of erbium hydroxide, 5-30 parts of ammonium persulfate, 5-15 parts of acetic acid solution, and 850-950 parts of deionized water.

[0017] Preferably, the mass ratio between the modification solution and the electrodeposited copper foam in step [3] is 100:17 to 24.

[0018] The positive effects of this invention are as follows: First, the oxide film on the surface of the copper foam is removed through an activation treatment step, and a tin-containing compound is deposited on the surface of the copper foam substrate to provide active sites for subsequent electrodeposition. Then, in a specific electrodeposition solution, a trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition voltage is applied to achieve co-deposition of tin, nickel, manganese, and chromium on the surface of the copper foam substrate. Finally, the tin, nickel, manganese, and chromium electrodeposition layer is modified with Er and oxygen atoms are introduced through a hydrothermal reaction in a modification solution to form a multi-element (Er, Ni, Mn, Sn, Cr, O elements) compound deposition layer with a micro-nano hierarchical porous structure on the surface, and finally the oxygen evolution material is obtained. The copper-based seawater electrolytic oxygen evolution material prepared in this invention has a surface deposition layer with numerous micron and nano-sized pores, resulting in a large reaction area for oxygen evolution in seawater electrolysis. Manganese oxides exhibit strong adsorption capacity and weak desorption capacity for oxygen adsorption intermediates in seawater electrolysis, while tin oxides show weak adsorption capacity and strong desorption capacity. The synergistic effect of manganese and tin oxides on the adsorption and desorption of oxygen adsorption intermediates in seawater electrolysis significantly improves the oxygen evolution activity. The synergistic effect of chromium and nickel effectively improves the corrosion resistance of the material while maintaining its oxygen evolution reactivity. Furthermore, experimental results show that the presence of erbium effectively improves the conductivity of the material and reduces the activation energy of the oxygen evolution reaction in seawater electrolysis. In summary, the oxygen evolution material prepared in this invention exhibits excellent reactivity and superior corrosion resistance in the field of seawater electrolysis oxygen evolution materials. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the preparation process of the seawater electrolytic oxygen material described in this invention;

[0020] Figure 2 This is a schematic diagram of the trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition voltage described in this invention;

[0021] Figure 3 This refers to the scanning electron microscope surface morphology and elemental distribution of Embodiment 1 of the present invention, wherein... Figure 3 a is a surface morphology diagram. Figure 3 b is Figure 3 Enlarged view of a local area in section a; Figure 3 c. Copper element distribution map Figure 3 d is the nickel element distribution map. Figure 3 e represents the chromium element distribution map. Figure 3 f is the distribution map of manganese element. Figure 3 g represents the distribution map of tin element. Figure 3 h represents the distribution map of erbium. Figure 3 i represents the oxygen element distribution map;

[0022] Figure 4 a is the anodic polarization curve of Comparative Example 1, Comparative Example 2 and Example 1 of the present invention at the beginning of simulated seawater electrolysis;

[0023] Figure 4 b represents the 100 mA·cm⁻¹ generated at the start of simulated seawater electrolysis in Comparative Examples 1, 2, and 1 of this invention. -2 The overpotential of the reaction current;

[0024] Figure 5 a is the anodic polarization curve of Comparative Example 1, Comparative Example 2 and Example 1 of the present invention after 200 hours of simulated seawater electrolysis;

[0025] Figure 5 b represents the 100 mA·cm⁻¹ generated after 200 hours of simulated seawater electrolysis in Comparative Examples 1, 2, and 1 of this invention. -2 The overpotential of the reaction current;

[0026] Figure 6 This is a comparison of the annual corrosion depth of Comparative Example 1, Comparative Example 2 and Example 1 of the present invention. Detailed Implementation

[0027] Reference Figure 1 This invention provides a method for preparing a foamed copper-based seawater electrolytic oxygen material, comprising the following steps performed in sequence:

[0028] Step [1] Dissolution of the oxide film on the surface of the copper foam substrate and surface tinning activation treatment, specifically including the following operations:

[0029] a1. Add 25-65 parts by weight of stannous sulfate, 20-50 parts by weight of citric acid, 50-90 parts by weight of ammonium sulfate, and 0.5-4 parts by weight of aminosulfonic acid to 800-900 parts by weight of deionized water and mix evenly to form an activation treatment solution.

[0030] a2. Immerse the copper foam in the activation solution (the mass ratio between the activation solution and the copper foam is 100:11-18) and soak at 25-30°C for 3-5 hours to perform surface activation treatment. Then remove the copper foam and wash it several times with deionized water. Dry it at room temperature for 12-18 hours to obtain activated copper foam.

[0031] Step [2] involves forming a tin-nickel-manganese-chromium multi-element electrodeposition layer on the surface of a copper foam substrate, specifically including the following operations:

[0032] b1. Add 20-40 parts by weight of stannous sulfate, 60-100 parts by weight of nickel methanesulfonate, 40-60 parts by weight of manganese dihydrogen phosphate, 40-70 parts by weight of chromium acetate, 10-30 parts by weight of disodium DL-hydroxysuccinate, and 15-30 parts by weight of acetic acid solution with a mass fraction of 36% to 700-850 parts by weight of deionized water to form an electrodeposition solution;

[0033] b2. The activated foam copper obtained after step [1] is immersed in the electrodeposition solution (the mass ratio between the activation treatment solution and the activated foam copper is 100:6~9). The activated foam copper is used as the working electrode and stainless steel is used as the counter electrode. The water bath is heated to 50~70°C, and then electrodeposition is performed for 20~35 minutes with a trapezoidal / half-cycle sinusoidal anisotropic potential. Finally, an electrodeposited foam copper with a tin-nickel-manganese-chromium multi-element electrodeposition layer formed on the surface is obtained.

[0034] Among them, such as Figure 2 As shown, the specific operation of electrodeposition using a trapezoidal / half-cycle sinusoidal anisotropic potential is as follows: the electrodeposition voltage is linearly decreased from 0V at a rate of 0.6V / s-4.5V / s, reaching -0.15 to -1.8V after 0.25 to 0.5s and then held for 0.5 to 1.5s; then the electrodeposition voltage is linearly increased at a rate of 0.8V / s-4.5V / s, reaching 0V after 0.18 to 0.5s; then a positive half-cycle sinusoidal electrodeposition voltage with an amplitude of 0.25 to 0.8V and a period of 0.8 to 2s is applied to the activated copper foam, and finally held at 0V for 0.5 to 1.3s, thus completing one trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition cycle.

[0035] Step [3] involves surface treatment (Er modification and introduction of oxygen atoms) of the tin-nickel-manganese-chromium multi-element electrodeposited layer, specifically including the following operations:

[0036] c1. Add 20-50 parts by weight of erbium chloride, 10-25 parts by weight of erbium hydroxide, 5-30 parts by weight of ammonium persulfate, and 5-15 parts by weight of 36% acetic acid solution to 850-950 parts by weight of deionized water and mix to form a modification solution.

[0037] c2. The electrodeposited copper foam obtained after step [2] is immersed in the modification solution (the mass ratio between the modification solution and the electrodeposited copper foam is 100:17~24), reacted at 110-140℃ for 6-8 hours, the copper foam sample is taken out and cleaned with deionized water, dried at room temperature for 5-7 hours, and the copper foam-based seawater electrolytic oxygen material is obtained after drying.

[0038] The preferred embodiments of the present invention will be described below by way of example.

[0039] Example 1

[0040] Preferred embodiment 1 of the present invention provides a method for preparing a foamed copper-based seawater electrolytic oxygen desorption material, comprising the following steps performed in sequence:

[0041] Step [1] Dissolution of the oxide film on the surface of the copper foam substrate and surface tinning activation treatment, specifically including the following operations:

[0042] a1. Add 45 parts by weight of stannous sulfate, 40 parts by weight of citric acid, 70 parts by weight of ammonium sulfate, and 3 parts by weight of aminosulfonic acid to 850 parts by weight of deionized water and mix evenly to form an activation treatment solution.

[0043] a2. Immerse the copper foam in the activation solution (the mass ratio of the activation solution to the copper foam is 100:15) and soak at 28°C for 4 hours to perform surface activation treatment. Then take out the copper foam and wash it several times with deionized water. Dry it at room temperature for 16 hours to obtain activated copper foam.

[0044] Step [2] involves forming a tin-nickel-manganese-chromium multi-element electrodeposition layer on the surface of a copper foam substrate, specifically including the following operations:

[0045] b1. Add 30 parts by weight of stannous sulfate, 80 parts by weight of nickel methanesulfonate, 50 parts by weight of manganese dihydrogen phosphate, 60 parts by weight of chromium acetate, 25 parts by weight of disodium DL-hydroxysuccinate, and 25 parts by weight of acetic acid solution with a mass fraction of 36% to 800 parts by weight of deionized water to form an electrodeposition solution.

[0046] b2. The activated foam copper obtained after step [1] is immersed in the electrodeposition solution (the mass ratio between the activation treatment solution and the activated foam copper is 100:8). The activated foam copper is used as the working electrode and stainless steel is used as the counter electrode. The water bath is heated to 65°C, and then electrodeposition is performed for 30 minutes with a trapezoidal / half-cycle sinusoidal anisotropic potential. Finally, an electrodeposited foam copper with a tin-nickel-manganese-chromium multi-element electrodeposition layer formed on the surface is obtained.

[0047] The specific operation of electrodeposition using a trapezoidal / half-cycle sinusoidal anisotropic potential is as follows: the electrodeposition voltage is linearly decreased from 0V at a rate of 3.6V / s, reaching -1.8V after 0.5s and holding for 1s; then the electrodeposition voltage is linearly increased at a rate of 3.6V / s, reaching 0V after 0.5s; then a positive half-cycle sinusoidal electrodeposition voltage with an amplitude of 0.8V and a period of 1.2s is applied, and finally, after returning to 0V, it is held for 1s, thus completing one trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition cycle.

[0048] Step [3] involves surface treatment (Er modification and introduction of oxygen atoms) of the tin-nickel-manganese-chromium multi-element electrodeposited layer, specifically including the following operations:

[0049] c1. Add 30 parts by weight of erbium chloride, 20 parts by weight of erbium hydroxide, 10 parts by weight of ammonium persulfate, and 10 parts by weight of 36% acetic acid solution to 900 parts by weight of deionized water and mix to form a modification solution.

[0050] c2. The electrodeposited copper foam obtained after step [2] is immersed in the modification solution (the mass ratio between the modification solution and the electrodeposited copper foam is 100:19), reacted at 120°C for 8 hours, the copper foam sample is taken out and cleaned with deionized water, dried at room temperature for 6 hours, and the copper foam-based seawater electrolytic oxygen material is obtained after drying, which is recorded as Example 1. Its surface morphology and elemental distribution are as follows. Figure 3 As shown in a~i, where Figure 3 The exposed portion of the copper foam substrate in image a represents the substrate morphology after the surface electrodeposited layer has been removed. Figure 3 b is Figure 3 The magnified image of the local morphology of the frame-shaped region in section a shows that its surface has a large number of pores with nanometer and micrometer-sized dimensions. Figure 3 di indicates that nickel, chromium, manganese, tin, erbium, and oxygen elements are relatively uniformly distributed in the electrodeposited layer.

[0051] Comparative Example 1

[0052] Comparative Example 1 provides a method for preparing a copper-based seawater electrolytic oxygen desorption material, which differs from Example 1 in that it does not perform step [3] (the step of surface treatment of the tin-nickel-manganese-chromium multi-element electrodeposited layer), that is, Comparative Example 1 includes the following steps performed in sequence:

[0053] A method for preparing a foamed copper-based seawater electrolytic oxygen desorption material includes the following steps performed in sequence:

[0054] Step [1] Dissolution of the oxide film on the surface of the copper foam substrate and surface tinning activation treatment, specifically including the following operations:

[0055] a1. Add 45 parts by weight of stannous sulfate, 40 parts by weight of citric acid, 70 parts by weight of ammonium sulfate, and 3 parts by weight of aminosulfonic acid to 850 parts by weight of deionized water and mix evenly to form an activation treatment solution.

[0056] a2. Immerse the copper foam in the activation solution (the mass ratio of the activation solution to the copper foam is 100:15) and soak at 28°C for 4 hours to perform surface activation treatment. Then take out the copper foam and wash it several times with deionized water. Dry it at room temperature for 16 hours to obtain activated copper foam.

[0057] Step [2] involves forming a tin-nickel-manganese-chromium multi-element electrodeposition layer on the surface of a copper foam substrate, specifically including the following operations:

[0058] b1. Add 30 parts by weight of stannous sulfate, 80 parts by weight of nickel methanesulfonate, 50 parts by weight of manganese dihydrogen phosphate, 60 parts by weight of chromium acetate, 25 parts by weight of disodium DL-hydroxysuccinate, and 25 parts by weight of acetic acid solution with a mass fraction of 36% to 800 parts by weight of deionized water to form an electrodeposition solution.

[0059] b2. The activated foam copper obtained after step [1] is immersed in the electrodeposition solution (the mass ratio between the activation treatment solution and the activated foam copper is 100:8). The activated foam copper is used as the working electrode and stainless steel is used as the counter electrode. The water bath is heated to 65°C, and then electrodeposition is performed for 30 minutes with a trapezoidal / half-cycle sinusoidal anisotropic potential. Finally, an electrodeposited foam copper with a tin-nickel-manganese-chromium multi-element electrodeposition layer formed on the surface is obtained, which is referred to as Comparative Example 1.

[0060] The specific operation of electrodeposition using a trapezoidal / half-cycle sinusoidal anisotropic potential is as follows: the electrodeposition voltage is linearly decreased from 0V at a rate of 3.6V / s, reaching -1.8V after 0.5s and holding for 1s; then the electrodeposition voltage is linearly increased at a rate of 3.6V / s, reaching 0V after 0.5s; then a positive half-cycle sinusoidal electrodeposition voltage with an amplitude of 0.8V and a period of 1.2s is applied, and finally, after returning to 0V, it is held for 1s, thus completing one trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition cycle.

[0061] Comparative Example 2

[0062] Comparative Example 2 provides a method for preparing a foamed copper-based seawater electrolytic oxygen material. Unlike Example 1, in step [3], only oxygen is introduced in the surface treatment without Er modification. That is, Comparative Example 2 includes the following steps performed in sequence:

[0063] Step [1] Dissolution of the oxide film on the surface of the copper foam substrate and surface tinning activation treatment, specifically including the following operations:

[0064] a1. Add 45 parts by weight of stannous sulfate, 40 parts by weight of citric acid, 70 parts by weight of ammonium sulfate, and 3 parts by weight of aminosulfonic acid to 850 parts by weight of deionized water and mix evenly to form an activation treatment solution.

[0065] a2. Immerse the copper foam in the activation solution (the mass ratio of the activation solution to the copper foam is 100:15) and soak at 28°C for 4 hours to perform surface activation treatment. Then take out the copper foam and wash it several times with deionized water. Dry it at room temperature for 16 hours to obtain activated copper foam.

[0066] Step [2] involves forming a tin-nickel-manganese-chromium multi-element electrodeposition layer on the surface of a copper foam substrate, specifically including the following operations:

[0067] b1. Add 30 parts by weight of stannous sulfate, 80 parts by weight of nickel methanesulfonate, 50 parts by weight of manganese dihydrogen phosphate, 60 parts by weight of chromium acetate, 25 parts by weight of disodium DL-hydroxysuccinate, and 25 parts by weight of acetic acid solution with a mass fraction of 36% to 800 parts by weight of deionized water to form an electrodeposition solution.

[0068] b2. The activated foam copper obtained after step [1] is immersed in the electrodeposition solution (the mass ratio between the activation treatment solution and the activated foam copper is 100:8). The activated foam copper is used as the working electrode and stainless steel is used as the counter electrode. The water bath is heated to 65°C, and then electrodeposition is performed for 30 minutes with a trapezoidal / half-cycle sinusoidal anisotropic potential. Finally, an electrodeposited foam copper with a tin-nickel-manganese-chromium multi-element electrodeposition layer formed on the surface is obtained.

[0069] The specific operation of electrodeposition using a trapezoidal / half-cycle sinusoidal anisotropic potential is as follows: the electrodeposition voltage is linearly decreased from 0V at a rate of 3.6V / s, reaching -1.8V after 0.5s and holding for 1s; then the electrodeposition voltage is linearly increased at a rate of 3.6V / s, reaching 0V after 0.5s; then a positive half-cycle sinusoidal electrodeposition voltage with an amplitude of 0.8V and a period of 1.2s is applied, and finally, after returning to 0V, it is held for 1s, thus completing one trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition cycle.

[0070] Step [3] involves surface treatment (introducing oxygen atoms) of the tin-nickel-manganese-chromium multi-element electrodeposited layer, specifically including the following operations:

[0071] c1. Add 10 parts by weight of ammonium persulfate and 10 parts by weight of 36% acetic acid solution to 900 parts by weight of deionized water and mix to form a modification solution;

[0072] c2. The electrodeposited copper foam obtained after step [2] is immersed in the modification solution (the mass ratio between the modification solution and the electrodeposited copper foam is 100:19), reacted at 120°C for 8 hours, the copper foam sample was taken out and cleaned with deionized water, dried at room temperature for 6 hours, and the copper foam-based seawater electrolytic oxygen material was obtained after drying, which is referred to as Comparative Example 2.

[0073] To evaluate the electrochemical reactivity and corrosion resistance of Examples 1, 1, and 2 in the electrolysis of seawater for oxygen evolution, a 3.5 wt% NaCl solution was prepared using deionized water as simulated seawater. Comparative Example 1, 2, and 1 were used as working electrodes, platinum as auxiliary electrodes, and a saturated calomel electrode as a reference electrode. The anodic polarization curves of Comparative Example 1, 2, and 1 were measured at the start of electrolysis and after 200 hours of operation, respectively, using a constant voltage of -1.8 V in the simulated seawater electrolysis hydrogen evolution reaction. The anodic polarization curves and the anodic polarization curves at 100 mA·cm⁻¹ were also tested. -2 The overpotential of the reaction current, and the test results are as follows: Figure 4 ( Figure 4 a and Figure 4 b) and Figure 5 ( Figure 5 a and Figure 5 As shown in b), the figure shows that Example 1 generated 100 mA·cm⁻¹ at the beginning of simulated seawater electrochemical oxygen desorption and after 200 hours. -2 The overpotentials of the current were 248 mV and 287 mV, respectively, which were significantly lower than the corresponding overpotentials of Comparative Example 1 and Example 2, demonstrating its excellent activity and stability in the oxygen evolution reaction of seawater electrolysis. The comparison of the experimental results of Example 1 and Comparative Example 2 shows that the modification of the Er element in the electrodeposition layer has a significant impact on the reactivity and stability of the final oxygen evolution material. This may be because erbium atoms have an unfilled 4f electronic structure, which can generate multiple electronic energy levels, effectively improving the conductivity of the material in the oxygen evolution reaction of seawater electrolysis and reducing the activation energy of the oxygen evolution reaction of seawater electrolysis.

[0074] In addition, the weight difference between Comparative Example 1, Comparative Example 2, and Example 1 after 200 hours of electrolytic oxygen reaction in the simulated seawater at a constant voltage of -1.8V was measured using the formula:

[0075] V w =ΔW / S·t

[0076] Where V w Let be the gravimetric corrosion rate, ΔW be the weight difference before and after 200 hours of hydrogen electrolysis reaction, S be the sample surface area, and t be the 200-hour hydrogen electrolysis time. Calculate the gravimetric corrosion rate for this process, and then apply the formula:

[0077] V d =8.76V w / ρ

[0078] Where V d For the annual thickness corrosion rate, V w The annual thickness corrosion rate was calculated for Comparative Example 1, Comparative Example 2, and Example 1, where ρ is the weight corrosion rate and ρ is the average density of the sample. The results are as follows: Figure 6 As shown in the figure, the annual thickness corrosion rates of Example 1, Comparative Example 1 and Comparative Example 2 are 0.07 mm, 0.8 mm and 0.5 mm, respectively. Example 1 reaches the corrosion resistance level of the metal corrosion resistance level ten standard.

[0079] To illustrate this further in detail, three more embodiments are provided below.

[0080] Example 2

[0081] Preferred embodiment 2 of the present invention provides a method for preparing a foamed copper-based seawater electrolytic oxygen material, comprising the following steps performed in sequence:

[0082] Step [1] Dissolution of the oxide film on the surface of the copper foam substrate and surface tinning activation treatment, specifically including the following operations:

[0083] a1. Add 25 parts by weight of stannous sulfate, 20 parts by weight of citric acid, 52 parts by weight of ammonium sulfate, and 0.7 parts by weight of aminosulfonic acid to 800 parts by weight of deionized water and mix evenly to form an activation treatment solution.

[0084] a2. Immerse the copper foam in the activation solution (the mass ratio of the activation solution to the copper foam is 100:11) and soak at 25°C for 5 hours to perform surface activation treatment. Then take out the copper foam and wash it several times with deionized water. Dry it at room temperature for 12 hours to obtain activated copper foam.

[0085] Step [2] involves forming a tin-nickel-manganese-chromium multi-element electrodeposition layer on the surface of a copper foam substrate, specifically including the following operations:

[0086] b1. Add 20 parts by weight of stannous sulfate, 60 parts by weight of nickel methanesulfonate, 40 parts by weight of manganese dihydrogen phosphate, 45 parts by weight of chromium acetate, 13 parts by weight of disodium DL-hydroxysuccinate, and 15 parts by weight of acetic acid solution with a mass fraction of 36% to 700 parts by weight of deionized water to form an electrodeposition solution.

[0087] b2. The activated foam copper obtained after step [1] is immersed in the electrodeposition solution (the mass ratio between the activation treatment solution and the activated foam copper is 100:6). The activated foam copper is used as the working electrode and stainless steel is used as the counter electrode. The water bath is heated to 50°C, and then electrodeposition is performed for 35 minutes with a trapezoidal / half-cycle sinusoidal anisotropic potential. Finally, an electrodeposited foam copper with a tin-nickel-manganese-chromium multi-element electrodeposition layer formed on the surface is obtained.

[0088] The specific operation of electrodeposition using a trapezoidal / half-cycle sinusoidal anisotropic potential is as follows: the electrodeposition voltage is linearly decreased from 0V at a rate of 3.8V / s, reaching -1.52V after 0.4s and held for 0.5s; then the electrodeposition voltage is linearly increased at a rate of 3.8V / s, reaching 0V after 0.4s; then a positive half-cycle sinusoidal electrodeposition voltage with an amplitude of 0.6V and a period of 1.6s is applied, and the voltage is held for 0.6s after returning to 0V, thus completing one trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition cycle.

[0089] Step [3] involves surface treatment (Er modification and introduction of oxygen atoms) of the tin-nickel-manganese-chromium multi-element electrodeposited layer, specifically including the following operations:

[0090] c1. Add 20 parts by weight of erbium chloride, 11 parts by weight of erbium hydroxide, 9 parts by weight of ammonium persulfate, and 5 parts by weight of 36% acetic acid solution to 850 parts by weight of deionized water and mix to form a modification solution.

[0091] c2. The electrodeposited copper foam obtained after step [2] is immersed in the modification solution (the mass ratio between the modification solution and the electrodeposited copper foam is 100:17), reacted at 110°C for 8 hours, the copper foam sample is taken out and cleaned with deionized water, dried at room temperature for 7 hours, and the copper foam-based seawater electrolytic oxygen material is obtained after drying.

[0092] Example 3

[0093] Preferred embodiment 3 of the present invention provides a method for preparing a foamed copper-based seawater electrolytic oxygen material, comprising the following steps performed in sequence:

[0094] Step [1] Dissolution of the oxide film on the surface of the copper foam substrate and surface tinning activation treatment, specifically including the following operations:

[0095] a1. Add 65 parts by weight of stannous sulfate, 50 parts by weight of citric acid, 90 parts by weight of ammonium sulfate, and 3.5 parts by weight of aminosulfonic acid to 900 parts by weight of deionized water and mix evenly to form an activation treatment solution.

[0096] a2. Immerse the copper foam in the activation solution (the mass ratio between the activation solution and the copper foam is 100:18) and soak at 30°C for 3 hours to perform surface activation treatment. Then take out the copper foam and wash it several times with deionized water. Dry it at room temperature for 18 hours to obtain activated copper foam.

[0097] Step [2] involves forming a tin-nickel-manganese-chromium multi-element electrodeposition layer on the surface of a copper foam substrate, specifically including the following operations:

[0098] b1. Add 39 parts by weight of stannous sulfate, 100 parts by weight of nickel methanesulfonate, 60 parts by weight of manganese dihydrogen phosphate, 66 parts by weight of chromium acetate, 28 parts by weight of disodium DL-hydroxysuccinate, and 30 parts by weight of acetic acid solution with a mass fraction of 36% to 850 parts by weight of deionized water to form an electrodeposition solution.

[0099] b2. The activated foam copper obtained after step [1] is immersed in the electrodeposition solution (the mass ratio between the activation treatment solution and the activated foam copper is 100:9). The activated foam copper is used as the working electrode and stainless steel is used as the counter electrode. The water bath is heated to 70°C, and then electrodeposition is performed for 20 minutes with a trapezoidal / half-cycle sinusoidal anisotropic potential. Finally, an electrodeposited foam copper with a tin-nickel-manganese-chromium multi-element electrodeposition layer formed on the surface is obtained.

[0100] The specific operation of electrodeposition using a trapezoidal / half-cycle sinusoidal anisotropic potential is as follows: the electrodeposition voltage is linearly decreased from 0V at a rate of 1V / s, reaching -0.3V after 0.3s and holding for 1.5s; then the electrodeposition voltage is linearly increased at a rate of 1V / s, reaching 0V after 0.3s; then a positive half-cycle sinusoidal electrodeposition voltage with an amplitude of 0.25V and a period of 1s is applied, returning to 0V and holding for 0.6s, thus completing one trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition cycle.

[0101] Step [3] involves surface treatment (Er modification and introduction of oxygen atoms) of the tin-nickel-manganese-chromium multi-element electrodeposited layer, specifically including the following operations:

[0102] c1. Add 49 parts by weight of erbium chloride, 25 parts by weight of erbium hydroxide, 30 parts by weight of ammonium persulfate, and 13 parts by weight of acetic acid solution with a mass fraction of 36% to 950 parts by weight of deionized water and mix to form a modification solution.

[0103] c2. The electrodeposited copper foam obtained after step [2] is immersed in the modification solution (the mass ratio between the modification solution and the electrodeposited copper foam is 100:24), reacted at 140°C for 6 hours, the copper foam sample is taken out and cleaned with deionized water, dried at room temperature for 5 hours, and the copper foam-based seawater electrolytic oxygen material is obtained after drying.

[0104] Example 4

[0105] Preferred embodiment 4 of the present invention provides a method for preparing a foamed copper-based seawater electrolytic oxygen material, comprising the following steps performed in sequence:

[0106] Step [1] Dissolution of the oxide film on the surface of the copper foam substrate and surface tinning activation treatment, specifically including the following operations:

[0107] a1. Add 45 parts by weight of stannous sulfate, 35 parts by weight of citric acid, 70 parts by weight of ammonium sulfate, and 2.3 parts by weight of aminosulfonic acid to 850 parts by weight of deionized water and mix evenly to form an activation treatment solution.

[0108] a2. Immerse the copper foam in the activation solution (the mass ratio between the activation solution and the copper foam is 100:14.5) and soak at 28°C for 4 hours to perform surface activation treatment. Then take out the copper foam and wash it several times with deionized water. Dry it at room temperature for 15 hours to obtain activated copper foam.

[0109] Step [2] involves forming a tin-nickel-manganese-chromium multi-element electrodeposition layer on the surface of a copper foam substrate, specifically including the following operations:

[0110] b1. Add 30 parts by weight of stannous sulfate, 80 parts by weight of nickel methanesulfonate, 50 parts by weight of manganese dihydrogen phosphate, 55 parts by weight of chromium acetate, 20 parts by weight of disodium DL-hydroxysuccinate, and 23 parts by weight of acetic acid solution with a mass fraction of 36% to 790 parts by weight of deionized water to form an electrodeposition solution.

[0111] b2. The activated foam copper obtained after step [1] is immersed in the electrodeposition solution (the mass ratio between the activation treatment solution and the activated foam copper is 100:7). The activated foam copper is used as the working electrode and stainless steel is used as the counter electrode. The water bath is heated to 60°C, and then electrodeposition is performed for 28 minutes with a trapezoidal / half-cycle sinusoidal anisotropic potential. Finally, an electrodeposited foam copper with a tin-nickel-manganese-chromium multi-element electrodeposition layer formed on the surface is obtained.

[0112] The specific operation of electrodeposition using a trapezoidal / half-cycle sinusoidal anisotropic potential is as follows: the electrodeposition voltage is linearly decreased from 0V at a rate of 2.5V / s, reaching -0.65V after 0.26s and holding for 1s; then the electrodeposition voltage is linearly increased at a rate of 2.5V / s, reaching 0V after 0.26s; then a positive half-cycle sinusoidal electrodeposition voltage with an amplitude of 0.5V and a period of 1.4s is applied, returning to 0V and holding for 0.9s, thus completing one trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition cycle.

[0113] Step [3] involves surface treatment (Er modification and introduction of oxygen atoms) of the tin-nickel-manganese-chromium multi-element electrodeposited layer, specifically including the following operations:

[0114] c1. Add 35 parts by weight of erbium chloride, 19 parts by weight of erbium hydroxide, 20 parts by weight of ammonium persulfate, and 10 parts by weight of acetic acid solution with a mass fraction of 36% to 900 parts by weight of deionized water and mix to form a modification solution.

[0115] c2. The electrodeposited copper foam obtained after step [2] is immersed in the modification solution (the mass ratio between the modification solution and the electrodeposited copper foam is 100:21), reacted at 125°C for 7 hours, the copper foam sample is taken out and cleaned with deionized water, dried at room temperature for 6 hours, and the copper foam-based seawater electrolytic oxygen material is obtained after drying.

[0116] The above description is only a preferred embodiment of the present invention. It should be understood that the above description of the embodiments is only for the purpose of helping to understand the method and core idea of ​​the present invention, and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, etc. made within the idea and principle of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a foamed copper-based seawater electrolytic oxygen desorption material, characterized in that, It includes the following steps performed in sequence: Step [1] Add a certain amount of stannous sulfate, citric acid, ammonium sulfate and aminosulfonic acid to deionized water and mix to form an activation treatment solution; immerse the copper foam substrate in the activation treatment solution for surface activation treatment to obtain activated copper foam. Step [2] Add a certain amount of stannous sulfate, nickel methanesulfonate, manganese dihydrogen phosphate, chromium acetate, disodium DL-hydroxysuccinate, and acetic acid solution with a mass fraction of 36% to deionized water and mix to form an electrodeposition solution; immerse activated foam copper in the electrodeposition solution and use it as the working electrode, and stainless steel as the counter electrode, and perform electrodeposition under water bath heating with a trapezoidal / half-cycle sinusoidal anisotropic potential to obtain electrodeposited foam copper with an electrodeposition layer formed on the surface; Step [3] Add a certain amount of erbium chloride, erbium hydroxide, ammonium persulfate, and acetic acid solution with a mass fraction of 36% to deionized water and mix to form a modification solution; immerse the electrodeposited copper foam in this modification solution and react at 110-140℃ for 6-8 hours, and obtain the copper foam-based seawater electrolytic oxygen material after drying.

2. The method for preparing a foamed copper-based seawater electrolytic oxygen desorption material according to claim 1, characterized in that, The components of the activation treatment solution are as follows by weight: 25-65 parts stannous sulfate, 20-50 parts citric acid, 50-90 parts ammonium sulfate, 0.5-4 parts aminosulfonic acid, and 800-900 parts deionized water.

3. The method for preparing a foamed copper-based seawater electrolytic oxygen desorption material according to claim 1, characterized in that: The mass ratio between the activation treatment liquid and the foamed copper in step [1] is 100:11 to 18; the surface activation treatment time is 3 to 5 hours.

4. The method for preparing a foamed copper-based seawater electrolytic oxygen desorption material according to claim 1, characterized in that, The weight proportions of each component in the electrodeposition solution are as follows: 20-40 parts stannous sulfate, 60-100 parts nickel methanesulfonate, 40-60 parts manganese dihydrogen phosphate, 40-70 parts chromium acetate, 10-30 parts disodium DL-hydroxysuccinate, 15-30 parts acetic acid solution, and 700-850 parts deionized water.

5. The method for preparing a foamed copper-based seawater electrolytic oxygen desorption material according to claim 1, characterized in that: The mass ratio between the activation treatment solution and the activated copper foam in step [2] is 100:6-9; the water bath heating temperature is 50-70℃; and the electrodeposition time is 20-35 minutes.

6. The method for preparing a foamed copper-based seawater electrolytic oxygen desorption material according to claim 1, characterized in that, The specific operation of electrodeposition with trapezoidal / half-cycle sinusoidal anisotropic potential described in step [2] is as follows: the electrodeposition voltage is linearly reduced from 0V at a rate of 0.6V / s-4.5V / s, and after 0.25-0.5s it reaches -0.15--1.8V and is held for 0.5-1.5s; then the electrodeposition voltage is linearly increased at a rate of 0.8V / s-4.5V / s, and after 0.18-0.5s it reaches 0V; then a positive half-cycle sinusoidal electrodeposition voltage with an amplitude of 0.25-0.8V and a period of 0.8-2s is applied, and finally it is held at 0V for 0.5-1.3s, thus completing one trapezoidal / half-cycle sinusoidal anisotropic potential electrodeposition cycle.

7. The method for preparing a foamed copper-based seawater electrolytic oxygen desorption material according to claim 1, characterized in that, The components of the modified solution are as follows by weight: 20-50 parts of erbium chloride, 10-25 parts of erbium hydroxide, 5-30 parts of ammonium persulfate, 5-15 parts of acetic acid solution, and 850-950 parts of deionized water.

8. The method for preparing a foamed copper-based seawater electrolytic oxygen desorption material according to claim 1, characterized in that: The mass ratio between the modification solution and the electrodeposited copper foam in step [3] is 100:17-24.

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