Preparation method and device of ternary non-noble metal layered hydroxide electrocatalytic material

Abstract

The application relates to the technical field of electrocatalysis, and discloses a preparation method and device of a ternary non-noble metal layered hydroxide electrocatalytic material, which comprises the following steps: immersing pre-processed foam nickel in a test reaction solution to obtain immersed foam nickel, performing a hydrothermal reaction on the immersed foam nickel to obtain nickel-iron-titanium double-layer hydroxide, judging whether a low overpotential scan voltammogram set exists in a linear scan voltammogram set, if the low overpotential scan voltammogram set exists, extracting an optimal linear scan voltammogram, identifying a nearby titanium doping molar fraction curve, obtaining a target titanium doping molar fraction according to the optimal titanium doping molar fraction and the nearby titanium doping molar fraction curve, and preparing the ternary non-noble metal layered hydroxide electrocatalytic material according to the target titanium doping molar fraction. The main purpose of the application is to solve the problems of high cost, poor corrosion resistance and low electrocatalytic efficiency of the current electrocatalyst used for water electrolysis.

Description

Technical Field

[0001] This invention relates to a method and apparatus for preparing ternary non-precious metal layered hydroxide electrocatalytic materials, belonging to the field of electrocatalyst technology. Background Technology

[0002] With the increasing consumption of fossil fuels and the growing severity of environmental pollution, hydrogen energy, as a renewable and clean energy source, has gradually attracted attention. Water electrolysis, capable of large-scale production of high-purity hydrogen, is considered one of the most promising methods for hydrogen production. However, its large demand for scarce freshwater resources limits its development. Therefore, utilizing abundant and renewable seawater can effectively alleviate the freshwater shortage problem in the field of water electrolysis for hydrogen production, making the development of seawater electrolysis technology crucial for the development of hydrogen energy. The oxygen evolution reaction (OER), as an important half-reaction in seawater electrolysis, is a key step in hydrogen energy conversion technology. Because seawater contains a large amount of chloride ions and other corrosive ions, it places high demands on the corrosion resistance of the catalyst.

[0003] Currently, the most widely used commercially available OER catalysts are ruthenium-based oxide nanoparticles supported on carbon black. Ruthenium chloride nanoparticles are synthesized hydrothermally, then mixed with carbon black, and subjected to ultrasonication, heat treatment, and cooling to obtain RuO2 nanoparticles with a particle size of approximately 7–9 nm distributed on the surface of a carbon support—this is the RuO2 catalyst. However, ruthenium / iridium-based oxides, as precious metals, are scarce and expensive, limiting their wider application in production. In harsh environments such as seawater electrolysis, precious metal-based catalysts exhibit poor corrosion resistance and are easily corroded by chloride ions, resulting in limited lifespan. Therefore, current electrocatalysts used for water electrolysis suffer from high cost, poor corrosion resistance, and low electrocatalytic efficiency. Summary of the Invention

[0004] This invention provides a method, apparatus, and computer-readable storage medium for preparing ternary non-precious metal layered hydroxide electrocatalytic materials. Its main purpose is to solve the problems of high cost, poor corrosion resistance, and low electrocatalytic efficiency of current electrocatalysts used for water electrolysis.

[0005] To achieve the above objectives, the present invention provides a method for preparing a ternary non-noble metal layered hydroxide electrocatalytic material, comprising:

[0006] The pre-constructed nickel foam is cleaned to obtain target cleaned nickel foam. The target cleaned nickel foam is immersed in a pre-prepared dilute nitric acid solution for 1 hour, then rinsed with deionized water and dried to obtain pre-treated nickel foam. The molar fraction of titanium doping gradient is obtained.

[0007] The titanium doping molar fraction was extracted sequentially from the titanium doping gradient molar fraction. 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride and 5 mmol urea were weighed. Based on the titanium doping molar fraction, the number of titanium doping moles was calculated using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate.

[0008] Weigh out the required amount of titanium trichloride according to the required amount of titanium doping test moles. Add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea and the required amount of titanium trichloride test moles to 30 ml of deionized water and stir until dissolved evenly to obtain the test reaction solution.

[0009] The pretreated nickel foam is immersed in the test reaction solution to obtain immersion nickel foam. The immersion nickel foam is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain hydrothermal nickel foam.

[0010] After alternating cleaning of the hydrothermal foam nickel with deionized water and pre-prepared anhydrous ethanol, the hydrothermal foam nickel is placed in a preset room temperature environment for drying and growth to obtain nickel-iron-titanium bilayer hydroxide.

[0011] The nickel-iron-titanium bilayer hydroxides with various titanium doping molar fractions are summarized to obtain a set of nickel-iron-titanium bilayer hydroxides. The set of nickel-iron-titanium bilayer hydroxides is then subjected to linear sweep voltammetry to obtain a set of linear sweep voltammetric curves, and a reference sweep voltammetric curve is obtained.

[0012] Based on the reference scan voltammetry curve, determine whether there is a preset low overpotential scan voltammetry curve set in the linear scan voltammetry curve set. The low overpotential scan voltammetry curve set refers to the set of linear scan voltammetry curves with an overpotential lower than that of the reference scan voltammetry curve under the same current density.

[0013] If there is no low overpotential scanning voltammetric curve set in the linear scanning voltammetric curve set, then update the titanium doping gradient mole fraction and return to the steps described above of sequentially extracting the titanium doping mole fraction from the titanium doping gradient mole fraction.

[0014] If a set of low overpotential scanning voltammetric curves exists within the set of linear scanning voltammetric curves, then the optimal linear scanning voltammetric curve is extracted from the set of low overpotential scanning voltammetric curves.

[0015] Identify the optimal titanium doping mole fraction of the optimal linear sweep voltammetric curve, and identify the adjacent titanium doping mole fraction curves of the optimal titanium doping mole fraction, wherein the adjacent titanium doping mole fraction curves include: a first adjacent titanium doping mole fraction curve and a second adjacent titanium doping mole fraction curve.

[0016] The target titanium doping molar fraction is obtained based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves, and a ternary non-noble metal layered hydroxide electrocatalytic material is prepared based on the target titanium doping molar fraction.

[0017] Optionally, the step of cleaning the pre-constructed nickel foam to obtain the target cleaned nickel foam includes:

[0018] The nickel foam is initially cleaned in pre-prepared acetone, and then ultrasonically cleaned until the initial cleaning and ultrasonic cleaning reach a preset cleaning frequency to obtain initially cleaned nickel foam.

[0019] After rinsing the pre-cleaned nickel foam with pre-acquired deionized water, the pre-cleaned nickel foam is ultrasonically cleaned for a preset ultrasonic cleaning time to obtain the target cleaned nickel foam.

[0020] Optionally, obtaining the molar fraction of the titanium doping gradient includes:

[0021] Based on the preset initial threshold for titanium doping mole fraction, the preset gradient value for titanium doping mole fraction, and the number of titanium doping mole fraction tests, the titanium doping gradient mole fraction is calculated using the following formula:

[0022] f i = f1 + (i-1) × g, i ≤ I

[0023] Among them, f i f1 represents the i-th titanium doping mole fraction in the titanium doping gradient mole fraction, f1 represents the initial threshold of titanium doping mole fraction, g represents the titanium doping mole fraction gradient value, and I represents the number of titanium doping mole fraction tests.

[0024] Optionally, the step of calculating the number of moles of titanium doping based on the titanium doping mole fraction using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate includes:

[0025] The number of moles of titanium doped was calculated using the following formula based on the stated molar fraction of titanium doping, and using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate:

[0026] n = (0.99 × 10 -3 +0.33×10 -3 +n)×f

[0027] Where n represents the number of moles of titanium doped in the test, and f represents the mole fraction of titanium doping.

[0028] Optionally, the hydrothermal reaction of the impregnated nickel foam at 120°C for 12 hours to obtain hydrothermal nickel foam includes:

[0029] After transferring the impregnated nickel foam to a pre-constructed high-pressure reactor, the high-pressure reactor is placed in a pre-constructed muffle furnace to obtain hydrothermal nickel foam, wherein the high-pressure reactor is lined with polytetrafluoroethylene;

[0030] The nickel foam to be hydrothermally reacted was subjected to a hydrothermal reaction at 120°C for 12 hours to obtain hydrothermally reacted nickel foam.

[0031] The hydrothermal reactive nickel foam is obtained by cooling the nickel foam to a preset room temperature.

[0032] Optionally, obtaining the reference scan voltammetric curve includes:

[0033] Add 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, and 5 mmol urea to 30 ml of deionized water and stir until dissolved to obtain the control reaction solution.

[0034] The pretreated nickel foam is immersed in the control reaction solution to obtain control immersion nickel foam. The control immersion nickel foam is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain control hydrothermal nickel foam.

[0035] After alternating cleaning of the control hydrothermal foam nickel with deionized water and anhydrous ethanol, the control hydrothermal foam nickel was placed in the room temperature environment for drying and growth to obtain nickel-iron-based bilayer hydroxide.

[0036] The nickel-iron-based bilayer hydroxide was subjected to linear sweep voltammetry to obtain a reference sweep voltammetric curve.

[0037] Optionally, the updating of the titanium doping gradient mole fraction includes:

[0038] The last titanium doping mole fraction is extracted from the titanium doping gradient mole fraction. Using the last titanium doping mole fraction and the titanium doping mole fraction gradient value, the initial value of the titanium doping mole fraction is calculated using the following formula:

[0039] f1′=f I +g

[0040] Where f1′ represents the initial molar fraction of titanium doping, f I This represents the I-th titanium doping mole fraction in the titanium doping gradient mole fraction;

[0041] Using the initial value of the titanium doping mole fraction, the gradient value of the titanium doping mole fraction, and the number of titanium doping mole fraction tests, the iterative titanium doping gradient mole fraction is calculated using the following formula:

[0042] f if' = f1' + (i-1) × g, i ≤ I

[0043] Among them, f i ′ represents the mole fraction of titanium doping in the i-th iteration of the titanium doping gradient;

[0044] The titanium doping gradient mole fraction is updated using the iterative titanium doping gradient mole fraction.

[0045] Optionally, the step of extracting the optimal linear scan voltammetric curve from the low overpotential scan voltammetric curve set includes:

[0046] Based on the preset intercept current density, the intercept line of the low overpotential scanning volt-ampere curve set is drawn to obtain the intercept intersection point set, wherein the intercept line is c = i′, where c represents the functional expression of the intercept line and i′ represents the intercept current density.

[0047] Extract the minimum interception intersection from the set of interception intersections, wherein the minimum interception intersection refers to the interception intersection with the smallest overpotential in the set of interception intersections;

[0048] The optimal linear scanning voltammetric curve passing through the minimum intercept intersection point is extracted from the set of low overpotential scanning voltammetric curves.

[0049] Optionally, obtaining the target titanium doping molar fraction based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves includes:

[0050] Based on the preset adjustment spacing molar fraction and the optimal titanium doping molar fraction, the first and second adjustment titanium doping molar fractions are calculated using the following formula:

[0051]

[0052] in, f represents the first debug titanium doping molar fraction. z f represents the optimal molar fraction of titanium doping. d Indicates the mole fraction of the adjustment interval. This indicates the molar fraction of titanium doping in the second tuning test;

[0053] Based on the first adjusted titanium doping molar fraction, the first titanium doping molar number is calculated using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate.

[0054] Weigh the first adjustment titanium trichloride according to the first titanium doping adjustment molar number, add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea and the first adjustment titanium trichloride to 30 ml deionized water and stir until dissolved evenly to obtain the first adjustment reaction solution;

[0055] The pre-treated foamed nickel is immersed in the first debugging reaction solution to obtain the first immersion foamed nickel. The first immersion foamed nickel is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain the first hydrothermal foamed nickel.

[0056] After alternating cleaning of the first hydrothermal foam nickel with deionized water and anhydrous ethanol, the first hydrothermal foam nickel was dried and grown at room temperature to obtain the first nickel-iron-titanium bilayer hydroxide.

[0057] Based on the second adjusted titanium doping molar fraction, the second titanium doping molar number is calculated using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate.

[0058] Weigh the second-adjustment titanium trichloride according to the second titanium doping adjustment molar number, add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea and the second-adjustment titanium trichloride to 30 ml deionized water and stir until dissolved evenly to obtain the second-adjustment reaction solution;

[0059] The pre-treated foamed nickel is immersed in the second debugging reaction solution to obtain the second immersion foamed nickel. The second immersion foamed nickel is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain the second hydrothermal foamed nickel.

[0060] After alternating cleaning with deionized water and anhydrous ethanol, the second hydrothermal foam nickel was dried and grown at room temperature to obtain the second nickel-iron-titanium bilayer hydroxide.

[0061] Linear sweep voltammetry was performed on the first nickel-iron-titanium bilayer hydroxide and the second nickel-iron-titanium bilayer hydroxide to obtain the first linear sweep voltammetric curve and the second linear sweep voltammetric curve.

[0062] Using the intercepting straight line, the first intercepting intersection point, the second intercepting intersection point, and the optimal intercepting intersection point are respectively intercepted in the first linear scanning voltammetry curve, the second linear scanning voltammetry curve, and the optimal linear scanning voltammetry curve;

[0063] Identify the first intersection point overpotential, the second intersection point overpotential, and the optimal intersection point overpotential of the first interception intersection point, the second interception intersection point, and the optimal intersection point, respectively.

[0064] Determine whether the overpotential at the first intersection point is greater than the overpotential at the optimal intersection point;

[0065] If the first intersection overpotential is greater than the optimal intersection overpotential, then the refined titanium doping mole fraction gradient value is calculated based on the optimal titanium doping mole fraction, the second adjusted titanium doping mole fraction, and the number of titanium doping mole fraction tests.

[0066] Determine whether the refined titanium doping mole fraction gradient value is greater than a preset standard gradient threshold;

[0067] If the refined titanium doping mole fraction gradient value is greater than the standard gradient threshold, the titanium doping mole fraction test number is updated according to the preset incremental test number, and the above steps of calculating the refined titanium doping mole fraction gradient value based on the optimal titanium doping mole fraction, the second debug titanium doping mole fraction and the titanium doping mole fraction test number are returned.

[0068] If the refined titanium doping mole fraction gradient value is not greater than the standard gradient threshold, then the refined titanium doping gradient mole fraction is calculated based on the optimal titanium doping mole fraction, the second adjusted titanium doping mole fraction, and the refined titanium doping mole fraction gradient value.

[0069] A refined nickel-iron-titanium bilayer hydroxide set was prepared based on the refined titanium doping gradient molar fraction and 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride and 5 mmol urea.

[0070] Linear scanning voltammetry was performed on the refined nickel-iron-titanium bilayer hydroxide set to obtain a refined linear scanning voltammetry curve set. The target linear scanning voltammetry curve was extracted from the refined linear scanning voltammetry curve set using the truncated straight line.

[0071] Identify the target titanium doping mole fraction corresponding to the target linear scan voltammetric curve;

[0072] If the first intersection overpotential is not greater than the optimal intersection overpotential, then the refined titanium doping mole fraction gradient value is calculated based on the optimal titanium doping mole fraction, the first debug titanium doping mole fraction, and the number of titanium doping mole fraction tests.

[0073] Determine whether the refined titanium doping mole fraction gradient value is greater than the standard gradient threshold;

[0074] If the refined titanium doping mole fraction gradient value is greater than the standard gradient threshold, the titanium doping mole fraction test number is updated according to the incremental test number, and the above steps of calculating the refined titanium doping mole fraction gradient value based on the optimal titanium doping mole fraction, the first debug titanium doping mole fraction, and the titanium doping mole fraction test number are returned.

[0075] If the refined titanium doping mole fraction gradient value is not greater than the standard gradient threshold, then the refined titanium doping gradient mole fraction is calculated based on the optimal titanium doping mole fraction, the first debugged titanium doping mole fraction, and the refined titanium doping mole fraction gradient value.

[0076] A refined nickel-iron-titanium bilayer hydroxide set was prepared based on the refined titanium doping gradient molar fraction and 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride and 5 mmol urea.

[0077] Linear scanning voltammetry was performed on the refined nickel-iron-titanium bilayer hydroxide set to obtain a refined linear scanning voltammetry curve set. The target linear scanning voltammetry curve was extracted from the refined linear scanning voltammetry curve set using the truncated straight line.

[0078] Identify the target titanium doping mole fraction corresponding to the target linear scan voltammetric curve.

[0079] To address the above problems, the present invention also provides an apparatus for preparing a ternary non-noble metal layered hydroxide electrocatalytic material, the apparatus comprising:

[0080] A pre-treatment module for nickel foam is used to clean pre-constructed nickel foam to obtain target cleaned nickel foam. The target cleaned nickel foam is immersed in a pre-prepared dilute nitric acid solution for 1 hour, then rinsed with deionized water and dried to obtain pre-treated nickel foam and obtain the molar fraction of titanium doping gradient.

[0081] The test reaction solution preparation module is used to sequentially extract the titanium doping molar fraction from the titanium doping gradient molar fraction. It weighs 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, and 5 mmol urea. Based on the titanium doping molar fraction, it calculates the number of titanium doping moles using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate. Based on the number of titanium doping moles, it weighs the required number of titanium trichloride moles. The 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea, and the required number of titanium trichloride moles are added to 30 ml of deionized water and stirred until uniformly dissolved to obtain the test reaction solution.

[0082] A nickel-iron-titanium bilayer hydroxide growth module is used to immerse the pre-treated foamed nickel in the test reaction solution to obtain immersion foamed nickel, perform a hydrothermal reaction on the immersion foamed nickel at 120°C for 12 hours to obtain hydrothermal foamed nickel; after alternately cleaning the hydrothermal foamed nickel with deionized water and pre-prepared anhydrous ethanol, the hydrothermal foamed nickel is placed in a preset room temperature environment for drying and growth to obtain nickel-iron-titanium bilayer hydroxide;

[0083] The optimal linear sweep voltammetry curve identification module is used to summarize nickel-iron-titanium bilayer hydroxides with various titanium doping molar fractions to obtain a nickel-iron-titanium bilayer hydroxide set. Linear sweep voltammetry is then performed on this set to obtain a linear sweep voltammetry curve set, and a reference sweep voltammetry curve is obtained. Based on the reference sweep voltammetry curve, it is determined whether a preset low overpotential sweep voltammetry curve set exists within the linear sweep voltammetry curve set. The low overpotential sweep voltammetry curve set refers to the set of linear sweep voltammetry curves with an overpotential lower than that of the reference sweep voltammetry curve at the same current density. If no low overpotential sweep voltammetry curve set exists within the linear sweep voltammetry curve set, the titanium doping gradient molar fraction is updated, and the process returns to the steps described above for sequentially extracting the titanium doping molar fraction from the titanium doping gradient molar fraction. If a low overpotential sweep voltammetry curve set exists within the linear sweep voltammetry curve set, the optimal linear sweep voltammetry curve is extracted from this low overpotential sweep voltammetry curve set.

[0084] A nickel-iron-titanium ternary alloy hydroxide preparation module is used to identify the optimal titanium doping molar fraction of the optimal linear scanning voltammetric curve, and to identify the adjacent titanium doping molar fraction curves of the optimal titanium doping molar fraction, wherein the adjacent titanium doping molar fraction curves include: a first adjacent titanium doping molar fraction curve and a second adjacent titanium doping molar fraction curve; to obtain a target titanium doping molar fraction based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves, and to prepare a ternary non-noble metal layered hydroxide electrocatalytic material based on the target titanium doping molar fraction.

[0085] To address the above problems, the present invention also provides an electronic device, the electronic device comprising:

[0086] At least one processor; and,

[0087] A memory communicatively connected to the at least one processor; wherein,

[0088] The memory stores instructions that can be executed by the at least one processor to implement the above-described method for preparing ternary non-noble metal layered hydroxide electrocatalytic materials.

[0089] To address the aforementioned problems, the present invention also provides a computer-readable storage medium storing at least one instruction, which is executed by a processor in an electronic device to implement the preparation method of the ternary non-noble metal layered hydroxide electrocatalytic material described above.

[0090] Compared to the problems described in the background art, this invention requires the preparation of nickel-iron-titanium bilayer hydroxide in three steps. The first step is to obtain pre-treated nickel foam, the second step is to prepare the test reaction solution, and the third step is to dry and grow the nickel-iron-titanium bilayer hydroxide. In the first step, the pre-constructed nickel foam needs to be cleaned to obtain target cleaned nickel foam. Then, the target cleaned nickel foam is soaked in a pre-prepared dilute nitric acid solution for 1 hour, rinsed with deionized water, and dried to obtain pre-treated nickel foam. At this point, the second step can be carried out. First, the pre-treated nickel foam is immersed in the test reaction solution to obtain immersion nickel foam. Then, the nickel foam is dried at 120°C. Hydrothermal nickel foam is obtained by immersion in liquid-based nickel foam and subjected to a hydrothermal reaction for 12 hours. The foam is then alternately cleaned with deionized water and pre-prepared anhydrous ethanol. Finally, the foam is dried and grown in a preset room temperature environment to produce nickel-iron-titanium bilayer hydroxides. Since linear sweep voltammetry (LSV) is required to identify the nickel-iron-titanium bilayer hydroxides with different titanium doping molar fractions, the LSV set is tested to obtain a set of LSV curves. To extract the optimal LSV curve from this set, a low overpotential curve needs to be extracted first. The scan voltammetry curve set can be used to determine whether a preset low overpotential scan voltammetry curve set exists within the linear scan voltammetry curve set. If no low overpotential scan voltammetry curve set exists, the titanium doping gradient mole fraction is updated, and a new linear scan voltammetry curve set is obtained. If a low overpotential scan voltammetry curve set exists, the optimal linear scan voltammetry curve is extracted from that set. However, once the optimal linear scan voltammetry curve is obtained, it may not be the optimal linear scan voltammetry curve within the titanium doping mole fraction range of the low overpotential scan voltammetry curve set. The voltammetric curve requires identifying the optimal titanium doping molar fraction for the optimal linear sweep voltammetric curve, and then identifying the adjacent titanium doping molar fraction curves. Based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves, the target titanium doping molar fraction is obtained. Finally, a ternary non-noble metal layered hydroxide electrocatalytic material is prepared based on the target titanium doping molar fraction. Therefore, the main purpose of the preparation method, apparatus, electronic equipment, and computer-readable storage medium of the ternary non-noble metal layered hydroxide electrocatalytic material proposed in this invention is to solve the problems of high cost, poor corrosion resistance, and low electrocatalytic efficiency of current electrocatalysts used for water electrolysis. Attached Figure Description

[0091] Figure 1This is a schematic flowchart of a method for preparing a ternary non-noble metal layered hydroxide electrocatalytic material according to an embodiment of the present invention;

[0092] Figure 2 This is a schematic SEM image of an iron-titanium bilayer hydroxide (NiFeTi-LDH) provided in an embodiment of the present invention.

[0093] Figure 3 This is a schematic diagram of the XRD curves of iron-titanium bilayer hydroxide (NiFeTi-LDH) and nickel-iron bilayer hydroxide (NiFe-LDH) provided in an embodiment of the present invention;

[0094] Figure 4 This is a schematic diagram of the Raman spectra of nickel-iron-titanium double-layer hydroxide (NiFeTi-LDH) and nickel-iron-based double-layer hydroxide (NiFe-LDH) provided in an embodiment of the present invention;

[0095] Figure 5 This is a schematic diagram of linear sweep voltammetric curves of nickel-iron-titanium bilayer hydroxide (NiFeTi-LDH) and nickel-iron-based bilayer hydroxide (NiFe-LDH) with different titanium doping concentrations provided in an embodiment of the present invention.

[0096] Figure 6 A schematic diagram illustrating the electrocatalytic stability of nickel-iron-based bilayer hydroxide (NiFe-LDH) and nickel-iron-titanium bilayer hydroxide (NiFeTi-LDH) with a titanium doping molar fraction of 3% provided in an embodiment of the present invention;

[0097] Figure 7 This is a functional block diagram of a device for preparing ternary non-precious metal layered hydroxide electrocatalytic materials according to an embodiment of the present invention;

[0098] Figure 8 This is a schematic diagram of an electronic device for implementing the preparation method of the ternary non-noble metal layered hydroxide electrocatalytic material according to an embodiment of the present invention.

[0099] The objectives, features, and advantages of this invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0100] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0101] This application provides a method for preparing a ternary non-precious metal layered hydroxide electrocatalytic material. The execution entity of this method includes, but is not limited to, at least one of the following electronic devices configured to execute the method provided in this application: a server, a terminal, etc. In other words, the method for preparing the ternary non-precious metal layered hydroxide electrocatalytic material can be executed by software or hardware installed on a terminal device or a server device. The server includes, but is not limited to, a single server, a server cluster, a cloud server, or a cloud server cluster.

[0102] Example 1:

[0103] Reference Figure 1 The diagram shown is a schematic flow chart of a method for preparing a ternary non-noble metal layered hydroxide electrocatalytic material according to an embodiment of the present invention. In this embodiment, the method for preparing the ternary non-noble metal layered hydroxide electrocatalytic material includes:

[0104] S1. Clean the pre-constructed nickel foam to obtain target cleaned nickel foam. Soak the target cleaned nickel foam in a pre-prepared dilute nitric acid solution for 1 hour, then rinse the target cleaned nickel foam with deionized water and air dry to obtain pre-treated nickel foam and obtain the titanium doping gradient molar fraction.

[0105] Explained, the term "Ni Foam" (NF) refers to nickel foam sheets of moderate size. "Pre-treated nickel foam" refers to nickel foam that has undergone pre-treatment. "Titanium doping gradient molar fraction" refers to a gradient sequence of the molar fraction of doped titanium, such as 1%, 3%, 6%, 9%, and 12%. For example, when the molar number of nickel chloride hexahydrate (NiCl6·6H2O) in the test reaction solution is 0.99 mmol, the molar number of ferric nitrate nonahydrate (Fe(NO3)3·9H2O) is 0.33 mmol, and the molar number of titanium trichloride (TiCl3) is 0.013 mmol, then the molar fraction of doped titanium is... The test reaction solution can be found in the following examples.

[0106] In this embodiment of the invention, the step of cleaning the pre-constructed nickel foam to obtain the target cleaned nickel foam includes:

[0107] The nickel foam is initially cleaned in pre-prepared acetone, and then ultrasonically cleaned until the initial cleaning and ultrasonic cleaning reach a preset cleaning frequency to obtain initially cleaned nickel foam.

[0108] After rinsing the pre-cleaned nickel foam with pre-acquired deionized water, the pre-cleaned nickel foam is ultrasonically cleaned for a preset ultrasonic cleaning time to obtain the target cleaned nickel foam.

[0109] Furthermore, the ultrasonic cleaning refers to performing ultrasonic cleaning treatment in an ultrasonic cleaner, and the ultrasonic cleaning time for the nickel foam can be 3 minutes. The cleaning frequency refers to the number of times the preliminary cleaning and ultrasonic cleaning are alternated, which can be three times. For example, the nickel foam is initially cleaned in acetone, then ultrasonically cleaned, and this step is repeated three times. Since the surface of the nickel foam may have grease or organic contaminants, it is necessary to perform preliminary cleaning and ultrasonic cleaning to ensure thorough cleaning.

[0110] Understandably, to thoroughly remove acetone residue, the initially cleaned nickel foam can be rinsed with deionized water and then ultrasonically cleaned again to obtain the target cleaned nickel foam. The ultrasonic cleaning time can be 10 minutes.

[0111] Furthermore, after obtaining the target cleaned nickel foam, it needs to be removed and gently shaken dry. Then, the target cleaned nickel foam is immersed in a dilute nitric acid solution for approximately 1 hour. This helps activate the surface of the nickel foam, thereby increasing the number of active sites on its surface. After 1 hour of immersion, the target cleaned nickel foam needs to be rinsed with a large amount of deionized water to remove any nitric acid residue. Finally, the rinsed target cleaned nickel foam is air-dried for later use, yielding pre-treated nickel foam.

[0112] In this embodiment of the invention, obtaining the molar fraction of titanium doping gradient includes:

[0113] Based on the preset initial threshold for titanium doping mole fraction, the preset gradient value for titanium doping mole fraction, and the number of titanium doping mole fraction tests, the titanium doping gradient mole fraction is calculated using the following formula:

[0114] f i = f1 + (i-1) × g, i ≤ I

[0115] Among them, f i f1 represents the i-th titanium doping mole fraction in the titanium doping gradient mole fraction, f1 represents the initial threshold of titanium doping mole fraction, g represents the titanium doping mole fraction gradient value, and I represents the number of titanium doping mole fraction tests.

[0116] Understandably, the initial threshold for titanium doping mole fraction refers to a preset initial titanium doping mole fraction used to calculate the titanium doping gradient mole fraction, for example, the initial threshold for titanium doping mole fraction can be 1%. The titanium doping mole fraction gradient value refers to the difference between titanium doping mole fractions in the titanium doping gradient mole fraction, for example, when the titanium doping gradient mole fraction is 1%, 3%, or 5%, the titanium doping mole fraction gradient value is 2%. The number of titanium doping mole fraction tests refers to the number of titanium doping mole fractions in the titanium doping gradient mole fraction.

[0117] S2. Sequentially extract the titanium doping molar fraction from the titanium doping gradient molar fraction, weigh 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, and 5 mmol urea, and calculate the number of titanium doping moles based on the titanium doping molar fraction using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate.

[0118] Understandably, the molar number of titanium doping tests refers to the number of moles of titanium element doped.

[0119] In this embodiment of the invention, the step of calculating the number of moles of titanium doping based on the titanium doping mole fraction using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate includes:

[0120] The number of moles of titanium doped was calculated using the following formula based on the stated molar fraction of titanium doping, and using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate:

[0121] n = (0.99 × 10 -3 +0.33×10 -3 +n)×f

[0122] Where n represents the number of moles of titanium doped in the test, and f represents the mole fraction of titanium doping.

[0123] For example, when the molar fraction of titanium doping is 1%, the number of moles of titanium doping tested is 0.013 mmol.

[0124] S3. Weigh out the required amount of titanium trichloride according to the required amount of titanium doping test moles. Add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea and the required amount of titanium trichloride test moles to 30 ml of deionized water and stir until dissolved evenly to obtain the test reaction solution.

[0125] Understandably, the molecular formula of titanium trichloride is TiCl3; therefore, the required molar amount of titanium trichloride for the test can be directly weighed according to the molar amount of titanium doping. Adding ammonium fluoride and urea can adjust the pH of the test reaction solution and promote the formation of layered hydroxides.

[0126] S4. Immerse the pretreated foamed nickel in the test reaction solution to obtain impregnated foamed nickel. Perform a hydrothermal reaction on the impregnated foamed nickel at 120°C for 12 hours to obtain hydrothermal foamed nickel.

[0127] Understandably, the immersion foam nickel refers to pre-treated foam nickel that is completely immersed in the test reaction solution. The hydrothermal foam nickel refers to immersion foam nickel that has undergone a hydrothermal reaction and been cooled to room temperature.

[0128] In this embodiment of the invention, the hydrothermal reaction of the impregnated nickel foam at 120°C for 12 hours to obtain hydrothermal nickel foam includes:

[0129] After transferring the impregnated nickel foam to a pre-constructed high-pressure reactor, the high-pressure reactor is placed in a pre-constructed muffle furnace to obtain hydrothermal nickel foam, wherein the high-pressure reactor is lined with polytetrafluoroethylene;

[0130] The nickel foam to be hydrothermally reacted was subjected to a hydrothermal reaction at 120°C for 12 hours to obtain hydrothermally reacted nickel foam.

[0131] The hydrothermal reactive nickel foam is obtained by cooling the nickel foam to a preset room temperature.

[0132] Understandably, in order to ensure the stability of hydrothermal reaction conditions during the hydrothermal reaction process, it is necessary to place the high-pressure reactor with built-in impregnated nickel foam inside a muffle furnace for hydrothermal reaction.

[0133] S5. After alternating cleaning of the hydrothermal foam nickel with deionized water and pre-prepared anhydrous ethanol, the hydrothermal foam nickel is placed in a preset room temperature environment for drying and growth to obtain nickel-iron-titanium bilayer hydroxide.

[0134] Understandably, alternating cleaning of the hydrothermal nickel foam can remove unreacted substances and byproducts remaining on its surface. After alternating cleaning, the hydrothermal nickel foam needs to be allowed to air dry at room temperature. Upon air drying, titanium-doped nickel-iron bilayer hydroxide (NiFeTi-LDH) nanosheet structures will grow on the hydrothermal nickel foam. Through the above hydrothermal reaction, well-dispersed and uniformly morphological Ti-doped NiFe-based bilayer hydroxide (NiFeTi-LDH) can be obtained, exhibiting excellent performance in applications such as electrocatalysis.

[0135] S6. Summarize the nickel-iron-titanium bilayer hydroxides with various titanium doping molar fractions to obtain a nickel-iron-titanium bilayer hydroxide set. Perform linear sweep voltammetry on the nickel-iron-titanium bilayer hydroxide set to obtain a linear sweep voltammetry curve set and obtain a reference sweep voltammetry curve.

[0136] Explained, the reference scan voltammetry curve refers to the linear scan voltammetry curve of the nickel-iron bilayer hydroxide obtained when the molar fraction of titanium doping is 0 (i.e., undoped titanium). When the molar fraction of titanium doping gradient is 1%, 3%, 6%, 9%, or 12%, the set of linear scan voltammetry curves and the reference scan voltammetry curve can be found in [reference needed]. Figure 5As shown.

[0137] In this embodiment of the invention, obtaining the reference scan voltammetric curve includes:

[0138] Add 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, and 5 mmol urea to 30 ml of deionized water and stir until dissolved to obtain the control reaction solution.

[0139] The pretreated nickel foam is immersed in the control reaction solution to obtain control immersion nickel foam. The control immersion nickel foam is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain control hydrothermal nickel foam.

[0140] After alternating cleaning of the control hydrothermal foam nickel with deionized water and anhydrous ethanol, the control hydrothermal foam nickel was placed in the room temperature environment for drying and growth to obtain nickel-iron-based bilayer hydroxide.

[0141] The nickel-iron-based bilayer hydroxide was subjected to linear sweep voltammetry to obtain a reference sweep voltammetric curve.

[0142] Understandably, since the linear sweep voltammetry curve of nickel-iron bilayer hydroxide with a titanium doping mole fraction of 0 is needed as a reference curve for the linear sweep voltammetry curve set, all preparation processes, except for the difference in preparation conditions of not doping titanium, need to be kept consistent.

[0143] Furthermore, the linear sweep voltammetry test process is as follows: in an alkaline simulated seawater solution, 1 cm... 2 Nickel-iron-titanium bilayer hydroxide (NiFeTi-LDH) or nickel-iron-based bilayer hydroxide (NiFe-LDH) was used as the working electrode, a graphite rod as the counter electrode, and Ag / AgCl as the reference electrode. Linear sweep voltammetry was performed under three-electrode system conditions. Raman spectra of the nickel-iron-titanium bilayer hydroxide (NiFeTi-LDH) and nickel-iron-based bilayer hydroxide (NiFe-LDH) are provided below. Figure 4 As shown. The XRD patterns of the iron-titanium bilayer hydroxide (NiFeTi-LDH) and the nickel-iron bilayer hydroxide (NiFe-LDH) are shown in the figure. Figure 3 As shown, the SEM image of the iron-titanium bilayer hydroxide (NiFeTi-LDH) is referred to [reference needed]. Figure 2 As shown.

[0144] S7. Determine whether a preset low overpotential scanning voltammetry curve set exists in the linear scanning voltammetry curve set based on the reference scanning voltammetry curve.

[0145] Furthermore, the low overpotential scan voltammetric curve set refers to the set of linear scan voltammetric curves with overpotentials smaller than the reference scan voltammetric curve at the same current density. See also... Figure 5 As shown, Figure 5 The electrocatalytic performance of undoped Ti-based nickel-iron bilayer hydroxide (NiFe-LDH) and NiFe-Ti-LDH with different titanium doping gradient molar fractions in the oxygen evolution reaction (OER) was compared. At low current densities, the OER performance of NiFeTi-LDH with a titanium doping molar fraction of 3% and undoped NiFe-LDH were similar in their linear sweep voltammetric curves (at a current density of 100 mA·cm⁻¹). -2 At that time, the overpotential difference between the two is less than 2mV. Figure 5 The diagram shows the linear scan voltammogram (CVT) corresponding to NiFe-LDH (nickel-iron bilayer hydroxide) as the reference scan voltammogram. To the left of this reference scan voltammogram is the linear scan voltammogram corresponding to NiFeTi-LDH (3% Ti) with a titanium doping molar fraction of 3% (the first curve from left to right). In this case, the linear scan voltammogram corresponding to NiFeTi-LDH (3% Ti) with a titanium doping molar fraction of 3% is a low overpotential scan voltammogram. At this point, the number of low overpotential scan voltammograms in the set is 1. Figure 5 It can be seen that when the current density is 1000 mA·cm -2 At this point, the overpotential of nickel-iron-titanium bilayer hydroxide with a titanium doping molar fraction of 3% was 485.4 mV, while the overpotential of undoped nickel-iron-based bilayer hydroxide was 495.7 mV. At this point, the electrocatalytic activity of nickel-iron-titanium bilayer hydroxide with a titanium doping molar fraction of 3% was significantly better than that of nickel-iron-titanium bilayer hydroxide with other titanium doping molar fractions in terms of both overpotential and electrocatalytic activity.

[0146] Furthermore, the electrocatalytic stability of the nickel-iron-based bilayer hydroxide (NiFe-LDH) and the nickel-iron-titanium bilayer hydroxide (NiFeTi-LDH) with a titanium doping molar fraction of 3% can be found in [reference needed]. Figure 6 At the same current density (1 A·cm) -2 After 600 hours of continuous testing, the performance of nickel-iron-based double-layer hydroxide (NiFe-LDH) showed a significant decline after 200 hours, while the catalytic performance of nickel-iron-titanium double-layer hydroxide (NiFeTi-LDH) with a titanium doping molar fraction of 3% remained stable for nearly 600 hours. This demonstrates that nickel-iron-titanium double-layer hydroxide (NiFeTi-LDH) with a titanium doping molar fraction of 3% achieved better OER stability in alkaline seawater than nickel-iron-based double-layer hydroxide (NiFe-LDH).

[0147] If there is no low overpotential scanning voltammetry curve set in the linear scanning voltammetry curve set, then execute S8 and update the titanium doping gradient mole fraction.

[0148] In this embodiment of the invention, updating the molar fraction of the titanium doping gradient includes:

[0149] The last titanium doping mole fraction is extracted from the titanium doping gradient mole fraction. Using the last titanium doping mole fraction and the titanium doping mole fraction gradient value, the initial value of the titanium doping mole fraction is calculated using the following formula:

[0150] f1′=fI I +g

[0151] Where f1′ represents the initial molar fraction of titanium doping, f I This represents the I-th titanium doping mole fraction in the titanium doping gradient mole fraction;

[0152] Using the initial value of the titanium doping mole fraction, the gradient value of the titanium doping mole fraction, and the number of titanium doping mole fraction tests, the iterative titanium doping gradient mole fraction is calculated using the following formula:

[0153] f i f' = f1' + (i-1) × g, i ≤ I

[0154] Among them, f i ′ represents the mole fraction of titanium doping in the i-th iteration of the titanium doping gradient;

[0155] The titanium doping gradient mole fraction is updated using the iterative titanium doping gradient mole fraction.

[0156] Understandably, the last titanium doping mole fraction refers to the last titanium doping mole fraction in the titanium doping gradient mole fraction, and the initial value of the titanium doping mole fraction refers to the first titanium doping mole fraction in the updated titanium doping gradient mole fraction.

[0157] Return to the steps described above for sequentially extracting the molar fraction of titanium doping from the titanium doping gradient molar fraction.

[0158] Understandably, when there is no low overpotential scan voltammetry curve set in the linear scan voltammetry curve set, it indicates that the electrocatalytic activity of each linear scan voltammetry curve in the linear scan voltammetry curve set is less than that of the reference scan voltammetry curve. Therefore, it is necessary to obtain a new linear scan voltammetry curve set using the updated titanium doping gradient molar fraction.

[0159] If a set of low overpotential scanning voltammetric curves exists in the set of linear scanning voltammetric curves, then execute S9 to extract the optimal linear scanning voltammetric curve from the set of low overpotential scanning voltammetric curves.

[0160] Furthermore, the optimal linear sweep voltammetric curve refers to the set of low overpotential sweep voltammetric curves that has the smallest overpotential under the same current density.

[0161] In this embodiment of the invention, the step of extracting the optimal linear scanning voltammetric curve from the low overpotential scanning voltammetric curve set includes:

[0162] Based on the preset intercept current density, the intercept line of the low overpotential scanning volt-ampere curve set is drawn to obtain the intercept intersection point set, wherein the intercept line is c = i′, where c represents the functional expression of the intercept line and i′ represents the intercept current density.

[0163] Extract the minimum interception intersection from the set of interception intersections, wherein the minimum interception intersection refers to the interception intersection with the smallest overpotential in the set of interception intersections;

[0164] The optimal linear scanning voltammetric curve passing through the minimum intercept intersection point is extracted from the set of low overpotential scanning voltammetric curves.

[0165] Understandably, the intercepted intersection point refers to the intersection point of the intercepted straight line and the low overpotential scanning voltammetric curve.

[0166] S10. Identify the optimal titanium doping mole fraction of the optimal linear sweep voltammetric curve, and identify the adjacent titanium doping mole fraction curves of the optimal titanium doping mole fraction.

[0167] Understandably, the optimal titanium doping molar fraction refers to the titanium doping gradient molar fraction corresponding to the optimal linear sweep voltammetric curve.

[0168] Specifically, the adjacent titanium doping molar fraction curves include: a first adjacent titanium doping molar fraction curve and a second adjacent titanium doping molar fraction curve. See also... Figure 5 As shown, the optimal linear sweep voltammetry curve is the linear sweep voltammetry curve corresponding to nickel-iron-titanium bilayer hydroxide (NiFeTi-LDH) with a titanium doping molar fraction of 3%. The first nearest titanium doping molar fraction curve refers to the titanium doping molar fraction that is greater than the optimal titanium doping molar fraction and closest to the optimal titanium doping molar fraction in the titanium doping gradient. See reference. Figure 5 Linear sweep voltammetric curves for a medium doping gradient molar fraction of 6%. The second nearest titanium doping molar fraction curve refers to the titanium doping molar fraction that is less than the optimal titanium doping molar fraction and closest to the optimal titanium doping molar fraction in the titanium doping gradient molar fraction, see reference. Figure 5 Linear sweep voltammetric curves with a doping gradient molar fraction of 1%.

[0169] S11. Obtain the target titanium doping molar fraction based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves, and prepare a ternary non-noble metal layered hydroxide electrocatalytic material based on the target titanium doping molar fraction.

[0170] Understandably, the target titanium doping molar fraction refers to the optimal titanium doping molar fraction among titanium doping gradient molar fractions whose titanium doping molar fraction gradient value is not greater than a standard gradient threshold. The standard gradient threshold refers to a preset titanium doping molar fraction gradient value used to improve the precision of the electrocatalytic performance of the nickel-iron-titanium ternary alloy hydroxide electrocatalyst, for example, 0.2%. The nickel-iron-titanium ternary alloy hydroxide electrocatalyst refers to a nickel-iron-titanium bilayer hydroxide (NiFeTi-LDH) prepared according to the target titanium doping molar fraction.

[0171] In this embodiment of the invention, obtaining the target titanium doping molar fraction based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves includes:

[0172] Based on the preset adjustment spacing molar fraction and the optimal titanium doping molar fraction, the first and second adjustment titanium doping molar fractions are calculated using the following formula:

[0173]

[0174] in, f represents the first debug titanium doping molar fraction. z f represents the optimal molar fraction of titanium doping. d Indicates the mole fraction of the adjustment interval. This indicates the molar fraction of titanium doping in the second tuning test;

[0175] Based on the first adjusted titanium doping molar fraction, the first titanium doping molar number is calculated using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate.

[0176] Weigh the first adjustment titanium trichloride according to the first titanium doping adjustment molar number, add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea and the first adjustment titanium trichloride to 30 ml deionized water and stir until dissolved evenly to obtain the first adjustment reaction solution;

[0177] The pre-treated foamed nickel is immersed in the first debugging reaction solution to obtain the first immersion foamed nickel. The first immersion foamed nickel is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain the first hydrothermal foamed nickel.

[0178] After alternating cleaning of the first hydrothermal foam nickel with deionized water and anhydrous ethanol, the first hydrothermal foam nickel was dried and grown at room temperature to obtain the first nickel-iron-titanium bilayer hydroxide.

[0179] Based on the second adjusted titanium doping molar fraction, the second titanium doping molar number is calculated using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate.

[0180] Weigh the second-adjustment titanium trichloride according to the second titanium doping adjustment molar number, add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea and the second-adjustment titanium trichloride to 30 ml deionized water and stir until dissolved evenly to obtain the second-adjustment reaction solution;

[0181] The pre-treated foamed nickel is immersed in the second debugging reaction solution to obtain the second immersion foamed nickel. The second immersion foamed nickel is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain the second hydrothermal foamed nickel.

[0182] After alternating cleaning with deionized water and anhydrous ethanol, the second hydrothermal foam nickel was dried and grown at room temperature to obtain the second nickel-iron-titanium bilayer hydroxide.

[0183] Linear sweep voltammetry was performed on the first nickel-iron-titanium bilayer hydroxide and the second nickel-iron-titanium bilayer hydroxide to obtain the first linear sweep voltammetric curve and the second linear sweep voltammetric curve.

[0184] Using the intercepting straight line, the first intercepting intersection point, the second intercepting intersection point, and the optimal intercepting intersection point are respectively intercepted in the first linear scanning voltammetry curve, the second linear scanning voltammetry curve, and the optimal linear scanning voltammetry curve;

[0185] Identify the first intersection point overpotential, the second intersection point overpotential, and the optimal intersection point overpotential of the first interception intersection point, the second interception intersection point, and the optimal intersection point, respectively.

[0186] Determine whether the overpotential at the first intersection point is greater than the overpotential at the optimal intersection point;

[0187] If the first intersection overpotential is greater than the optimal intersection overpotential, then obtain the second nearest titanium doping mole fraction of the second nearest titanium doping mole fraction curve;

[0188] The refined titanium doping mole fraction gradient value is calculated based on the optimal titanium doping mole fraction, the second adjacent titanium doping mole fraction, and the number of titanium doping mole fraction tests.

[0189] Determine whether the refined titanium doping mole fraction gradient value is greater than a preset standard gradient threshold;

[0190] If the refined titanium doping mole fraction gradient value is greater than the standard gradient threshold, the number of titanium doping mole fraction tests is updated according to the preset incremental test number, and the above steps of calculating the refined titanium doping mole fraction gradient value based on the optimal titanium doping mole fraction, the second adjacent titanium doping mole fraction and the number of titanium doping mole fraction tests are returned.

[0191] If the refined titanium doping mole fraction gradient value is not greater than the standard gradient threshold, then the refined titanium doping gradient mole fraction is calculated based on the optimal titanium doping mole fraction, the second adjacent titanium doping mole fraction, and the refined titanium doping mole fraction gradient value.

[0192] A refined nickel-iron-titanium bilayer hydroxide set was prepared based on the refined titanium doping gradient molar fraction and 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride and 5 mmol urea.

[0193] Linear scanning voltammetry was performed on the refined nickel-iron-titanium bilayer hydroxide set to obtain a refined linear scanning voltammetry curve set. The target linear scanning voltammetry curve was extracted from the refined linear scanning voltammetry curve set using the truncated straight line.

[0194] Identify the target titanium doping mole fraction corresponding to the target linear scan voltammetric curve;

[0195] If the first intersection overpotential is not greater than the optimal intersection overpotential, then obtain the first adjacent titanium doping mole fraction of the first adjacent titanium doping mole fraction curve.

[0196] The refined titanium doping mole fraction gradient value is calculated based on the optimal titanium doping mole fraction, the first adjacent titanium doping mole fraction, and the number of titanium doping mole fraction tests.

[0197] Determine whether the refined titanium doping mole fraction gradient value is greater than the standard gradient threshold;

[0198] If the refined titanium doping mole fraction gradient value is greater than the standard gradient threshold, the titanium doping mole fraction test number is updated according to the incremental test number, and the above steps of calculating the refined titanium doping mole fraction gradient value based on the optimal titanium doping mole fraction, the first adjacent titanium doping mole fraction, and the titanium doping mole fraction test number are returned.

[0199] If the refined titanium doping mole fraction gradient value is not greater than the standard gradient threshold, then the refined titanium doping gradient mole fraction is calculated based on the optimal titanium doping mole fraction, the first adjacent titanium doping mole fraction, and the refined titanium doping mole fraction gradient value.

[0200] A refined nickel-iron-titanium bilayer hydroxide set was prepared based on the refined titanium doping gradient molar fraction and 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride and 5 mmol urea.

[0201] Linear scanning voltammetry was performed on the refined nickel-iron-titanium bilayer hydroxide set to obtain a refined linear scanning voltammetry curve set. The target linear scanning voltammetry curve was extracted from the refined linear scanning voltammetry curve set using the truncated straight line.

[0202] Identify the target titanium doping mole fraction corresponding to the target linear scan voltammetric curve.

[0203] Explained, the adjustment interval mole fraction refers to a preset mole fraction interval value used to calculate the first and second adjustment titanium doping mole fractions. The adjustment interval mole fraction value should be as small as possible within the limits of experimental accuracy (ensuring that the optimal titanium doping mole fraction and the first and second adjustment titanium doping mole fractions are monotonically changing). Otherwise, it will affect the accuracy of the embodiments of the present invention. For example, when the optimal titanium doping mole fraction is 3%, the adjustment interval mole fraction can be 0.1%, then the first and second adjustment titanium doping mole fractions are 3.1% and 2.9%, respectively.

[0204] Furthermore, the preparation processes of the first nickel-iron-titanium bilayer hydroxide and the second nickel-iron-titanium bilayer hydroxide are the same as those of the nickel-iron-titanium bilayer hydroxide, and will not be repeated here.

[0205] Explained, the first interception intersection point, the second interception intersection point, and the optimal interception intersection point refer to the intersection points of the intercepted straight line with the first linear scanning voltammetric curve, the second linear scanning voltammetric curve, and the optimal linear scanning voltammetric curve, respectively. The first intersection point overpotential, the second intersection point overpotential, and the optimal intersection point overpotential refer to the overpotentials corresponding to the first interception intersection point, the second interception intersection point, and the optimal interception intersection point, respectively.

[0206] Furthermore, the refined titanium doping mole fraction gradient value refers to the titanium doping mole fraction range being the second nearest titanium doping mole fraction and the optimal titanium doping mole fraction, or the optimal titanium doping mole fraction and the first nearest titanium doping mole fraction. The number of titanium doping mole fractions is the titanium doping mole fraction gradient value at the time of the titanium doping mole fraction test. The incremental test number can be 1. In this case, the updated titanium doping mole fraction test number is the previous titanium doping mole fraction test number plus 1.

[0207] Explained, when the first intersection overpotential is greater than the optimal intersection overpotential, it indicates that the overpotential between the optimal intersection overpotential and the first intersection overpotential is increasing. Since the overpotential interval curve corresponding to the initial threshold of titanium doping mole fraction and the I-th titanium doping mole fraction in the titanium doping gradient first decreases and then increases, there exists a minimum overpotential value. When the overpotential between the optimal intersection overpotential and the first intersection overpotential is increasing, it indicates that the optimal intersection overpotential and the first intersection overpotential are to the right of the minimum overpotential value (in the overpotential interval curve). At this time, the target titanium doping mole fraction is between the second adjacent titanium doping mole fraction and the optimal titanium doping mole fraction. Therefore, it is necessary to calculate the refined titanium doping mole fraction gradient value based on the optimal titanium doping mole fraction, the second adjacent titanium doping mole fraction, and the number of titanium doping mole fraction tests.

[0208] Furthermore, when the overpotential at the first intersection point is not greater than the overpotential at the optimal intersection point, it indicates that the overpotential between the optimal intersection point overpotential and the first intersection point overpotential is decreasing. Since the overpotential interval curve corresponding to the initial threshold of titanium doping mole fraction and the I-th titanium doping mole fraction in the titanium doping gradient first decreases and then increases, there exists a minimum overpotential value. When the overpotential between the optimal intersection point overpotential and the first intersection point overpotential is decreasing, it indicates that the optimal intersection point overpotential and the first intersection point overpotential are to the left of the minimum overpotential value (in the overpotential interval curve). At this time, the target titanium doping mole fraction is between the first adjacent titanium doping mole fraction and the optimal titanium doping mole fraction. Therefore, it is necessary to calculate the refined titanium doping mole fraction gradient value based on the optimal titanium doping mole fraction, the first adjacent titanium doping mole fraction, and the number of titanium doping mole fraction tests.

[0209] Compared to the problems described in the background art, this invention requires the preparation of nickel-iron-titanium bilayer hydroxide in three steps. The first step is to obtain pre-treated nickel foam, the second step is to prepare the test reaction solution, and the third step is to dry and grow the nickel-iron-titanium bilayer hydroxide. In the first step, the pre-constructed nickel foam needs to be cleaned to obtain target cleaned nickel foam. Then, the target cleaned nickel foam is soaked in a pre-prepared dilute nitric acid solution for 1 hour, rinsed with deionized water, and dried to obtain pre-treated nickel foam. At this point, the second step can be carried out. First, the pre-treated nickel foam is immersed in the test reaction solution to obtain immersion nickel foam. Then, the nickel foam is dried at 120°C. Hydrothermal nickel foam is obtained by immersion in liquid-based nickel foam and subjected to a hydrothermal reaction for 12 hours. The foam is then alternately cleaned with deionized water and pre-prepared anhydrous ethanol. Finally, the foam is dried and grown in a preset room temperature environment to produce nickel-iron-titanium bilayer hydroxides. Since linear sweep voltammetry (LSV) is required to identify the nickel-iron-titanium bilayer hydroxides with different titanium doping molar fractions, the LSV set is tested to obtain a set of LSV curves. To extract the optimal LSV curve from this set, a low overpotential curve needs to be extracted first. The scan voltammetry curve set can be used to determine whether a preset low overpotential scan voltammetry curve set exists within the linear scan voltammetry curve set. If no low overpotential scan voltammetry curve set exists, the titanium doping gradient mole fraction is updated, and a new linear scan voltammetry curve set is obtained. If a low overpotential scan voltammetry curve set exists, the optimal linear scan voltammetry curve is extracted from that set. However, once the optimal linear scan voltammetry curve is obtained, it may not be the optimal linear scan voltammetry curve within the titanium doping mole fraction range of the low overpotential scan voltammetry curve set. The voltammetric curve requires identifying the optimal titanium doping molar fraction for the optimal linear sweep voltammetric curve, and then identifying the adjacent titanium doping molar fraction curves. Based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves, the target titanium doping molar fraction is obtained. Finally, a ternary non-noble metal layered hydroxide electrocatalytic material is prepared based on the target titanium doping molar fraction. Therefore, the main purpose of the preparation method, apparatus, electronic equipment, and computer-readable storage medium of the ternary non-noble metal layered hydroxide electrocatalytic material proposed in this invention is to solve the problems of high cost, poor corrosion resistance, and low electrocatalytic efficiency of current electrocatalysts used for water electrolysis.

[0210] Example 2:

[0211] like Figure 7The diagram shown is a functional block diagram of a device for preparing ternary non-precious metal layered hydroxide electrocatalytic materials according to an embodiment of the present invention.

[0212] The apparatus 100 for preparing ternary non-precious metal layered hydroxide electrocatalytic materials according to the present invention can be installed in an electronic device. Depending on the functions to be performed, the apparatus 100 may include a nickel foam pretreatment module 101, a test reaction solution preparation module 102, a nickel-iron-titanium bilayer hydroxide growth module 103, an optimal linear scanning voltammetric curve identification module 104, and a nickel-iron-titanium ternary alloy hydroxide preparation module 105. The module described in this invention can also be referred to as a unit, which refers to a series of computer program segments that can be executed by the processor of an electronic device and can perform a fixed function, and are stored in the memory of the electronic device.

[0213] The pre-treatment module 101 for nickel foam is used to clean the pre-constructed nickel foam to obtain target cleaned nickel foam. The target cleaned nickel foam is soaked in a pre-prepared dilute nitric acid solution for 1 hour, then rinsed with deionized water and dried to obtain pre-treated nickel foam and obtain the molar fraction of titanium doping gradient.

[0214] The test reaction solution preparation module 102 is used to sequentially extract the titanium doping molar fraction from the titanium doping gradient molar fraction, weigh 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, and 5 mmol urea, and calculate the number of titanium doping moles using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate based on the titanium doping molar fraction; weigh the number of titanium trichloride moles based on the number of titanium doping moles, add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea, and the number of titanium trichloride moles to 30 ml of deionized water and stir until dissolved evenly to obtain the test reaction solution;

[0215] The nickel-iron-titanium bilayer hydroxide growth module 103 is used to immerse the pre-treated foamed nickel in the test reaction solution to obtain immersion foamed nickel, perform a hydrothermal reaction on the immersion foamed nickel at 120°C for 12 hours to obtain hydrothermal foamed nickel; after performing alternating cleaning of the hydrothermal foamed nickel with deionized water and pre-prepared anhydrous ethanol, the hydrothermal foamed nickel is placed in a preset room temperature environment for drying and growth to obtain nickel-iron-titanium bilayer hydroxide;

[0216] The optimal linear scan voltammetry curve identification module 104 is used to summarize nickel-iron-titanium bilayer hydroxides with various titanium doping molar fractions to obtain a nickel-iron-titanium bilayer hydroxide set. Linear scan voltammetry is then performed on this set to obtain a linear scan voltammetry curve set and a reference scan voltammetry curve. Based on the reference scan voltammetry curve, it is determined whether a preset low overpotential scan voltammetry curve set exists within the linear scan voltammetry curve set. The low overpotential scan voltammetry curve set refers to the set of linear scan voltammetry curves with an overpotential lower than that of the reference scan voltammetry curve at the same current density. If no low overpotential scan voltammetry curve set exists within the linear scan voltammetry curve set, the titanium doping gradient molar fraction is updated, and the process returns to the previous steps of sequentially extracting the titanium doping molar fraction from the titanium doping gradient molar fraction. If a low overpotential scan voltammetry curve set exists within the linear scan voltammetry curve set, the optimal linear scan voltammetry curve is extracted from this set.

[0217] The nickel-iron-titanium ternary alloy hydroxide preparation module 105 is used to identify the optimal titanium doping molar fraction of the optimal linear scanning voltammetric curve, and to identify the adjacent titanium doping molar fraction curves of the optimal titanium doping molar fraction, wherein the adjacent titanium doping molar fraction curves include: a first adjacent titanium doping molar fraction curve and a second adjacent titanium doping molar fraction curve; to obtain the target titanium doping molar fraction based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves, and to prepare a ternary non-noble metal layered hydroxide electrocatalytic material based on the target titanium doping molar fraction.

[0218] In detail, the modules in the ternary non-noble metal layered hydroxide electrocatalytic material preparation apparatus 100 described in this embodiment of the invention employ the same methods as described above during use. Figure 1 The preparation method of the ternary non-precious metal layered hydroxide electrocatalytic material described herein uses the same technical means and can produce the same technical effect, so it will not be repeated here.

[0219] Example 3:

[0220] like Figure 8 The diagram shown is a schematic diagram of an electronic device for realizing a method for preparing ternary non-noble metal layered hydroxide electrocatalytic materials according to an embodiment of the present invention.

[0221] The electronic device 1 may include a processor 10, a memory 11, a bus 12 and a communication interface 13, and may also include a computer program stored in the memory 11 and executable on the processor 10, such as a preparation program for a ternary non-precious metal layered hydroxide electrocatalytic material.

[0222] The memory 11 includes at least one type of readable storage medium, such as flash memory, portable hard drive, multimedia card, card-type memory (e.g., SD or DX memory), magnetic memory, disk, optical disk, etc. In some embodiments, the memory 11 can be an internal storage unit of the electronic device 1, such as a portable hard drive. In other embodiments, the memory 11 can be an external storage device of the electronic device 1, such as a plug-in portable hard drive, SmartMediaCard (SMC), SecureDigital (SD) card, or FlashCard. Furthermore, the memory 11 can include both internal and external storage units of the electronic device 1. The memory 11 can be used not only to store application software and various types of data installed on the electronic device 1, such as the code for the preparation program of ternary non-precious metal layered hydroxide electrocatalyst materials, but also to temporarily store data that has been output or will be output.

[0223] In some embodiments, the processor 10 may be composed of integrated circuits, such as a single packaged integrated circuit or multiple integrated circuits with the same or different functions, including combinations of one or more central processing units (CPUs), microprocessors, digital processing chips, graphics processors, and various control chips. The processor 10 is the control unit of the electronic device, connecting various components of the entire electronic device through various interfaces and lines. It executes programs or modules stored in the memory 11 (e.g., the preparation program of ternary non-precious metal layered hydroxide electrocatalytic materials) and calls data stored in the memory 11 to perform various functions of the electronic device 1 and process data.

[0224] The bus can be a Peripheral Component Interconnect (PCI) bus or an Extended Industry Standard Architecture (EISA) bus, etc. This bus can be divided into an address bus, a data bus, a control bus, etc. The bus is configured to enable communication between the memory 11 and at least one processor 10, etc.

[0225] Figure 8 Only electronic devices with components are shown; it will be understood by those skilled in the art that... Figure 8The structure shown does not constitute a limitation on the electronic device 1, and may include fewer or more components than shown, or combine certain components, or have different component arrangements.

[0226] For example, although not shown, the electronic device 1 may also include a power supply (such as a battery) to power the various components. Preferably, the power supply can be logically connected to the at least one processor 10 through a power management device, thereby enabling functions such as charging management, discharging management, and power consumption management. The power supply may also include one or more DC or AC power supplies, recharging devices, power fault detection circuits, power converters or inverters, power status indicators, and other arbitrary components. The electronic device 1 may also include various sensors, Bluetooth modules, Wi-Fi modules, etc., which will not be described in detail here.

[0227] Furthermore, the electronic device 1 may also include a network interface. Optionally, the network interface may include a wired interface and / or a wireless interface (such as a Wi-Fi interface, a Bluetooth interface, etc.), which is typically used to establish communication connections between the electronic device 1 and other electronic devices.

[0228] Optionally, the electronic device 1 may further include a user interface, which may be a display, an input unit (such as a keyboard), or a standard wired or wireless interface. Optionally, in some embodiments, the display may be an LED display, a liquid crystal display, a touch-sensitive liquid crystal display, or an OLED (Organic Light-Emitting Diode) touchscreen. The display may also be appropriately referred to as a screen or display unit, used to display information processed in the electronic device 1 and to display a visual user interface.

[0229] It should be understood that the embodiments described are for illustrative purposes only and are not limited to this structure in the scope of the patent application.

[0230] The preparation program for the ternary non-noble metal layered hydroxide electrocatalytic material stored in the memory 11 of the electronic device 1 is a combination of multiple instructions. When run in the processor 10, it can achieve the following:

[0231] The pre-constructed nickel foam is cleaned to obtain target cleaned nickel foam. The target cleaned nickel foam is immersed in a pre-prepared dilute nitric acid solution for 1 hour, then rinsed with deionized water and dried to obtain pre-treated nickel foam. The molar fraction of titanium doping gradient is obtained.

[0232] The titanium doping molar fraction was extracted sequentially from the titanium doping gradient molar fraction. 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride and 5 mmol urea were weighed. Based on the titanium doping molar fraction, the number of titanium doping moles was calculated using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate.

[0233] Weigh out the required amount of titanium trichloride according to the required amount of titanium doping test moles. Add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea and the required amount of titanium trichloride test moles to 30 ml of deionized water and stir until dissolved evenly to obtain the test reaction solution.

[0234] The pretreated nickel foam is immersed in the test reaction solution to obtain immersion nickel foam. The immersion nickel foam is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain hydrothermal nickel foam.

[0235] After alternating cleaning of the hydrothermal foam nickel with deionized water and pre-prepared anhydrous ethanol, the hydrothermal foam nickel is placed in a preset room temperature environment for drying and growth to obtain nickel-iron-titanium bilayer hydroxide.

[0236] The nickel-iron-titanium bilayer hydroxides with various titanium doping molar fractions are summarized to obtain a set of nickel-iron-titanium bilayer hydroxides. The set of nickel-iron-titanium bilayer hydroxides is then subjected to linear sweep voltammetry to obtain a set of linear sweep voltammetric curves, and a reference sweep voltammetric curve is obtained.

[0237] Based on the reference scan voltammetry curve, determine whether there is a preset low overpotential scan voltammetry curve set in the linear scan voltammetry curve set. The low overpotential scan voltammetry curve set refers to the set of linear scan voltammetry curves with an overpotential lower than that of the reference scan voltammetry curve under the same current density.

[0238] If there is no low overpotential scanning voltammetric curve set in the linear scanning voltammetric curve set, then update the titanium doping gradient mole fraction and return to the steps described above of sequentially extracting the titanium doping mole fraction from the titanium doping gradient mole fraction.

[0239] If a set of low overpotential scanning voltammetric curves exists within the set of linear scanning voltammetric curves, then the optimal linear scanning voltammetric curve is extracted from the set of low overpotential scanning voltammetric curves.

[0240] Identify the optimal titanium doping mole fraction of the optimal linear sweep voltammetric curve, and identify the adjacent titanium doping mole fraction curves of the optimal titanium doping mole fraction, wherein the adjacent titanium doping mole fraction curves include: a first adjacent titanium doping mole fraction curve and a second adjacent titanium doping mole fraction curve.

[0241] The target titanium doping molar fraction is obtained based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves, and a ternary non-noble metal layered hydroxide electrocatalytic material is prepared based on the target titanium doping molar fraction.

[0242] Specifically, the processor 10's implementation method for the above instructions can be found in [reference needed]. Figures 1 to 7 The descriptions of the relevant steps in the corresponding embodiments are not repeated here.

[0243] Furthermore, if the modules / units integrated in the electronic device 1 are implemented as software functional units and sold or used as independent products, they can be stored in a computer-readable storage medium. The computer-readable storage medium can be volatile or non-volatile. For example, the computer-readable medium may include: any entity or device capable of carrying the computer program code, a recording medium, a USB flash drive, a portable hard drive, a magnetic disk, an optical disk, a computer memory, or a read-only memory (ROM).

[0244] The present invention also provides a computer-readable storage medium storing a computer program, which, when executed by a processor of an electronic device, can perform the following:

[0245] The pre-constructed nickel foam is cleaned to obtain target cleaned nickel foam. The target cleaned nickel foam is immersed in a pre-prepared dilute nitric acid solution for 1 hour, then rinsed with deionized water and dried to obtain pre-treated nickel foam. The molar fraction of titanium doping gradient is obtained.

[0246] The titanium doping molar fraction was extracted sequentially from the titanium doping gradient molar fraction. 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride and 5 mmol urea were weighed. Based on the titanium doping molar fraction, the number of titanium doping moles was calculated using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate.

[0247] Weigh out the required amount of titanium trichloride according to the required amount of titanium doping test moles. Add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea and the required amount of titanium trichloride test moles to 30 ml of deionized water and stir until dissolved evenly to obtain the test reaction solution.

[0248] The pretreated nickel foam is immersed in the test reaction solution to obtain immersion nickel foam. The immersion nickel foam is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain hydrothermal nickel foam.

[0249] After alternating cleaning of the hydrothermal foam nickel with deionized water and pre-prepared anhydrous ethanol, the hydrothermal foam nickel is placed in a preset room temperature environment for drying and growth to obtain nickel-iron-titanium bilayer hydroxide.

[0250] The nickel-iron-titanium bilayer hydroxides with various titanium doping molar fractions are summarized to obtain a set of nickel-iron-titanium bilayer hydroxides. The set of nickel-iron-titanium bilayer hydroxides is then subjected to linear sweep voltammetry to obtain a set of linear sweep voltammetric curves, and a reference sweep voltammetric curve is obtained.

[0251] Based on the reference scan voltammetry curve, determine whether there is a preset low overpotential scan voltammetry curve set in the linear scan voltammetry curve set. The low overpotential scan voltammetry curve set refers to the set of linear scan voltammetry curves with an overpotential lower than that of the reference scan voltammetry curve under the same current density.

[0252] If there is no low overpotential scanning voltammetric curve set in the linear scanning voltammetric curve set, then update the titanium doping gradient mole fraction and return to the steps described above of sequentially extracting the titanium doping mole fraction from the titanium doping gradient mole fraction.

[0253] If a set of low overpotential scanning voltammetric curves exists within the set of linear scanning voltammetric curves, then the optimal linear scanning voltammetric curve is extracted from the set of low overpotential scanning voltammetric curves.

[0254] Identify the optimal titanium doping mole fraction of the optimal linear sweep voltammetric curve, and identify the adjacent titanium doping mole fraction curves of the optimal titanium doping mole fraction, wherein the adjacent titanium doping mole fraction curves include: a first adjacent titanium doping mole fraction curve and a second adjacent titanium doping mole fraction curve.

[0255] The target titanium doping molar fraction is obtained based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves, and a ternary non-noble metal layered hydroxide electrocatalytic material is prepared based on the target titanium doping molar fraction.

[0256] The modules described as separate components may or may not be physically separate. The components shown as modules may or may not be physical units; that is, they may be located in one place or distributed across multiple network units. Some or all of the modules can be selected to achieve the purpose of this embodiment according to actual needs.

[0257] Furthermore, the functional modules in the various embodiments of the present invention can be integrated into one processing unit, or each unit can exist physically separately, or two or more units can be integrated into one unit. The integrated unit can be implemented in hardware or in the form of hardware plus software functional modules.

[0258] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention.

[0259] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a ternary non-noble metal layered hydroxide electrocatalytic material, characterized in that, The method includes: The pre-constructed nickel foam is cleaned to obtain target cleaned nickel foam. The target cleaned nickel foam is immersed in a pre-prepared dilute nitric acid solution for 1 hour, then rinsed with deionized water and dried to obtain pre-treated nickel foam. The molar fraction of titanium doping gradient is obtained. The titanium doping molar fraction was extracted sequentially from the titanium doping gradient molar fraction. 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride and 5 mmol urea were weighed. Based on the titanium doping molar fraction, the number of titanium doping moles was calculated using the 0.99 mmol nickel chloride hexahydrate and 0.33 mmol ferric nitrate nonahydrate. Weigh out the required amount of titanium trichloride according to the required amount of titanium doping test moles. Add the 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride, 5 mmol urea and the required amount of titanium trichloride test moles to 30 ml of deionized water and stir until dissolved evenly to obtain the test reaction solution. The pretreated nickel foam is immersed in the test reaction solution to obtain immersion nickel foam. The immersion nickel foam is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain hydrothermal nickel foam. After alternating cleaning of the hydrothermal foam nickel with deionized water and pre-prepared anhydrous ethanol, the hydrothermal foam nickel is placed in a preset room temperature environment for drying and growth to obtain nickel-iron-titanium bilayer hydroxide. The nickel-iron-titanium bilayer hydroxides with various titanium doping molar fractions are summarized to obtain a set of nickel-iron-titanium bilayer hydroxides. The set of nickel-iron-titanium bilayer hydroxides is then subjected to linear sweep voltammetry to obtain a set of linear sweep voltammetric curves, and a reference sweep voltammetric curve is obtained. Based on the reference scan voltammetry curve, determine whether there is a preset low overpotential scan voltammetry curve set in the linear scan voltammetry curve set. The low overpotential scan voltammetry curve set refers to the set of linear scan voltammetry curves with an overpotential lower than that of the reference scan voltammetry curve under the same current density. If there is no low overpotential scanning voltammetric curve set in the linear scanning voltammetric curve set, then update the titanium doping gradient mole fraction and return to the steps described above of sequentially extracting the titanium doping mole fraction from the titanium doping gradient mole fraction. If a set of low overpotential scanning voltammetric curves exists within the set of linear scanning voltammetric curves, then the optimal linear scanning voltammetric curve is extracted from the set of low overpotential scanning voltammetric curves. Identify the optimal titanium doping mole fraction of the optimal linear sweep voltammetric curve, and identify the adjacent titanium doping mole fraction curves of the optimal titanium doping mole fraction, wherein the adjacent titanium doping mole fraction curves include: a first adjacent titanium doping mole fraction curve and a second adjacent titanium doping mole fraction curve. The target titanium doping molar fraction is obtained based on the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curves, and a ternary non-noble metal layered hydroxide electrocatalytic material is prepared based on the target titanium doping molar fraction. The process of obtaining the molar fraction of titanium doping gradient includes: According to the preset titanium doping mole fraction starting threshold, the preset titanium doping mole fraction gradient value and the titanium doping mole fraction test number, a titanium doping gradient mole fraction is calculated by using the following formula: f i = fi + (i - 1) x g, i < I wherein f i represents the i-th titanium doping mole fraction in the titanium doping gradient mole fraction, f1 represents the titanium doping mole fraction starting threshold value, g represents the titanium doping mole fraction gradient value, and I represents the titanium doping mole fraction test number; The titanium doping test mole number is calculated according to the titanium doping mole fraction by using the 0.99 mmol nickel chloride hexahydrate and the 0.33 mmol ferric nitrate nonahydrate, and the titanium doping test mole number is calculated according to the titanium doping mole fraction by using the 0.99 mmol nickel chloride hexahydrate and the 0.33 mmol ferric nitrate nonahydrate. The titanium doping test mole number is calculated according to the titanium doping mole fraction by using the 0.99 mmol nickel chloride hexahydrate and the 0.33 mmol ferric nitrate nonahydrate, and the titanium doping test mole number is calculated according to the titanium doping mole fraction by using the 0.99 mmol nickel chloride hexahydrate and the 0.33 mmol ferric nitrate nonahydrate. n = (0.99 x 10 -3 + 0.33 x 10 -3 + n) x f Wherein, n represents the titanium doping test mole number, and f represents the titanium doping mole fraction.

2. The method for preparing a ternary non-noble metal layered hydroxide electrocatalytic material according to claim 1, characterized in that, The pre-constructed nickel foam is washed to obtain a target washed nickel foam, including: The nickel foam is subjected to preliminary washing in pre-configured acetone and then subjected to ultrasonic washing until the preliminary washing and ultrasonic washing reach a preset washing frequency to obtain a preliminary washed nickel foam; The preliminary washed nickel foam is washed with pre-acquired deionized water and then subjected to ultrasonic washing according to a preset ultrasonic washing time to obtain a target washed nickel foam.

3. The method for preparing a ternary non-noble metal layered double hydroxide electrocatalytic material according to claim 1, characterized in that, The immersion liquid nickel foam is subjected to hydrothermal reaction at 120 DEG C for 12 hours to obtain a hydrothermal nickel foam, including: The immersion liquid nickel foam is transferred to a pre-constructed high-pressure reaction kettle, and the high-pressure reaction kettle is placed in a pre-constructed muffle furnace to obtain a to-be-hydrothermally-treated nickel foam, wherein the high-pressure reaction kettle is lined with polytetrafluoroethylene; The to-be-hydrothermally-treated nickel foam is subjected to 120 DEG C hydrothermal reaction for 12 hours to obtain a hydrothermal reaction nickel foam; The hydrothermal reaction nickel foam is cooled to a preset room temperature to obtain a hydrothermal nickel foam.

4. The method for preparing a ternary non-noble metal layered double hydroxide electrocatalytic material according to claim 1, characterized in that, The reference scan voltammogram is obtained, including: 0.99 mmol nickel chloride hexahydrate, 0.33 mmol ferric nitrate nonahydrate, 5 mmol ammonium fluoride and 5 mmol urea are added to 30 ml deionized water and stirred until dissolved uniformly to obtain a control reaction solution; The pre-processed nickel foam is immersed in the control reaction solution to obtain a control immersion liquid nickel foam, which is subjected to hydrothermal reaction at 120 DEG C for 12 hours to obtain a control hydrothermal nickel foam; The control hydrothermal nickel foam is subjected to alternating washing with deionized water and the anhydrous ethanol, and then placed in the room temperature environment for drying growth to obtain a nickel-iron-based double-layer hydroxide; The nickel-iron-based double-layer hydroxide is subjected to linear scan voltammetry test to obtain a reference scan voltammogram.

5. The method for preparing a ternary non-noble metal layered double hydroxide electrocatalytic material according to claim 1, characterized in that, The titanium doping gradient mole fraction is updated, including: The last titanium doping mole fraction is extracted from the titanium doping gradient mole fraction, and a titanium doping mole fraction starting value is calculated by using the last titanium doping mole fraction and the titanium doping mole fraction gradient value by using the following formula: f1 ′ = f I + g wherein fi ′ represents the initial value of the titanium doping mole fraction, f I represents the first titanium doping mole fraction in the titanium doping gradient mole fraction; The titanium doping mole fraction starting value, the titanium doping mole fraction gradient value and the titanium doping mole fraction test number are used to calculate an iterative titanium doping gradient mole fraction by using the following formula: f i ′ = f1 ′ + (i - 1) x g, i < I wherein f i ′ denotes the i-th iteration titanium doping mole fraction in the iteration titanium doping gradient mole fraction; The titanium doping gradient mole fraction is updated by using the iterative titanium doping gradient mole fraction.

6. The method for preparing a ternary non-noble metal layered double hydroxide electrocatalytic material according to claim 1, characterized in that, The extracting the optimal linear sweep voltammetry curve in the low overpotential sweep voltammetry curve set comprises: According to the preset intercept current density, an intercept straight line of the set of low overpotential scanning voltammograms is obtained, wherein the intercept straight line is c=i ′ wherein c represents a function expression of the intercept straight line, i ′ represents the intercept current density; The minimum intercept intersection is extracted from the intercept intersection set, wherein the minimum intercept intersection refers to the intercept intersection with the minimum overpotential in the intercept intersection set; The optimal linear sweep voltammetry curve over the minimum intercept intersection is extracted from the low overpotential sweep voltammetry curve set.

7. The method for preparing a ternary non-noble metal layered double hydroxide electrocatalytic material according to claim 6, characterized in that, The obtaining the target titanium doping molar fraction according to the optimal titanium doping molar fraction and the adjacent titanium doping molar fraction curve comprises: According to the preset debugging interval molar fraction and the optimal titanium doping molar fraction, the first debugging titanium doping molar fraction and the second debugging titanium doping molar fraction are calculated by using the following formula: wherein, represents the first tuning titanium dopant mole fraction, f z represents the optimum titanium dopant mole fraction, f d represents the tuning interval mole fraction, represents the second tuning titanium dopant mole fraction; According to the first debugging titanium doping molar fraction, the first titanium doping debugging molar number is calculated by using the 0.99 mmol of nickel chloride hexahydrate and the 0.33 mmol of iron nitrate nonahydrate; According to the first titanium doping debugging molar number, the first debugging titanium trichloride is weighed, the 0.99 mmol of nickel chloride hexahydrate, the 0.33 mmol of iron nitrate nonahydrate, 5 mmol of ammonium fluoride, 5 mmol of urea and the first debugging titanium trichloride are added into 30 ml of deionized water and stirred until uniformly dissolved to obtain a first debugging reaction solution; The pre-treatment foam nickel is immersed in the first debugging reaction solution to obtain first immersion foam nickel, and the first immersion foam nickel is subjected to hydrothermal reaction at 120°C for 12 h to obtain first hydrothermal foam nickel; After the first hydrothermal foam nickel is subjected to alternating cleaning by using deionized water and anhydrous ethanol, the first hydrothermal foam nickel is placed in a room temperature environment for drying growth to obtain first nickel-iron-titanium double-layer hydroxide; According to the second debugging titanium doping molar fraction, the second titanium doping debugging molar number is calculated by using the 0.99 mmol of nickel chloride hexahydrate and the 0.33 mmol of iron nitrate nonahydrate; According to the second titanium doping debugging molar number, the second debugging titanium trichloride is weighed, the 0.99 mmol of nickel chloride hexahydrate, the 0.33 mmol of iron nitrate nonahydrate, 5 mmol of ammonium fluoride, 5 mmol of urea and the second debugging titanium trichloride are added into 30 ml of deionized water and stirred until uniformly dissolved to obtain a second debugging reaction solution; The pre-treatment foam nickel is immersed in the second debugging reaction solution to obtain second immersion foam nickel, and the second immersion foam nickel is subjected to hydrothermal reaction at 120°C for 12 h to obtain second hydrothermal foam nickel; After the second hydrothermal foam nickel is subjected to alternating cleaning by using deionized water and anhydrous ethanol, the second hydrothermal foam nickel is placed in a room temperature environment for drying growth to obtain second nickel-iron-titanium double-layer hydroxide; The first nickel-iron-titanium double-layer hydroxide and the second nickel-iron-titanium double-layer hydroxide are respectively subjected to linear sweep voltammetry test to obtain a first linear sweep voltammetry curve and a second linear sweep voltammetry curve; The intercept straight line is used to intercept a first intercept intersection, a second intercept intersection and an optimal intercept intersection in the first linear sweep voltammetry curve, the second linear sweep voltammetry curve and the optimal linear sweep voltammetry curve respectively. Identify the first intersection overpotential, the second intersection overpotential and the best intersection overpotential of the first intersection point, the second intersection point and the best intersection point of the first intercept respectively; Determine whether the first intersection overpotential is greater than the best intersection overpotential; If the first intersection overpotential is greater than the best intersection overpotential, calculate the refined titanium doping mole fraction gradient value according to the best titanium doping mole fraction, the second debugging titanium doping mole fraction and the titanium doping mole fraction test number; Determine whether the refined titanium doping mole fraction gradient value is greater than the preset standard gradient threshold value; If the refined titanium doping mole fraction gradient value is greater than the standard gradient threshold value, update the titanium doping mole fraction test number according to the preset incremental test number, and return to the step of calculating the refined titanium doping mole fraction gradient value according to the best titanium doping mole fraction, the second debugging titanium doping mole fraction and the titanium doping mole fraction test number; If the refined titanium doping mole fraction gradient value is not greater than the standard gradient threshold value, calculate the refined titanium doping gradient mole fraction according to the best titanium doping mole fraction, the second debugging titanium doping mole fraction and the refined titanium doping mole fraction gradient value; Prepare a refined nickel-iron-titanium double-layer hydroxide set according to the refined titanium doping gradient mole fraction and 0.99 mmol of nickel chloride hexahydrate, 0.33 mmol of iron nitrate nonahydrate, 5 mmol of ammonium fluoride and 5 mmol of urea; Perform linear sweep voltammetry test on the refined nickel-iron-titanium double-layer hydroxide set to obtain a refined linear sweep voltammetry curve set, and extract a target linear sweep voltammetry curve from the refined linear sweep voltammetry curve set using the intercept straight line; Identify the target titanium doping mole fraction corresponding to the target linear sweep voltammetry curve; If the first intersection overpotential is not greater than the best intersection overpotential, calculate the refined titanium doping mole fraction gradient value according to the best titanium doping mole fraction, the first debugging titanium doping mole fraction and the titanium doping mole fraction test number; Determine whether the refined titanium doping mole fraction gradient value is greater than the standard gradient threshold value; If the refined titanium doping mole fraction gradient value is greater than the standard gradient threshold value, update the titanium doping mole fraction test number according to the incremental test number, and return to the step of calculating the refined titanium doping mole fraction gradient value according to the best titanium doping mole fraction, the first debugging titanium doping mole fraction and the titanium doping mole fraction test number; If the refined titanium doping mole fraction gradient value is not greater than the standard gradient threshold value, calculate the refined titanium doping gradient mole fraction according to the best titanium doping mole fraction, the first debugging titanium doping mole fraction and the refined titanium doping mole fraction gradient value; Prepare a refined nickel-iron-titanium double-layer hydroxide set according to the refined titanium doping gradient mole fraction and 0.99 mmol of nickel chloride hexahydrate, 0.33 mmol of iron nitrate nonahydrate, 5 mmol of ammonium fluoride and 5 mmol of urea; The linear sweep voltammetry test is performed on the refined nickel-iron-titanium double-layer hydroxide set to obtain a refined linear sweep voltammetry curve set, and the target linear sweep voltammetry curve is extracted from the refined linear sweep voltammetry curve set by using the intercept straight line. The target linear sweep voltammetry curve corresponds to a target titanium doping molar fraction.

8. A device for the preparation of ternary non-noble metal layered hydroxide electrocatalytic material using the method according to claim 1, characterized by, The device comprises: A foam nickel pre-treatment module is configured to clean a pre-constructed foam nickel to obtain a target cleaned foam nickel. The target cleaned foam nickel is soaked in a pre-configured dilute nitric acid solution for 1 hour, then rinsed with deionized water and dried to obtain a pre-treatment foam nickel. The titanium doping gradient molar fraction is obtained. A test reaction solution preparation module is configured to sequentially extract titanium doping molar fractions from the titanium doping gradient molar fraction. 0.99 mmol of nickel chloride hexahydrate, 0.33 mmol of iron nitrate nonahydrate, 5 mmol of ammonium fluoride, and 5 mmol of urea are weighed. The titanium doping test molar number is calculated based on the titanium doping molar fraction and the 0.99 mmol of nickel chloride hexahydrate and the 0.33 mmol of iron nitrate nonahydrate. The test molar number of titanium trichloride is weighed according to the titanium doping test molar number. The 0.99 mmol of nickel chloride hexahydrate, the 0.33 mmol of iron nitrate nonahydrate, the 5 mmol of ammonium fluoride, the 5 mmol of urea, and the test molar number of titanium trichloride are added to 30 ml of deionized water and stirred until dissolved uniformly to obtain a test reaction solution. A nickel-iron-titanium double-layer hydroxide growth module is configured to immerse the pre-treatment foam nickel in the test reaction solution to obtain an immersion foam nickel. The immersion foam nickel is subjected to a hydrothermal reaction at 120°C for 12 hours to obtain a hydrothermal foam nickel. The hydrothermal foam nickel is subjected to alternating cleaning with deionized water and pre-configured anhydrous ethanol, and then dried and grown in a pre-set room temperature environment to obtain a nickel-iron-titanium double-layer hydroxide. An optimal linear sweep voltammetry curve identification module is configured to collect nickel-iron-titanium double-layer hydroxides of various titanium doping molar fractions to obtain a set of nickel-iron-titanium double-layer hydroxides. The set of nickel-iron-titanium double-layer hydroxides is subjected to linear sweep voltammetry test to obtain a set of linear sweep voltammetry curves, and a reference scan voltammetry curve is obtained. It is determined whether there is a pre-set low overpotential scan voltammetry curve set in the set of linear sweep voltammetry curves based on the reference scan voltammetry curve, wherein the low overpotential scan voltammetry curve set refers to a set of linear sweep voltammetry curves with an overpotential less than that of the reference scan voltammetry curve under the same current density. If there is no low overpotential scan voltammetry curve set in the set of linear sweep voltammetry curves, the titanium doping gradient molar fraction is updated, and the step of sequentially extracting titanium doping molar fractions from the titanium doping gradient molar fraction is returned. If there is a low overpotential scan voltammetry curve set in the set of linear sweep voltammetry curves, an optimal linear sweep voltammetry curve is extracted from the low overpotential scan voltammetry curve set. The nickel-iron-titanium ternary alloy hydroxide preparation module is used for identifying an optimal titanium doping mole fraction of an optimal linear sweep voltammetry curve, identifying a titanium doping mole fraction curve adjacent to the optimal titanium doping mole fraction, wherein the titanium doping mole fraction curve adjacent to the optimal titanium doping mole fraction comprises a first titanium doping mole fraction curve adjacent to the optimal titanium doping mole fraction and a second titanium doping mole fraction curve adjacent to the optimal titanium doping mole fraction; obtaining a target titanium doping mole fraction according to the optimal titanium doping mole fraction and the titanium doping mole fraction curve adjacent to the optimal titanium doping mole fraction, and preparing a ternary non-noble metal layered hydroxide electrocatalytic material according to the target titanium doping mole fraction.

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