A squarate complex derived nickel-iron based double metal hydroxide, a method of preparation and an electrode
By forming a nickel-iron-based bimetallic hydroxide derived from a squaric acid complex with an interactive micron-sized pore structure on the surface of nickel foam, the problems of high overpotential and catalyst stability in the anodic oxygen evolution reaction were solved, achieving high efficiency, high current density, and long-term stability, thus promoting the large-scale application of hydrogen production by water electrolysis.
Patent Information
- Application Number
- CN202411780298.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-05
- Publication Date
- 2025-12-26
- Estimated Expiration
- 2044-12-05
AI Technical Summary
In existing water electrolysis hydrogen production technologies, the oxygen evolution reaction at the anode has a large reaction energy barrier and slow kinetics, resulting in high overpotential. Furthermore, the catalyst is not firmly bonded to the substrate material, making it difficult to maintain stability under high current conditions, which limits the efficiency and large-scale application of water electrolysis hydrogen production.
By using a nickel-iron-based bimetallic hydroxide derived from a squaric acid complex, an interactive micron-scale pore structure is formed on the surface of nickel foam through hydrothermal treatment and electrochemical activation and reconstruction methods. Combined with a nickel-derived catalyst and substrate, the stability and activity of the catalyst are improved.
It achieves an ultra-high current density of up to 3000 mA/cm2 and long-term stability of over 100 hours under high current conditions, which significantly improves the current limit of the oxygen evolution reaction and supports the large-scale development of hydrogen production by water electrolysis.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the field of new material synthesis and technology, and particularly relates to a square acid complex derived nickel-iron based double metal hydroxide, a preparation method and an electrode. BACKGROUND
[0002] Electrolysis of water to produce hydrogen is one of the key technologies for hydrogen production. Currently, countries are working to develop water electrolysis hydrogen production technology to improve the efficiency of electrolysis devices, reduce hydrogen production costs and expand market size. Water electrolysis hydrogen is expected to play a key role in the global energy transition process. Using hydrogen energy, especially green hydrogen to replace fossil fuels, some energy-intensive industries are expected to achieve decarbonization.
[0003] The oxygen evolution reaction of the anode in water electrolysis has a large reaction energy barrier and slow kinetics, which is the main source of high overpotential in water electrolysis. Therefore, the development of efficient oxygen evolution reaction catalysts has become the focus of researchers at home and abroad. However, during the oxygen evolution reaction process, the catalyst will undergo surface reconstruction, causing changes in the chemical structure and physical properties of the catalytic interface. This not only causes dynamic evolution of the structure information of the catalytic interface, but also increases the complexity of the real catalytic surface structure-activity relationship analysis, leading to one-sided analysis and conclusions, limiting the synthesis of efficient oxygen evolution catalysts and the development of design strategies. At the same time, due to the existence of anode oxidation reconstruction, the oxidation and loss of many metal ions or ligand molecules have not been paid attention to. Reverse use of the anode oxidation reconstruction phenomenon to assist in building catalytic surface defects and molecular interlayer structures has become a very innovative and challenging unconventional preparation method. Currently, existing researches mostly focus on the intrinsic structure design of the initial catalyst, often ignoring the in-situ dynamic evolution of the catalytic structure during the reaction process.
[0004] At the same time, for the process of electrocatalytic water splitting, current researches often focus on theoretical mechanism exploration and laboratory small-scale testing, and real industrial application-oriented large current test data are in a state of vacancy. Under amperage level large current test conditions, the interface microenvironment of the anode and the gas-liquid transport efficiency will significantly affect the activity and stability of the electrocatalyst. Currently, most of the synthesis methods proposed by the researches mostly mechanically deposit or load the catalyst on the self-supporting substrate material, and the combination of the catalyst and the surface of the substrate material is not firm. Due to slow bubble diffusion and dense bubble impact under large current, the highest current density reported by them is mostly concentrated in 600mA / cm 2 ~1000mA / cm 2 . SUMMARY
[0005] In view of the above, the purpose of the present application is to provide a nickel-iron-based double metal hydroxide with high catalytic activity and long-term large current stability, at least partially solving the problems existing in the prior art. In order to achieve the purpose of the present application, the present application adopts the following technical solutions:
[0006] The present application provides a squaric acid complex derived nickel-iron-based double metal hydroxide with an interactive micrometer-scale pore structure.
[0007] Further, the squaric acid complex derived nickel-iron-based double metal hydroxide has a pore structure width of 4 microns to 8 microns.
[0008] The present application also provides a preparation method of the squaric acid complex derived nickel-iron-based double metal hydroxide, comprising the following steps:
[0009] A, pretreating the foamed nickel;
[0010] B, hydrothermally treating the treated foamed nickel in a squaric acid and iron salt solution to obtain a nickel-iron-based squaric acid complex precursor;
[0011] C, electrochemically activating and restructuring the prepared nickel-iron-based squaric acid complex precursor to obtain a squaric acid complex derived nickel-iron-based double metal hydroxide.
[0012] Further, the foamed nickel in step 1 has a thickness of 1-3 mm.
[0013] Further, the iron salt in step 2 is one of ferric nitrate, ferric chloride and ferric sulfate; the hydrothermal treatment temperature is 100-160℃, and the heating time is 4-8 hours; the molar ratio of squaric acid to iron salt in the hydrothermal treatment solution is 5:1.
[0014] Further, step 3 realizes the activation and restructuring process of the nickel-iron-based squaric acid complex precursor in an alkaline electrolyte by cyclic voltammetry.
[0015] Further, the alkaline electrolyte is 1 mol / L potassium hydroxide; the activation voltage range is 1-1.45V vs.RHE, and the activation is 10-50 cycles.
[0016] Further, it further comprises vacuum drying treatment of the squaric acid complex derived nickel-iron-based double metal hydroxide; the drying temperature is 60-120℃; and the drying time is 12-15h.
[0017] The present application also provides a squaric acid complex derived nickel-iron-based double metal hydroxide prepared by the above preparation method.
[0018] The application further provides an electrode comprising an electrolytic water oxygen evolution catalyst, wherein the electrolytic water oxygen evolution catalyst is the square acid complex derivative nickel-iron based double metal hydroxide or the square acid complex derivative nickel-iron based double metal hydroxide prepared by the preparation method.
[0019] According to the technical solution, the application provides a square acid complex derivative nickel-iron based double metal hydroxide, a preparation method thereof and an electrode comprising the square acid complex derivative nickel-iron based double metal hydroxide. The square acid complex derivative nickel-iron based double metal hydroxide has a natural pore structure on the surface, which can promote the rapid transfer and transmission of hydroxyl ions in the electrolyte, protons in the reaction intermediates and product oxygen molecules, so as to maintain high catalytic activity and long-term large current stability. The preparation method of the square acid complex derivative nickel-iron based double metal hydroxide is green, simple and efficient. The electrode comprising the square acid complex derivative nickel-iron based double metal hydroxide is expected to overcome the harsh conditions in a large current environment, and has important practical significance for realizing the large-scale development of electrolytic water green hydrogen. BRIEF DESCRIPTION OF DRAWINGS
[0020] In order to more clearly illustrate the technical solutions of the embodiments of the application, the drawings needed in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can be obtained by those skilled in the art without creative labor.
[0021] Figure 1 XRD pattern of the nickel-iron based square acid complex precursor prepared in Example 1;
[0022] Figure 2 SEM pattern of the square acid complex derivative nickel-iron based double metal hydroxide catalyst prepared in Example 1;
[0023] Figure 3 TEM-Mapping pattern of the square acid complex derivative nickel-iron based double metal hydroxide catalyst prepared in Example 1. DETAILED DESCRIPTION
[0024] The embodiments of the application will be described in detail below with reference to the drawings.
[0025] It should be noted that the following embodiments and features in the embodiments can be combined with each other without conflict; and all other embodiments obtained by those skilled in the art based on the embodiments in the present disclosure without creative labor are within the scope of protection of the present disclosure.
[0026] It is to be appreciated that various aspects of the embodiments described below are presented for the purpose of illustration and description. It is to be appreciated that the aspects described herein can be embodied in a wide variety of forms and that any particular structure and / or function described herein is merely illustrative. Based on the teachings provided herein one skilled in the art should appreciate that an aspect described herein can be implemented independently of any other aspects and that an aspect described herein can be implemented both as any number of software and / or hardware structures.
[0027] The application provides a foam nickel loaded square acid complex derived nickel-iron based double metal hydroxide, which can provide interactive microscale gas-liquid transmission channels and at least partially solve the problems existing in the current large current test technology of electrolytic water.
[0028] The application provides a preparation method of a square acid complex derived nickel-iron based double metal hydroxide, which comprises the following steps: pretreating a foam nickel mesh with an acid to remove surface oxides; hydrothermally treating the pretreated foam nickel mesh in a square acid and iron salt solution to obtain a nickel-iron based square acid complex precursor; and performing electrochemical activation reconstruction treatment on the precursor to obtain the square acid complex derived nickel-iron based double metal hydroxide.
[0029] In the embodiments of the application, the acid pretreatment is ultrasonic cleaning with 1 mol / L hydrochloric acid and 95% ethanol for 15-30 minutes.
[0030] In the specific embodiments of the application, the thickness of the foam nickel is 1-3 mm. Specifically, the thickness of the foam nickel is 1, 1.5, 2, 2.5 or 3 mm.
[0031] In the specific embodiments of the application, the iron salt is one of ferric nitrate, ferric chloride and ferric sulfate.
[0032] In the embodiments of the application, the hydrothermal treatment temperature is 100-160℃. Specifically, the temperature can be 100℃, 120℃, 140℃ or 160℃. The heating time can be 4 hours, 6 hours or 8 hours. In some specific embodiments, the reaction temperature is 100℃ and the heating time is 8 hours; in some specific embodiments, the reaction temperature is 120℃ and the heating time is 6 hours; in some specific embodiments, the reaction temperature is 140℃ and the heating time is 4 hours; and in some specific embodiments, the reaction temperature is 160℃ and the heating time is 4 hours.
[0033] In some embodiments, the molar ratio of squaric acid and iron salt in the hydrothermally treated solution is 5:1.
[0034] In some embodiments, the hydrothermally treated solution further comprises 0.3-0.5 g of polyvinylpyrrolidone as a morphology directing agent.
[0035] In some embodiments, the present application realizes the activation and reconstruction process of the nickel-iron-based squaric acid complex precursor in an alkaline electrolyte by cyclic voltammetry.
[0036] In some embodiments, the alkaline electrolyte is 1 mol / L potassium hydroxide; the activation voltage range is 1-1.45 V vs. RHE, and the activation is 10-50 cycles.
[0037] In some embodiments, the preparation method of the present application further comprises vacuum drying treatment of the nickel-iron-based double metal hydroxide derived from the squaric acid complex.
[0038] In some embodiments, the drying treatment conditions of the present application include a drying temperature of 60-120℃ and a drying time of 12-15h.
[0039] The preparation method of the present application uses the acidic environment provided by the squaric acid complex to directly etch the foam nickel mesh in situ to provide a nickel source. The self-sourced catalyst structure is more closely and firmly combined with the self-supporting substrate, and has a natural micron-scale channel to accelerate bubble transmission.
[0040] The present application confirms the successful preparation of the nickel-iron-based squaric acid complex precursor by X-ray diffraction analysis, and characterizes the micron-scale channel structure of the nickel-iron-based double metal hydroxide derived from the squaric acid complex by scanning electron microscopy.
[0041] The present application also provides an electrode comprising an electrolytic water oxygen evolution catalyst, wherein the electrolytic water oxygen evolution catalyst is the nickel-iron-based double metal hydroxide derived from the squaric acid complex. The nickel-iron-based double metal hydroxide derived from the squaric acid complex as an oxygen evolution electrocatalyst can provide an ultra-high current density of up to 3000 mA / cm and long-term stability of hundreds of hours, overcoming the harsh conditions in a large current environment and breaking through the current limit of the oxygen evolution reaction to 3000 mA / cm, which has important practical significance for the large-scale development of green hydrogen production by electrolytic water.
[0042] The present application will be described in conjunction with specific embodiments, but the present application is not limited to the following examples.
[0043] Example 1: Preparation of nickel-iron-based double metal hydroxide derived from squaric acid complex
[0044] The foamed nickel mesh was sequentially cleaned with 1 mol / L hydrochloric acid and 95% ethanol for 30 minutes and then dried in a vacuum drying oven. 0.3 g of polyvinylpyrrolidone, 5 mmol of squaric acid and 1 mmol of iron nitrate nonahydrate were fully dissolved in a polytetrafluoroethylene reactor containing 30 mL of deionized water. The acid-washed foamed nickel mesh was tilted and immersed in the above solution, and the reactor was assembled, heated to 120°C and maintained for 6 hours. After the reaction was completed, the product was washed and dried in a vacuum drying oven to obtain a nickel-iron-based squaric acid complex precursor.
[0045] The prepared precursor was treated by cyclic voltammetry in a standard three-electrode system in 1 mol / L potassium hydroxide electrolyte, and the scanning voltage range was 1-1.45 V vs. RHE (relative to the potential of the reversible hydrogen electrode); activated for 20 cycles. After the reaction was completed, the product was washed and dried in a vacuum drying oven at 120°C for 12 h to obtain a squaric acid complex-derived nickel-iron-based bimetallic hydroxide.
[0046] The nickel-iron-based squaric acid complex precursor was characterized by XRD, as shown in Figure 1 , the product had characteristic peaks attributed to metal squaric acid complexes, proving the successful preparation of the nickel-iron-based squaric acid complex precursor. As shown in Figure 2 , the SEM image showed that the surface of the skeleton structure of the foamed nickel mesh formed a uniform distribution of micron-sized channel structure, and the pore structure width was 4-8 microns. Figure 3 The TEM-Mapping image of the squaric acid complex-derived nickel-iron-based bimetallic hydroxide showed uniform distribution of elements Ni, Fe, C and O.
[0047] Example 2: Preparation of squaric acid complex-derived nickel-iron-based bimetallic hydroxide
[0048] The foamed nickel mesh was sequentially cleaned with 1 mol / L hydrochloric acid and 95% ethanol for 30 minutes and then dried in a vacuum drying oven. 0.3 g of polyvinylpyrrolidone, 5 mmol of squaric acid and 1 mmol of iron nitrate nonahydrate were fully dissolved in a polytetrafluoroethylene reactor containing 30 mL of deionized water. The acid-washed foamed nickel mesh was tilted and immersed in the above solution, and the reactor was assembled, heated to 120°C and maintained for 6 hours. After the reaction was completed, the product was washed and dried in a vacuum drying oven to obtain a nickel-iron-based squaric acid complex precursor.
[0049] The prepared precursor was treated by cyclic voltammetry in a standard three-electrode system in 1 mol / L potassium hydroxide electrolyte, and the scanning voltage range was 1-1.45 V vs. RHE (relative to the potential of the reversible hydrogen electrode); activated for 20 cycles. After the reaction was completed, the product was washed and dried in a vacuum drying oven to obtain a squaric acid complex-derived nickel-iron-based bimetallic hydroxide.
[0050] The prepared square acid complex derived nickel-iron based double metal hydroxide was characterized by XRD and SEM, and the results were similar to those of Example 1.
[0051] Example 3: Preparation of square acid complex derived nickel-iron based double metal hydroxide
[0052] The foam nickel mesh was sequentially cleaned with 1 mol / L hydrochloric acid and 95% ethanol for 30 minutes, and then dried in a vacuum drying oven. 0.3 g of polyvinylpyrrolidone, 5 mmol of square acid, and 1 mmol of iron sulfate were fully dissolved in a polytetrafluoroethylene reactor containing 30 mL of deionized water. The acid-washed foam nickel mesh was tilted and immersed in the above solution, and the reactor was assembled. After heating to 100°C for 8 hours, the product was washed and dried in a vacuum drying oven to obtain a nickel-iron square acid complex precursor.
[0053] The prepared precursor was treated by cyclic voltammetry in a 1M / L potassium hydroxide electrolyte using a standard three-electrode system, and the scanning voltage range was 1-1.45V vs. RHE; activated for 50 cycles. After the reaction was completed, the product was washed and dried in a vacuum drying oven at 60°C for 15h to obtain a square acid complex derived nickel-iron based double metal hydroxide.
[0054] The prepared square acid complex derived nickel-iron based double metal hydroxide was characterized by XRD and SEM, and the results were similar to those of Example 1.
[0055] Test Example 1:
[0056] The oxygen evolution performance of the catalyst sample prepared in Example 1 was tested in a 1M / L KOH solution at room temperature using a three-electrode system on a Gamry Reference 3000 electrochemical workstation. Among them, the Pt sheet electrode is the counter electrode, the Hg / HgO electrode is the reference electrode, and the prepared catalyst is the working electrode. The linear sweep voltammetry (LSV) curve was obtained by scanning at a speed of 5mV / s.
[0057] The preparation method of the nickel-iron double metal hydroxide is to sequentially clean the foam nickel mesh with 1 mol / L hydrochloric acid and 95% ethanol for 30 minutes, and then dry it in a vacuum drying oven to obtain a foam nickel mesh comparative sample. 0.6 g of urea, 2 mmol of nickel chloride, and 1 mmol of iron chloride were fully dissolved in a polytetrafluoroethylene reactor containing 30 mL of deionized water. The acid-washed foam nickel mesh was tilted and immersed in the above solution, and the reactor was assembled. After heating to 100°C for 8 hours, the product was washed and dried in a vacuum drying oven to obtain a nickel-iron double metal hydroxide.
[0058] Table 1: Electrochemical oxygen evolution performance of the square acid complex derived nickel-iron based double metal hydroxide according to the present application
[0059]
[0060] The results show that the square acid complex derived nickel-iron based double metal hydroxide catalyst prepared in Example 1 of the present application has excellent oxygen evolution performance, and can provide a large current density of 1000 mA / cm 2 , 2000 mA / cm 2 , 3000 mA / cm 2 at an overpotential of only 280 mV, 315 mV, 337 mV, respectively, far superior to the pure nickel-iron based double metal hydroxide catalyst.
[0061] The oxygen evolution performance of the square acid complex derived nickel-iron based double metal hydroxide prepared in Example 2 and Example 3 was tested using the same method, and the results were similar to the square acid complex derived nickel-iron based double metal hydroxide catalyst prepared in Example 1 of the present application, which had excellent oxygen evolution performance, far superior to the pure nickel-iron based double metal hydroxide catalyst.
[0062] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and any changes or replacements easily thought of by those skilled in the art within the technical scope disclosed by the present application should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims
1. A squarate complex derived nickel-iron based double metal hydroxide characterized in that, The micrometer-scale channel structure has interaction; the channel structure width is 4-8 micrometers; the preparation method comprises the following steps: A, pretreating the foamed nickel; B, performing hydrothermal treatment on the pretreated foamed nickel in a solution of squaric acid and iron salt to obtain a nickel-iron-based squaric acid complex precursor; the iron salt is one or more of ferric nitrate, ferric chloride and ferric sulfate; the hydrothermal treatment temperature is 100-160 DEG C, and the heating time is 4-8 hours; in the solution for the hydrothermal treatment, the molar ratio of squaric acid to iron salt is 5:1; C, performing electrochemical activation remodeling treatment on the prepared nickel-iron-based squaric acid complex precursor to obtain a squaric acid complex derivative nickel-iron-based bimetallic hydroxide; the activation remodeling process of the nickel-iron-based squaric acid complex precursor is realized in an alkaline electrolyte by cyclic voltammetry.
2. The method for preparing squaric acid complex-derivatized nickel-iron based double metal hydroxide according to claim 1, characterized in that, Comprise the following steps: A, pretreating the foamed nickel; B, performing hydrothermal treatment on the pretreated foamed nickel in a solution of squaric acid and iron salt to obtain a nickel-iron-based squaric acid complex precursor; the iron salt is one or more of ferric nitrate, ferric chloride and ferric sulfate; the hydrothermal treatment temperature is 100-160 DEG C, and the heating time is 4-8 hours; in the solution for the hydrothermal treatment, the molar ratio of squaric acid to iron salt is 5:1; C, performing electrochemical activation remodeling treatment on the prepared nickel-iron-based squaric acid complex precursor to obtain a squaric acid complex derivative nickel-iron-based bimetallic hydroxide; the activation remodeling process of the nickel-iron-based squaric acid complex precursor is realized in an alkaline electrolyte by cyclic voltammetry.
3. The preparation method according to claim 2, characterized in that, The thickness of the foamed nickel in step 1 is 1-3 mm.
4. The production method according to claim 2, characterized by, The alkaline electrolyte is 1 mol / L potassium hydroxide; the activation voltage range is 1-1.45 V vs. RHE, and the activation is 10-50 cycles.
5. The preparation method according to claim 2, characterized in that, Further comprising vacuum drying treatment on the squaric acid complex derivative nickel-iron-based bimetallic hydroxide.
6. The production method according to claim 5, wherein The drying temperature is 60-120 DEG C; the drying time is 12-15 h.
7. An electrode comprising an electrolytic water oxygen evolution catalyst, the electrolytic water oxygen evolution catalyst being the squaric acid complex derivative nickel-iron-based bimetallic hydroxide of claim 1.