Anode catalyst and rapid Joule heat preparation method and application thereof
The preparation of bimetallic heterostructure anode catalysts by rapid Joule heat treatment technology solves the problems of scarce anode catalyst resources and insufficient catalytic activity, and achieves high efficiency and low cost catalytic performance improvement, which is suitable for fields such as PEM water electrolysis and fuel cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-09
- Publication Date
- 2026-03-10
AI Technical Summary
Existing electrochemical anode catalysts suffer from problems such as resource scarcity, high price, easy agglomeration and dissolution, insufficient catalytic activity, and slow reaction kinetics. Traditional preparation methods are complex and energy-intensive, making it difficult to meet the application requirements of high-performance electrochemical energy devices.
A bimetallic heterostructure anode catalyst was prepared by using rapid Joule heat treatment technology, which involves reacting a mixed nickel and iron ion solution with a sodium ferrocyanide solution, combined with ultrasonic treatment of nickel foam and rapid Joule heat calcination.
It achieves a significant improvement in catalytic performance, reduces the overpotential of the oxygen evolution reaction (OER), shortens the catalyst preparation time, and reduces costs. It is suitable for applications such as PEM water electrolysis and fuel cells, and promotes the preparation of key materials for energy transformation.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of electrochemical electrode materials, in particular to a method for preparing an electrochemical (OER) oxygen evolution reaction catalytic material by means of rapid Joule heat treatment technology, an anode catalyst obtained by the method and application thereof. BACKGROUND
[0002] An anode catalyst is a core functional component of an electrochemical energy conversion and storage device (such as a fuel cell, a water electrolysis hydrogen production device, a flow battery, etc.), and its core role is to reduce the activation energy of the anode reaction and accelerate the electrochemical reaction kinetics, which directly determines the energy conversion efficiency, operation stability and industrialization cost of the device.
[0003] At present, the mainstream electrochemical anode catalysts are mainly divided into two categories: noble metal-based (Pt, Ru, Ir, etc.) and non-noble metal-based (transition metal compounds, carbon-based materials, single-atom catalysts, etc.). Although the noble metal-based catalysts have excellent catalytic activity and reaction selectivity, they are scarce in resources, expensive in price, and prone to particle agglomeration and dissolution loss during long-term operation, which limits the service life of the device; the non-noble metal-based catalysts have significant cost advantages, but have problems such as insufficient catalytic activity, slow reaction kinetics, weak resistance to poisoning (such as resistance to CO and resistance to intermediate product adsorption), which are difficult to meet the application requirements of high-performance devices.
[0004] Traditional anode catalyst preparation methods, such as high-temperature calcination, hydrothermal synthesis, and electrochemical deposition, usually have problems such as complex process, high energy consumption, and long production cycle, which further restrict the performance improvement and industrialization promotion of the anode catalyst.
[0005] Therefore, developing high-performance, low-cost electrochemical anode catalysts and efficient, controllable new preparation technologies has become a key breakthrough for promoting the industrialization of electrochemical energy devices. SUMMARY
[0006] The technical problem to be solved by the present application is to provide an anode catalyst and a rapid Joule heat preparation method and application thereof, so as to achieve the purpose of efficiently preparing an anode catalyst and improving its catalytic performance.
[0007] To solve the above technical problems, according to one aspect of the present application, a rapid Joule heat preparation method of an anode catalyst is provided, comprising: Step one, mixing a nickel ion solution and an iron ion solution to obtain a mixed metal ion solution; adding the mixed metal ion solution dropwise into a sodium ferrocyanide solution, and after mixing and dispersing, performing centrifugal separation and drying to obtain a precursor material; Step two, ultrasonically treating the foamed nickel with ethanol in sequence, and then immersing it in nitric acid for ultrasonic cleaning; Step three, mix the pre-processed foamed nickel with the precursor material obtained in step one, and conduct rapid joule heat treatment under inert gas protection, and obtain the anode catalyst after cooling.
[0008] As a preferred embodiment, in step one, the total molar ratio of the mixed metal ions of sodium ferrocyanide and nickel is equimolar.
[0009] As a preferred embodiment, in step one, the proportion of nickel ions in the total molar amount of mixed metal ions is 1% to 10%.
[0010] As a preferred embodiment, in step one, the nickel ion solution and the iron ion solution are corresponding nitrate solutions, acetate solutions, sulfate solutions or oxalate solutions.
[0011] As a preferred embodiment, in step one, the dropwise addition rate is 1.0 to 10 mL / min, and the mixing and dispersing time is 30 to 300 min.
[0012] As a preferred embodiment, in step three, the mixing method of foamed nickel and precursor material is to directly lay foamed nickel on the surface of the precursor material.
[0013] As a preferred embodiment, in step three, the mixing method of foamed nickel and precursor material is to lay foamed nickel above the precursor material, and the two are separated by carbon cloth.
[0014] As a preferred embodiment, in step three, the pulse discharge current of rapid joule heat treatment is 5 to 20 A, the highest temperature generated by rapid joule heat is 500 to 800℃, and the single discharge time of pulse discharge is 1 to 60 s.
[0015] According to another aspect of the present application, an anode catalyst prepared by the above method is provided.
[0016] According to another aspect of the present application, the use of the above-mentioned anode catalyst in an electrochemical oxygen evolution reaction is provided.
[0017] Compared with the prior art, the method for preparing an OER oxygen evolution reaction catalyst material by rapid joule heat treatment technology has the beneficial effects of: Traditional catalyst preparation requires 6-12 hours or even several days, and through simple and rapid joule heat technology, the construction of a bimetallic heterostructure can be realized in milliseconds to seconds, providing guidance for the rational design of a multi-metal heterostructure.
[0018] The anode catalyst material prepared by rapid joule heat treatment exhibits excellent electrochemical (OER) oxygen evolution reaction catalytic performance, and the current density is 10 mA cm -2The overpotential reaches 220 mV at a current density, which is reduced by about 30-100 mV compared with a commercial anode catalyst material prepared by a traditional method.
[0019] The method forms a virtuous cycle of "efficiency-structure-performance-cost", and the technology has achieved a breakthrough application in the fields of PEM electrolysis of water, fuel cells and the like, providing a key material preparation solution for energy transformation under the "double carbon" goal, and forming a full-chain economic value from cost savings to industry promotion. DETAILED DESCRIPTION
[0020] In view of the problems of insufficient operation stability and poor overall technical economy of the existing OER oxygen evolution reaction catalyst, the present application provides a method for rapidly preparing materials by means of transient heating, optimizing and improving the OER oxygen evolution reaction catalytic performance, and obtaining an OER oxygen evolution reaction catalyst material with high catalytic activity through a rapid Joule heating process.
[0021] A typical embodiment of the present application provides a rapid Joule heating preparation method of an anode catalyst, which comprises the following steps one to three.
[0022] Step one, precursor synthesis.
[0023] The nickel ion solution and the iron ion solution are mixed to obtain a mixed metal ion solution; the mixed metal ion solution is added dropwise into a sodium ferrocyanide solution, and after mixing and dispersing, centrifugal separation and drying are performed to obtain a precursor material.
[0024] The nickel ion solution and the iron ion solution in this step are usually corresponding nitrate solutions, acetate solutions, sulfate solutions or oxalate solutions, such as iron nitrate, nickel nitrate, iron acetate, nickel acetate, etc.
[0025] The total amount of sodium ferrocyanide and mixed metal ions of nickel and iron is in an equimolar ratio, for example, the mixed metal ions are composed of 4.5 mmol of iron nitrate and 0.5 mmol of nickel nitrate, the total molar amount of the two is 5 mmol, and the sodium ferrocyanide is also 5 mmol.
[0026] In a preferred embodiment, the proportion of nickel ions in the total molar amount of mixed metal ions is 1%-10%.
[0027] Exemplarily, the concentration of the nickel ion solution is 0.001-1.0 mol / L, and the concentration of the iron ion solution is 0.001-1.0 mol / L.
[0028] In this step, the mixed metal ion solution is preferably added dropwise to the sodium ferrocyanide solution at a constant rate, the dropwise addition rate is 1.0-10 mL / min, and the mixing and dispersing time is 30-300 min.
[0029] Step two, pretreatment of foamed nickel.
[0030] The foamed nickel is sequentially treated by ultrasonic treatment with ethanol and then immersed in nitric acid for ultrasonic cleaning, and the cleaning time is usually about 30 min.
[0031] Step three, rapid Joule heat treatment.
[0032] The foamed nickel pretreated in step two is mixed with the precursor material obtained in step one, and rapid Joule heat treatment is carried out under inert gas protection, and the anode catalyst is obtained after cooling.
[0033] The rapid Joule heat treatment is carried out in a rapid Joule heat device, and the foamed nickel mixed with the precursor material is placed in the rapid Joule heat device for calcination treatment, and the mixture is rapidly heated and cooled by pulse discharge to generate Joule heat.
[0034] The pulse discharge current of the rapid Joule heat treatment is 5-20 A, the maximum temperature generated by the rapid Joule heat is 500-800℃, and the single discharge time of the pulse discharge is 1-60 s. The inert gas protection atmosphere is preferably an argon atmosphere.
[0035] In this step, there are two ways to mix the foamed nickel with the precursor material. One is to directly lay the foamed nickel on the surface of the precursor material; the other is to lay the foamed nickel above the precursor material, and the two are separated by carbon cloth.
[0036] The nickel-iron-based catalyst material prepared by rapid Joule heat treatment is used as an anode, a platinum electrode is used as a cathode, and a KOH aqueous solution is used as an electrolyte to carry out an electrochemical oxygen evolution reaction at room temperature.
[0037] The technical solutions claimed by the present application are further described below through some examples. However, the examples and comparative examples are used to explain the embodiments of the present application and do not exceed the scope of the subject matter of the present application, and the protection scope of the present application is not limited by the examples. Unless otherwise specified, the materials and reagents used in the present application can be obtained from commercial products in the art. Example 1
[0038] In this embodiment, iron nitrate and nickel nitrate are selected as precursor synthesis raw materials.
[0039] (1) 4.5 mmol of iron nitrate and 0.5 mmol of nickel nitrate were dissolved in 100 mL of deionized water, and mixed and stirred for 10 min to obtain a mixed metal ion solution. The mixed metal ion solution was added to 0.05 mol / L, 100 mL of sodium ferrocyanide solution at a rate of 1 mL / min, and continuously stirred at room temperature for 120 min. After centrifugal separation, the precipitate was dried at 60℃ for 24 h to obtain a precursor material.
[0040] (2) The foamed nickel is placed in a beaker and treated with ethanol ultrasonically, and then immersed in a beaker containing nitric acid and ultrasonically cleaned for 30 min.
[0041] (3) The pretreated foamed nickel is laid flat on the surface of the precursor material and placed in a rapid joule heating device for calcination treatment under an argon atmosphere, the pulse discharge current of the rapid joule heating treatment is adjusted to 12 A, the maximum temperature generated by the rapid joule heating is 650 DEG C, and the single discharge time of the pulse discharge is 10 s.
[0042] (4) The catalyst material prepared by the rapid joule heating treatment is used as an anode, a platinum electrode is used as a cathode, and 1 mol / L KOH aqueous solution is used as an electrolyte, and an electrochemical oxygen evolution reaction is carried out at room temperature to test the OER oxygen evolution reaction catalytic performance.
[0043] Comparative Example 1 In this comparative example, iron nitrate and nickel nitrate are selected as the precursor synthesis raw materials.
[0044] (1) 4.5 mmol of iron nitrate and 0.5 mmol of nickel nitrate are dissolved in 100 mL of deionized water, mixed and stirred for 10 min to obtain a mixed metal ion solution. The mixed metal ion solution is added to 0.05 mol / L, 100 mL of sodium ferrocyanide solution at a rate of 1 mL / min, continuously stirred at room temperature for 120 min, centrifuged, and the precipitate is dried at 60 DEG C for 24 h to obtain a precursor material.
[0045] (2) Anhydrous ethanol is used as a dispersant and mixed with the precursor material in a planetary ball mill for 2 h (rotation speed 300-500 r / min), and after ensuring uniform dispersion of the raw materials, the mixture is dried at 80 DEG C for 12 h.
[0046] (3) The dried precursor is placed in a muffle furnace and calcined at 650 DEG C for 8 h under an air atmosphere, cooled, and ground through a 200 mesh sieve to obtain a uniform NiFe-based catalyst material.
[0047] (4) The NiFe-based catalyst material is used as an anode, a platinum electrode is used as a cathode, and 1 mol / L KOH aqueous solution is used as an electrolyte, and an electrochemical oxygen evolution reaction is carried out at room temperature to test the OER oxygen evolution reaction catalytic performance.
[0048] Example 2
[0049] In this example, iron acetate and nickel acetate are selected as the precursor synthesis raw materials.
[0050] (1) Dissolve 4.5 mmol of iron acetate and 0.5 mmol of nickel acetate in 100 mL of deionized water, mix and stir for 10 min to obtain a mixed metal ion solution. Add the mixed metal ion solution to a 0.05 mol / L, 100 mL sodium ferrocyanide solution at a rate of 2 mL / min, continuously stir at room temperature for 60 min, centrifuge and separate the precipitate, and then dry at 60°C for 24 h to obtain a precursor material.
[0051] (2) Place the nickel foam in a beaker and ultrasonically treat it with ethanol, then immerse it in a beaker containing nitric acid and ultrasonically clean it for 30 min.
[0052] (3) Place the pretreated nickel foam on top of the precursor material, separate it with a carbon cloth to prevent direct contact, and place it in a rapid joule heating device for calcination treatment in an argon atmosphere. Adjust the pulse discharge current of the rapid joule heating treatment to 15 A, the maximum temperature generated by the rapid joule heating to 700°C, and the single discharge time of the pulse discharge to 30 s.
[0053] (4) Use the catalyst material prepared by rapid joule heating treatment as the anode, a platinum electrode as the cathode, and 1 mol / L KOH aqueous solution as the electrolyte to perform an electrochemical oxygen evolution reaction at room temperature, and test its OER oxygen evolution reaction catalytic performance.
[0054] Comparative Example 2 In this comparative example, iron acetate and nickel acetate are used as precursor synthesis raw materials. (1) Dissolve 4.5 mmol of iron acetate and 0.5 mmol of nickel acetate in 100 mL of deionized water, add 0.15 mmol of urea (a slow-release alkali source), mix and stir for 30 min until completely dissolved; (2) Transfer the mixed solution to a 50 mL polytetrafluoroethylene-lined homogeneous reaction kettle with a filling degree of 80%, and perform homogeneous reaction at 120°C for 12 h, and then naturally cool to room temperature; (3) Place the cooled mixed solution in a high-speed centrifuge (10000 r / min, 15 min), wash it with deionized water and ethanol alternately for 3 times, and then vacuum dry at 60°C for 8 h to directly obtain a NiFe-based catalyst material; (4) Use the catalyst material prepared by hydrothermal synthesis as the anode, a platinum electrode as the cathode, and 1 mol / L KOH aqueous solution as the electrolyte to perform an electrochemical oxygen evolution reaction at room temperature, and test its OER oxygen evolution reaction catalytic performance.
[0055] Example 3
[0056] In this example, iron acetate and nickel acetate are used as precursor synthesis raw materials.
[0057] (1) 4.5 mmol of ferric nitrate and 0.5 mmol of nickel nitrate were dissolved in 100 mL of deionized water, mixed and stirred for 10 min to obtain a mixed metal ion solution. The mixed metal ion solution was added dropwise to 100 mL of 0.05 mol / L sodium ferrocyanide solution at a rate of 10 mL / min, continuously stirred at room temperature for 30 min, and the precipitate was separated by centrifugation and dried at 60°C for 24 h to obtain the precursor material.
[0058] (2) The foam nickel was placed in a beaker and treated with ethanol ultrasonic, and then immersed in a beaker containing nitric acid for ultrasonic cleaning for 30 min.
[0059] (3) The pretreated foam nickel was placed on the surface of the precursor material and subjected to calcination treatment in an argon atmosphere in a rapid joule heating device. The pulse discharge current of the rapid joule heating treatment was adjusted to 5 A, the maximum temperature generated by the rapid joule heating was 500°C, and the single discharge time of the pulse discharge was 1 s. Example 4
[0060] In this embodiment, iron oxalate and nickel oxalate were selected as the precursor synthesis raw materials.
[0061] (1) 4.95 mmol of ferric nitrate and 0.05 mmol of nickel nitrate were dissolved in 100 mL of deionized water, mixed and stirred for 10 min to obtain a mixed metal ion solution. The mixed metal ion solution was added dropwise to 100 mL of 0.05 mol / L sodium ferrocyanide solution at a rate of 1 mL / min, continuously stirred at room temperature for 300 min, and the precipitate was separated by centrifugation and dried at 60°C for 24 h to obtain the precursor material.
[0062] (2) The foam nickel was placed in a beaker and treated with ethanol ultrasonic, and then immersed in a beaker containing nitric acid for ultrasonic cleaning for 30 min.
[0063] (3) The pretreated foam nickel was placed on the surface of the precursor material and subjected to calcination treatment in an argon atmosphere in a rapid joule heating device. The pulse discharge current of the rapid joule heating treatment was adjusted to 20 A, the maximum temperature generated by the rapid joule heating was 800°C, and the single discharge time of the pulse discharge was 30 s.
[0064] The scope of protection of the present application is not limited to the above specific embodiments, and the present application can have various modifications and alterations for those skilled in the art, and any modifications, improvements and equivalent replacements made within the concept and principles of the present application shall be included in the scope of protection of the present application.
Claims
1. A rapid Joule heat preparation method of an anode catalyst, characterized by, The application relates to a preparation method of an anode catalyst. Step one: mixing a nickel ion solution and an iron ion solution to obtain a mixed metal ion solution; The mixed metal ion solution is added dropwise into a sodium ferrocyanide solution, and after mixing and dispersion, centrifugal separation and drying are carried out to obtain a precursor material; Step two: the foamed nickel is sequentially subjected to ultrasonic treatment with ethanol and ultrasonic cleaning in nitric acid; Step three: the foamed nickel pretreated in step two is mixed with the precursor material obtained in step one, and rapid joule heat treatment is carried out under inert gas protection, and an anode catalyst is obtained after cooling.
2. The rapid joule heating method for preparing an anode catalyst according to claim 1, characterized by: In step one, the total molar ratio of sodium ferrocyanide and the mixed metal ions of nickel and iron is equimolar.
3. The rapid joule heating method for preparing an anode catalyst according to claim 2, characterized by: In step one, the proportion of nickel ions in the total molar amount of mixed metal ions is 1% to 10%.
4. The rapid joule heating method for preparing an anode catalyst according to claim 1, 2 or 3, characterized by: In step one, the nickel ion solution and the iron ion solution are corresponding nitrate solutions, acetate solutions, sulfate solutions or oxalate solutions.
5. The rapid joule heating method for preparing an anode catalyst according to claim 4, characterized by: In step one, the dropwise adding speed is 1.0 to 10 mL / min, and the mixing and dispersion time is 30 to 300 min.
6. The rapid joule heating method for preparing an anode catalyst according to claim 1 or 5, characterized by: In step three, the mixing mode of the foamed nickel and the precursor material is that the foamed nickel is directly laid on the surface of the precursor material.
7. The rapid joule heating method for preparing an anode catalyst according to claim 6, characterized by: In step three, the mixing mode of the foamed nickel and the precursor material is that the foamed nickel is laid above the precursor material, and the two are isolated by carbon cloth.
8. The rapid joule heating method for preparing an anode catalyst according to claim 7, characterized by: In step three, the pulse discharge current of the rapid joule heat treatment is 5 to 20 A, the highest temperature generated by the rapid joule heat is 500 to 800 DEG C, and the single discharge time of the pulse discharge is 1 to 60 s.
9. An anode catalyst prepared by the method in any one of claims 1 to 8.
10. The application of the anode catalyst in claim 9 in an electrochemical oxygen evolution reaction.