A high-entropy alloy nanoparticle loaded carbon fiber cathode catalyst, a preparation method and application thereof in a full-solid high-low temperature zinc-air battery

Abstract

The application belongs to the field of zinc-air batteries, and particularly relates to a high-entropy alloy nanoparticle loaded carbon fiber cathode catalyst, a preparation method and application thereof in a full-solid high-low temperature zinc-air battery. The application comprises: (1) the high-entropy alloy nanoparticle loaded carbon fiber catalyst is obtained by electrospinning and subsequent high-temperature pyrolysis. (2) a full-solid high-low temperature zinc-air battery is assembled by taking zinc as a negative electrode, a PAA gel electrolyte as a solid electrolyte, and the high-entropy alloy nanoparticle loaded carbon fiber catalyst as a positive electrode. The prepared high-entropy alloy nanoparticle loaded carbon fiber cathode catalyst has a unique active adsorption structure of oxygen intermediates, and exhibits excellent oxygen reduction and oxygen evolution catalytic activity. In addition, the assembled battery can still maintain good cycle life in low-temperature and high-temperature environments.

Description

Technical Field

[0001] This invention belongs to the field of zinc-air battery technology, and particularly relates to a high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst, its preparation method, and its application in all-solid-state high and low temperature zinc-air batteries. Background Technology

[0002] With the ever-increasing demand for traditional fossil fuels, humanity urgently needs to develop new energy sources to replace them. Zinc-air batteries possess a high theoretical energy density (1086 Wh / kg). -1 Zinc-air batteries, characterized by low cost, high safety, and eco-friendliness, are among the most promising new chemical power sources. Due to the diversity of human activities, such as daily life in cold and hot regions, the ability of zinc-air batteries to survive and operate at extreme temperatures (-50 to 60°C) is highly desirable. The fundamental reactions at the cathode of a zinc-air battery under alkaline conditions include the oxygen reduction reaction (ORR) during discharge and the oxygen evolution reaction (OER) during charging. The high potential and low activity of existing oxygen catalysts result in slow ORR / OER reaction kinetics, limiting the overall efficiency of zinc-air batteries. Therefore, finding non-precious metal bifunctional electrocatalysts with high kinetics and low cost is crucial for the practical application of zinc-air batteries.

[0003] High entropy alloys (HEAs) are typically solid solution alloy phases composed of five or more near-equimolar principal elements with nearly equal atomic ratios. The different atomic sizes of each component can lead to lattice distortion and provide a wide variety of multi-element active sites on a single surface. Furthermore, the presence of multiple components promotes the formation of the solid solution phase and inhibits dislocation movement. These properties endow HEAs with unique characteristics such as corrosion resistance, strong fracture toughness, and high mechanical strength. The goal of HEAs is to adapt these characteristics by utilizing virtually unlimited combinations of elements to achieve any desired response. In catalysis, the adsorption behavior of reactants, intermediates, and products on the catalyst surface plays a crucial role. Compared to traditional alloy electrocatalysts, HEAs possess unique multi-element arrangements, exhibiting a variety of exotic structure-activity relationships, allowing for the tuning of catalytic performance under different limiting conditions. Summary of the Invention

[0004] The present invention firstly provides a method for preparing a carbon fiber cathode catalyst supported on high-entropy alloy nanoparticles (manganese, iron, cobalt, nickel, and ruthenium), which is used to solve the problems of low activity, slow reaction kinetics, and short service life of oxygen catalysts supported on existing zinc-air battery cathode materials.

[0005] The present invention also provides a method for preparing an all-solid-state zinc-air battery suitable for high and low temperatures, which solves the problems of narrow applicable temperature range of existing batteries and poor safety and flexibility of liquid batteries.

[0006] To achieve the above objectives, the specific technical solution adopted by the present invention is as follows:

[0007] A method for preparing a carbon fiber cathode catalyst supported on high-entropy alloy nanoparticles, comprising the following steps:

[0008] (1) Disperse the metal salt and polymer in a solvent and stir until homogeneous to obtain a precursor solution, wherein the metal salt includes four or five of manganese, iron, cobalt, nickel and ruthenium;

[0009] (2) Obtain the precursor by electrospinning the precursor solution obtained in step (1);

[0010] (3) After pre-oxidizing and calcining the precursor obtained in step (2), the high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst is obtained.

[0011] Preferably, in step (1), the metal salt is a chloride hydrate of manganese, iron, cobalt, nickel, and ruthenium, with a molar ratio of (0-1.6):(1.0-1.5):(1.0-1.5):(1.0-1.5):(0-1.5); the polymer is polyacrylonitrile, with a mass ratio of polymer to high-entropy alloy of (2-4):1; the solvent is N,N-dimethylformamide; and the stirring temperature is 30-80℃, and the stirring time is 6-12h.

[0012] Preferably, in step (2), the conditions for electrospinning are: the voltage difference between the anode and cathode is 16-21kV, the injection rate is 0.15-0.30mL / h, and the distance between the collector and the needle is 20-30cm.

[0013] Preferably, in step (3), the pre-oxidation conditions are: pre-oxidation at 200-250℃ for 2-4 hours in an air atmosphere; the calcination conditions are: calcination at 800-1000℃ for 2-4 hours in an atmosphere with a volume fraction of 5-10% H2 / Ar, with a heating rate of 2-3℃ / min.

[0014] A high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst prepared by the above preparation method.

[0015] Application of the above-mentioned high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst in an all-solid-state high and low temperature zinc-air battery.

[0016] Preferably, the zinc-air battery uses carbon cloth with the catalyst of claim 5 as the cathode, polished zinc foil as the anode, and acrylic gel as the electrolyte.

[0017] Preferably, the preparation method of the all-solid-state high and low temperature zinc-air battery is as follows:

[0018] S1. The catalyst according to claim 5 is dispersed in a mixed solution of isopropanol and naphthol, and sonicated for 1 ± 0.5 h to obtain a uniformly dispersed catalytic ink solution. This solution is then drop-coated onto carbon cloth with a loading of 2 ± 0.5 mg / cm³. -2 After being dried at room temperature, an air electrode was obtained.

[0019] S2. Sodium hydroxide was added dropwise to a mixed solution of acrylic acid and water, and N,N'-methylenebisacrylamide and potassium persulfate were added to polymerize the solution to obtain a gel electrolyte.

[0020] S3. After polishing the zinc sheet, a metallic negative electrode is obtained;

[0021] S4. Place the air electrode obtained in S1 and the metal negative electrode obtained in S3 on both sides of the gel electrolyte obtained in S2, and encapsulate them with an aluminum-plastic film to obtain the all-solid-state high and low temperature zinc-air battery.

[0022] Preferably, in step S1, the addition ratio of the catalyst, isopropanol, and naphthol is (10±2) mg:(900±100) uL:(100±10) uL; in step S2, the volume ratio of acrylic acid to water is (7-8):10, and a mixed solution is prepared under ice bath conditions; the concentration of sodium hydroxide in the mixed solution is 0.8-1 M; the concentration of N,N'-methylenebisacrylamide in the mixed solution is 0.2-0.3 mg / mL; and the concentration of potassium persulfate in the mixed solution is 5-7 mg / mL.

[0023] Preferably, the application temperature of the battery is -50℃ to 60℃.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] (1) The high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst prepared in this invention has a unique active adsorption structure of oxygen intermediates and exhibits excellent oxygen reduction and oxygen evolution catalytic activity.

[0026] (2) The all-solid-state high and low temperature zinc-air battery prepared by the present invention can still maintain good cycle life in low temperature and high temperature (-50~60℃) environments. Attached Figure Description

[0027] Figure 1 This is a scanning electron microscope image of the catalyst prepared in Example 1 of the present invention.

[0028] Figure 2 This is a transmission electron microscope (TEM) image of the catalyst prepared in Example 1 of the present invention.

[0029] Figure 3 The image shows the XRD pattern of the catalyst prepared in Example 1 of this invention.

[0030] Figure 4 These are comparative test graphs showing the oxygen reduction polarization curves of the catalysts prepared in Examples 1, 2, and 3 and Comparative Examples 1 and 2 of the present invention in a three-electrode system.

[0031] Figure 5 The graphs show the polarization curves of the oxygen evolution reaction in a three-electrode system for the catalysts prepared in Examples 1, 2, and 3 and Comparative Examples 1 and 2 of this invention.

[0032] Figure 6 The discharge curves and power density curves of the flexible solid-state zinc-air battery prepared according to the present invention in Example 1 and a commercially available mixture of Pt / C and RuO2 are shown under normal temperature conditions.

[0033] Figure 7 The figure shows the charge-discharge stability curves of the flexible solid-state zinc-air battery prepared according to the present invention using a mixture of Pt / C and RuO2 in Example 1, at room temperature and with a current density of 10 mA cm⁻¹. -2 .

[0034] Figure 8 The figure shows the charge-discharge stability curves of the flexible solid-state zinc-air battery prepared according to the present invention using a mixture of Pt / C and RuO2 in Example 1, at room temperature and with a current density of 50 mA cm⁻¹. -2 .

[0035] Figure 9 Examples 1, 2, and 3 show the charge-discharge stability curves of flexible solid-state zinc-air batteries prepared according to the technology of the present invention under low temperature (-50°C) conditions, with a current density of 5 mA cm⁻¹. -2 .

[0036] Figure 10 Examples 1, 2, and 3 show the charge-discharge stability curves of flexible solid-state zinc-air batteries prepared according to the technology of the present invention under low-temperature (-30°C) conditions, with a current density of 5 mA cm⁻¹. -2 .

[0037] Figure 11 Example 1 shows the constant current discharge specific capacity curve of the flexible solid-state zinc-air battery prepared according to the technology of the present invention under low temperature and high temperature conditions, with a current density of 5 mA cm⁻¹. -2 .

[0038] Figure 12 The discharge curves and power density curves of the flexible solid-state zinc-air battery prepared according to the technology of the present invention in Example 1 are shown under low temperature and high temperature conditions.

[0039] Figure 13Example 1 shows the charge-discharge stability curves of the flexible solid-state zinc-air battery prepared according to the technology of the present invention under low and high temperature conditions, with a current density of 5 mA cm⁻¹. -2 . Detailed Implementation

[0040] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further explains the invention. Similar parts in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the following detailed description is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0041] Example 1

[0042] A method for preparing a cathode catalyst of high-entropy alloy nanoparticles supported on carbon fiber (HEAs / CNF) for all-solid-state high and low temperature zinc-air batteries includes the following steps:

[0043] 1) Preparation of MnFeCoNiRu / PAN precursor: 50 mg of manganese chloride tetrahydrate (MnCl2·4H2O), 67 mg of ferric chloride hexahydrate (FeCl3·6H2O), 59 mg of cobalt chloride hexahydrate (CoCl3·6H2O), 59 mg of nickel chloride hexahydrate (NiCl3·6H2O), 56 mg of ruthenium chloride hydrate (RuCl3·3H2O), and 750 mg of polyacrylonitrile (PAN) were uniformly dispersed in 11 g of N,N-dimethylformamide solution and stirred at room temperature for 12 h. The prepared precursor solution was loaded into a syringe with a stainless steel needle and assembled on an electrospinning machine. The voltage difference between the anode and cathode was 20.5 kV, the injection rate was 0.25 mL / h, and the distance between the collector and the needle was 25 cm. MnFeCoNiRu / PAN was obtained by electrospinning.

[0044] 2) The MnFeCoNiRu / PAN precursor obtained in step 1) is placed in a tube furnace and calcined at 230°C for 3 hours in an air atmosphere for pre-oxidation. Then it is calcined at 950°C for 3 hours in a 5% H2 / Ar atmosphere to obtain the high-entropy alloy nanoparticle-supported carbon fiber catalyst MnFeCoNiRu / CNF required by this invention.

[0045] The high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst prepared above for all-solid-state high and low temperature zinc-air batteries maintains the basic morphology of the precursor material. For example... Figure 1 Figure 2 As shown, the diameter of carbon fibers is between 150 and 200 nanometers, while the average diameter of high-entropy alloy nanoparticles is approximately 10–25 nm.

[0046] Catalytic performance test:

[0047] Oxygen reduction and oxygen evolution performance tests were conducted using a three-electrode system. The working electrode was a glassy carbon electrode loaded with the catalyst prepared in Example 1, and the counter and reference electrodes were a silver / silver chloride electrode and a carbon rod, respectively. The test solution was a 0.1M potassium hydroxide solution. The catalytic ink consisted of 5 mg of catalyst material, 710 μL of isopropanol, 240 μL of deionized water, and 50 μL of naphthol. In this invention, 11 μL of the catalytic ink was dropped onto the glassy carbon electrode and air-dried for later use. The catalytic performance was compared with that of commercial Pt / C.

[0048] Zinc-air battery test:

[0049] a) Preparation of the air electrode: 10 mg of the catalyst prepared in Example 1 was dispersed in a mixed solution of 900 μL isopropanol and 100 μL naphthol, and sonicated for 1 h to obtain a uniformly dispersed catalytic ink solution. This solution was then dropped onto a 2*3 cm... 2 On a carbon cloth of a certain size, the loading amount is 2mg cm -2 The area is 1*1cm 2 It is dried at room temperature and used as the air electrode of a flexible solid-state zinc-air battery.

[0050] b) Preparation of gel electrolyte: 7.2 mL of acrylic acid was poured into 10 mL of water and stirred in an ice bath to prepare a mixed solution. Then, 0.8 M sodium hydroxide solution was slowly added dropwise to the acrylic acid solution. Finally, N,N'-methylenebisacrylamide (4 mg) and potassium persulfate (110 mg) were added to the solution and stirred for 1 h and then polymerized in an oven.

[0051] c) Preparation of the metal negative electrode: Cut the zinc sheet into 2*3cm pieces. 2 Sized and polished, it serves as the anode of a zinc-air battery.

[0052] d) Preparation of the zinc-air battery: The air electrode (a) and the zinc anode (c) were placed on either side of the gel electrolyte (b) and encapsulated with an aluminum-plastic film to obtain a flexible solid-state zinc-air battery with a sandwich structure. A commercial Pt / C and RuO2 mixture with a mass ratio of 1:1 was used as a control sample and tested under the same conditions.

[0053] Example 2

[0054] A method for preparing a catalyst, specifically including the following steps:

[0055] 1) Preparation of MnFeCoNi / PAN precursor: 63 mg of manganese chloride tetrahydrate (MnCl2·4H2O), 84 mg of ferric chloride hexahydrate (FeCl3·6H2O), 74 mg of cobalt chloride hexahydrate (CoCl3·6H2O), 74 mg of nickel chloride hexahydrate (NiCl3·6H2O), and 750 mg of polyacrylonitrile (PAN) were uniformly dispersed in 11 g of N,N-dimethylformamide solution and stirred at room temperature for 12 h. The prepared precursor solution was loaded into a syringe with a stainless steel needle and assembled on an electrospinning machine. The voltage difference between the anode and cathode was 20.5 kV, the injection rate was 0.25 mL / h, and the distance between the collector and the needle was 25 cm. MnFeCoNi / PAN was obtained by electrospinning.

[0056] 2) The MnFeCoNi / PAN precursor obtained in step 1) was placed in a tube furnace and calcined at 230°C for 3 hours in an air atmosphere for pre-oxidation. Then it was calcined at 950°C for 3 hours in a 5% H2 / Ar atmosphere and allowed to cool naturally to room temperature before being taken out for testing.

[0057] Example 2 differs from Example 1 in that the type and mass of the chloride salts are changed. The chloride salts in Example 2 are manganese chloride tetrahydrate, ferric chloride hexahydrate, cobalt chloride hexahydrate, and nickel chloride hexahydrate, with masses of 63 mg, 84 mg, 74 mg, and 74 mg, respectively.

[0058] Example 3

[0059] A method for preparing a catalyst, specifically including the following steps:

[0060] 1) Preparation of FeCoNiRu / PAN precursor: 84 mg of ferric chloride hexahydrate (FeCl3·6H2O), 74 mg of cobalt chloride hexahydrate (CoCl3·6H2O), 74 mg of nickel chloride hexahydrate (NiCl3·6H2O), 70 mg of ruthenium chloride hydrate (RuCl3·3H2O), and 750 mg of polyacrylonitrile (PAN) were uniformly dispersed in 11 g of N,N-dimethylformamide solution and stirred at room temperature for 12 h. The prepared precursor solution was loaded into a syringe with a stainless steel needle and assembled on an electrospinning machine. The voltage difference between the anode and cathode was 20.5 kV, the injection rate was 0.25 mL / h, and the distance between the collector and the needle was 25 cm. FeCoNiRu / PAN was obtained by electrospinning.

[0061] 2) The FeCoNiRu / PAN precursor obtained in step 1) was placed in a tube furnace and calcined at 230°C for 3 hours in an air atmosphere for pre-oxidation. Then it was calcined at 950°C for 3 hours in a 5% H2 / Ar atmosphere and allowed to cool naturally to room temperature before being taken out for testing.

[0062] Example 3 differs from Example 1 in that the type and mass of the chloride salts are changed. The chloride salts in Example 3 are ferric chloride hexahydrate, cobalt chloride hexahydrate, nickel chloride hexahydrate, and ruthenium chloride hydrate, with masses of 84 mg, 74 mg, 74 mg, and 70 mg, respectively.

[0063] Comparative Example 1

[0064] A method for preparing a catalyst, specifically including the following steps:

[0065] 1) Preparation of FeCoNi / PAN precursor: 112 mg of ferric chloride hexahydrate (FeCl3·6H2O), 98 mg of cobalt chloride hexahydrate (CoCl3·6H2O), 98 mg of nickel chloride hexahydrate (NiCl3·6H2O), and 750 mg of polyacrylonitrile (PAN) were uniformly dispersed in 11 g of N,N-dimethylformamide solution and stirred at room temperature for 12 h. The prepared precursor solution was loaded into a syringe with a stainless steel needle and assembled on an electrospinning machine. The voltage difference between the anode and cathode was 20.5 kV, the injection rate was 0.25 mL / h, and the distance between the collector and the needle was 25 cm. FeCoNi / PAN was obtained by electrospinning.

[0066] 2) The FeCoNi / PAN precursor obtained in step 1) was placed in a tube furnace and calcined at 230°C for 3 hours in an air atmosphere for pre-oxidation. Then it was calcined at 950°C for 3 hours in a 5% H2 / Ar atmosphere and allowed to cool naturally to room temperature before being taken out for testing.

[0067] The difference between Comparative Example 1 and Example 1 is that the types and masses of chloride salts were changed. The chloride salts in Comparative Example 1 were ferric chloride hexahydrate, cobalt chloride hexahydrate, and nickel chloride hexahydrate, with masses of 112 mg, 98 mg, and 98 mg, respectively.

[0068] Comparative Example 2

[0069] 1) Preparation of Ru / PAN precursor: 280 mg of ruthenium chloride hydrate (RuCl3·3H2O) and 750 mg of polyacrylonitrile (PAN) were uniformly dispersed in 11 g of N,N-dimethylformamide solution and stirred at room temperature for 12 h. The prepared precursor solution was loaded into a syringe with a stainless steel needle and assembled on an electrospinning machine. The voltage difference between the anode and cathode was 20.5 kV, the injection rate was 0.25 mL / h, and the distance between the collector and the needle was 25 cm. Ru / PAN was obtained by electrospinning.

[0070] 2) Place the Ru / PAN polyhedron obtained in step 1) in a tube furnace and heat it from room temperature to 900℃ at a rate of 2℃ / min under an argon atmosphere. Hold it at 900℃ for 2 hours and allow it to cool naturally to room temperature before taking it out for testing.

[0071] The difference between Comparative Example 2 and Example 1 is that no manganese chloride tetrahydrate, ferric chloride hexahydrate, cobalt chloride hexahydrate, and nickel chloride hexahydrate were added.

[0072] The catalyst described in Example 1 of this invention exhibits excellent oxygen reduction catalytic performance. Figure 4 The results are the linear voltammetric scan (LSV) results of oxygen reduction for the catalysts prepared in Examples 1, 2, 3 and Comparative Examples 1, 2, at a rotation speed of 1600 rpm. The half-wave potential of the catalyst prepared in Example 1 is 0.85 V at a rotation speed of 1600 rpm.

[0073] The catalyst described in Example 1 of this invention exhibits excellent oxygen evolution catalytic performance. Figure 5 The linear voltammetric scan (LSV) results for oxygen evolution of the catalysts prepared in Examples 1, 2, 3, and Comparative Examples 1, 2, are obtained by testing at a rotation speed of 1600 rpm. The catalyst prepared in Example 1 was tested at a current density of 10 mA cm⁻¹ at a rotation speed of 1600 rpm. -2 The overpotential at that time was 268mV.

[0074] The catalyst material prepared in Example 1 of this invention can be used as a cathode catalyst in rechargeable flexible solid-state zinc-air batteries. Figure 6 The discharge curves and power density curves of the catalyst material prepared in Example 1 and the flexible solid-state zinc-air battery prepared according to the present invention using Pt / C+RuO2 are shown at room temperature. Figure 6 As can be seen, under normal temperature conditions and a voltage of 0.4V, the current density of the catalyst material prepared in Example 1 of this invention can reach 400 mA cm⁻¹. -2 Higher than 158 mA cm⁻¹ of commercially available catalysts -2 The catalyst material prepared in Example 1 of this invention has a power density of approximately 168 mW / cm² at room temperature. -2 71 mW cm⁻¹ higher than commercially available catalysts -2 .

[0075] The catalyst material prepared in Example 1 of this invention can be used as a cathode catalyst in rechargeable flexible solid-state zinc-air batteries. Figure 7 Figure 8 shows the charge-discharge stability curves of the catalyst material prepared in Example 1 and the flexible solid-state zinc-air battery prepared according to the present invention using Pt / C+RuO2 at room temperature. Figure 7 As can be seen from Figure 8: Under normal temperature conditions, the current is 10.50 mA cm. -2 At that time, the catalyst material prepared in Example 1 of this invention can withstand 500 and 200 charge-discharge cycles, which is higher than that of commercial catalysts.

[0076] The catalyst material prepared in Example 1 of this invention can be used as a cathode catalyst in rechargeable flexible solid-state zinc-air batteries. Figure 11 The figure shows the discharge specific capacity curves of a flexible solid-state zinc-air battery prepared according to the present invention using the catalyst material prepared in Example 1, under low and high temperature environments. As can be seen from the figure, the battery can survive and operate at extreme temperatures (-50 to 60°C).

[0077] The catalyst material prepared in Example 1 of this invention can be used as a cathode catalyst to enable rechargeable flexible solid-state zinc-air batteries to survive and operate at extreme temperatures (-50 to 60°C). Figure 13 Charge-discharge stability curves of a flexible solid-state zinc-air battery prepared using the catalyst material prepared in Example 1 under high and low temperature conditions. From... Figure 13 It can be seen that the current is 5 mA cm under conditions of -50 and 60℃. -2 At that time, the catalyst material prepared in Example 1 of the present invention can be charged and discharged for 1000, 180 cycles.

[0078] Obviously, the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to list all the embodiments here. Any obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. The application of a high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst in an all-solid-state high- and low-temperature zinc-air battery, characterized in that, The zinc-air battery uses carbon cloth with the catalyst as the cathode, polished zinc foil as the anode, and acrylic gel as the electrolyte; the battery's operating temperature is -50 ℃ ~ 60 ℃. The catalyst is prepared in the following steps: (1) Disperse the metal salt and polymer in a solvent and stir until homogeneous to obtain a precursor solution, wherein the metal salt is manganese, iron, cobalt, nickel, or ruthenium; (2) Obtain the precursor by electrospinning the precursor solution obtained in step (1); (3) The precursor obtained in step (2) is pre-oxidized and calcined to obtain the high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst; the calcination is carried out in an atmosphere with a volume fraction of 5-10% H2 / Ar. In step (1), the metal salt is a chloride hydrate of manganese, iron, cobalt, nickel, and ruthenium, with a molar ratio of (0-1.6):(1.0-1.5):(1.0-1.5):(1.0-1.5):(0-1.5); the polymer is polyacrylonitrile, with a mass ratio of polymer to high-entropy alloy of (2-4):1; the solvent is N,N-dimethylformamide; and the stirring temperature is 20-80 ℃, and the stirring time is 6-12 h. In step (3), the pre-oxidation conditions are: pre-oxidation at 200-250 ℃ for 2-4 h in an air atmosphere; the calcination conditions are: calcination at 800-1000 ℃ for 2-4 h with a heating rate of 2-3 ℃ / min.

2. The application according to claim 1, characterized in that, In step (2), the conditions for electrospinning are: the voltage difference between the anode and cathode is 16-21 kV, the injection rate is 0.15-0.30 mL / h, and the distance between the collector and the needle is 20-30 cm.

3. The application according to claim 1, characterized in that, The preparation method of the all-solid-state high and low temperature zinc-air battery is as follows: S1. The catalyst was dispersed in a mixed solution of isopropanol and naphthol, and sonicated for 1 ± 0.5 h to obtain a uniformly dispersed catalytic ink solution. This solution was then drop-coated onto carbon cloth with a loading of 2 ± 0.5 mg / cm³. -2 After being dried at room temperature, an air electrode was obtained. S2. Sodium hydroxide was added dropwise to a mixed solution of acrylic acid and water, and N,N'-methylenebisacrylamide and potassium persulfate were added to polymerize the solution to obtain a gel electrolyte. S3. After polishing the zinc sheet, a metallic negative electrode is obtained; S4. Place the air electrode obtained in S1 and the metal negative electrode obtained in S3 on both sides of the gel electrolyte obtained in S2, and encapsulate them with an aluminum-plastic film to obtain the all-solid-state high and low temperature zinc-air battery.

4. The application according to claim 3, characterized in that, In step S1, the addition ratio of the catalyst, isopropanol, and naphthol is (10±2) mg: (900±100) uL: (100±10) uL; In step S2, the volume ratio of acrylic acid to water is (7-8):10, and a mixed solution is prepared under ice bath conditions; the concentration of sodium hydroxide in the mixed solution is 0.8-1 M; the concentration of N,N'-methylenebisacrylamide in the mixed solution is 0.2-0.3 mg / mL; and the concentration of potassium persulfate in the mixed solution is 5-7 mg / mL.

Images