CN-118448654-B - High-entropy alloy nanoparticle loaded carbon fiber cathode catalyst, preparation method and application thereof in all-solid-state high-low temperature zinc-air battery

Abstract

The invention belongs to the field of zinc-air batteries, and particularly relates to a high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst, a preparation method and application thereof in an all-solid-state high-low temperature zinc-air battery. The invention comprises (1) the high-entropy alloy nanoparticle supported carbon fiber catalyst is obtained by electrostatic spinning and subsequent pyrolysis. (2) The metal zinc is used as a negative electrode, the PAA gel electrolyte is used as a solid electrolyte, and the high-entropy alloy nanoparticle supported carbon fiber catalyst is used as a positive electrode to assemble the all-solid-state high-low temperature zinc-air battery. The high-entropy alloy nanoparticle supported carbon fiber cathode catalyst prepared by the invention has a unique oxygen intermediate active adsorption structure, and shows excellent oxygen reduction and oxygen precipitation catalytic activity. In addition, the assembled battery can still maintain good cycle life in low and high temperature environments.

Inventors

• LIU JUN
• GU TENGTENG
• ZHU MIN

Assignees

• 华南理工大学

Dates

Publication Date

20260508

Application Date

20240418

Claims (4)

1. 1. The application of the high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst in an all-solid-state high-low temperature zinc-air battery is characterized in that the zinc-air battery takes carbon cloth added with the catalyst as a cathode, polished zinc foil as an anode and acrylic acid gel as electrolyte, wherein the application temperature of the battery is-50 ℃ to 60 ℃; The preparation steps of the catalyst are as follows: (1) Dispersing metal salt and polymer in a solvent, and uniformly stirring to obtain a precursor solution, wherein the metal salt is manganese, iron, cobalt, nickel and ruthenium; (2) Carrying out electrostatic spinning on the precursor solution obtained in the step (1) to obtain a precursor; (3) Pre-oxidizing and calcining the precursor obtained in the step (2) to obtain the high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst, wherein the calcination is performed in an atmosphere with the volume fraction of 5-10% H 2 /Ar; In the step (1), the metal salt is chloridized hydrate of manganese, iron, cobalt, nickel and ruthenium, the molar ratio is (0-1.6): 1.0-1.5: (0-1.5), the polymer is polyacrylonitrile, the mass ratio of the polymer to the high-entropy alloy is (2-4): 1, the solvent is N, N-dimethylformamide, the stirring temperature is 20-80 ℃ and the stirring time is 6-12 h; In the step (3), the pre-oxidation condition is that 2-4 h is pre-oxidized under the air atmosphere at 200-250 ℃, the calcination condition is that 2-4 h is calcined under 800-1000 ℃, and the temperature rising rate is 2-3 ℃ per minute.
2. 2. The use according to claim 1, wherein in step (2), the electrospinning is carried out under conditions that the cathode-anode voltage 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. 3. The use according to claim 1, wherein the preparation method of the all-solid-state high-low temperature zinc-air battery is as follows: S1, dispersing the catalyst in a mixed solution of isopropanol and naphthol, carrying out ultrasonic treatment on the mixed solution by 1+/-0.5 h to obtain a uniformly dispersed catalytic ink solution, dripping the uniformly dispersed catalytic ink solution on carbon cloth, wherein the loading capacity is 2+/-0.5 mg cm -2 , and airing at room temperature to obtain an air electrode; s2, dripping sodium hydroxide into an acrylic acid and water mixed solution, and adding N, N' -methylene bisacrylamide and potassium persulfate for polymerization to obtain a gel electrolyte; s3, polishing the zinc sheet to obtain a metal negative electrode; And S4, respectively placing the air electrode obtained in the S1 and the metal negative electrode obtained in the S3 on two sides of the gel electrolyte obtained in the S2, and packaging by using an aluminum plastic film to obtain the all-solid-state high-low temperature zinc-air battery.
4. 4. The method according to claim 3, wherein in the step S1, the catalyst, isopropanol and naphthol are added in a ratio of (10+ -2) mg (900+ -100) uL (100+ -10) uL; In the step S2, the volume ratio of the acrylic acid to the water is (7-8): 10, a mixed solution is prepared under the ice bath condition, the concentration of the sodium hydroxide in the mixed solution is 0.8-1M, the concentration of the N, N' -methylenebisacrylamide in the mixed solution is 0.2-0.3 mg/mL, and the concentration of the potassium persulfate in the mixed solution is 5-7 mg/mL.

Description

High-entropy alloy nanoparticle loaded carbon fiber cathode catalyst, preparation method and application thereof in all-solid-state high-low temperature zinc-air battery Technical Field The invention belongs to the technical field of zinc-air batteries, and particularly relates to a high-entropy alloy nanoparticle-supported carbon fiber cathode catalyst, a preparation method and application thereof in an all-solid-state high-low temperature zinc-air battery. Background With the increasing demand for traditional fossil fuels, there is an urgent need for humans to develop new energy sources to replace traditional fuels. The zinc-air battery has the characteristics of high theoretical energy density (1086 Wh kg -1), low cost, high safety, ecological friendliness and the like, and is one of the most promising novel chemical power supplies. Due to the diversity of human activities, such as daily living in cold and hot areas, zinc-air batteries are highly sought after to survive and operate at extreme temperatures (-50-60 ℃). Basic reactions of zinc-air cell cathodes under alkaline conditions include oxygen reduction reactions upon discharge (ORR) and oxygen evolution reactions upon charge (OER). The existing oxygen catalyst has the characteristics of high potential and low activity, so that the ORR/OER reaction kinetics is slow, and the overall efficiency of the zinc-air battery is limited. Therefore, finding a non-noble metal bi-functional electrocatalyst with high kinetics and low cost is very important for practical application in zinc-air batteries. The high-entropy alloy (HEAs) is typically a solid solution alloy phase composed of five or more nearly equimolar main elements with approximately equal atomic ratios. The atomic size of each component is different, which can lead to lattice distortion and provide a wide variety of multielement active sites on a single surface. In addition, the presence of multiple components is beneficial to promote the formation of solid solution phases and inhibit dislocation movement. These properties impart HEAs unique properties such as corrosion resistance, strong fracture toughness, and high mechanical strength. The goal of HEA is to adapt these features by utilizing almost infinite possible combinations of elements to achieve any desired response. In the catalytic field, the adsorption behavior of reactants, intermediates and products on the catalyst surface plays a critical role. Compared with the traditional alloy electrocatalyst, HEAs has a unique multi-element arrangement mode, shows a plurality of peculiar structure-activity relations, and can adjust the catalytic performance under different limiting conditions. Disclosure of Invention The invention firstly provides a preparation method of a carbon fiber cathode catalyst loaded by high-entropy alloy nano particles (manganese, iron, cobalt, nickel and ruthenium), which is used for solving the problems of low activity, slow reaction kinetics, short service life and the like of an oxygen catalyst loaded on the cathode material of the traditional zinc-air battery. The invention further provides a preparation method of the all-solid-state zinc-air battery suitable for high and low temperatures, which is used for solving the problems of narrow applicable temperature range and poor safety and flexibility of the conventional battery. In order to achieve the purpose, the invention adopts the following specific technical scheme: the preparation method of the high-entropy alloy nanoparticle supported carbon fiber cathode catalyst comprises the following steps: (1) Dispersing metal salt and polymer in a solvent, and uniformly stirring to obtain a precursor solution, wherein the metal salt comprises four or five of manganese, iron, cobalt, nickel and ruthenium; (2) Carrying out electrostatic spinning on the precursor solution obtained in the step (1) to obtain a precursor; (3) And (3) pre-oxidizing and calcining the precursor obtained in the step (2) to obtain the high-entropy alloy nanoparticle supported carbon fiber cathode catalyst. Preferably, in the step (1), the metal salt is chloride hydrate of manganese, iron, cobalt, nickel and ruthenium, the molar ratio is (0-1.6): 1.0-1.5: (0-1.5), the polymer is polyacrylonitrile, the mass ratio of the polymer to the high-entropy alloy is (2-4): 1, the solvent is N, N-dimethylformamide, and the stirring temperature is 30-80 ℃ and the stirring time is 6-12h. Preferably, in the step (2), the condition of electrostatic spinning is that the voltage difference between anode and cathode is 16-21kV, the injection rate is 0.15-0.30mL/h, and the distance between a collector and a needle is 20-30cm. Preferably, in the step (3), the pre-oxidation condition is that the pre-oxidation is carried out for 2-4 hours under the air atmosphere at 200-250 ℃, the calcination condition is that the calcination is carried out for 2-4 hours under the atmosphere of 800-1000 ℃ with the volume fraction of 5-10%