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CN-122000366-A - Porous carbon fiber film electrode loaded with metal alloy nano particles for lithium oxygen/air battery and preparation method thereof

CN122000366ACN 122000366 ACN122000366 ACN 122000366ACN-122000366-A

Abstract

The invention discloses a porous carbon fiber membrane electrode loaded with metal alloy nano particles for a lithium oxygen/air battery and a preparation method thereof, wherein the preparation method comprises the steps of dissolving a carbon preparation agent in water, adding a pore-forming agent and a cross-linking agent, uniformly mixing to obtain spinning solution slurry, and carrying out electrostatic spinning and two-step sintering to form the porous carbon fiber membrane electrode; and (3) dropwise adding the mixed metal salt solution onto the porous carbon fiber film electrode, and thermally shocking the carbon to obtain the porous carbon fiber film electrode loaded with the metal alloy nano particles. The electrode containing abundant micropores, mesopores and macropores and loaded with alloy nano particles is constructed, the three-phase interface and the catalytic active site required by charge and discharge can be effectively increased, the catalytic reaction activity and the discharge capacity of the electrode are increased, the charge and discharge overpotential is reduced, and therefore the occurrence of side reactions is reduced.

Inventors

  • ZHANG XINBO
  • FAN YINGQI
  • LIU TONG
  • CAO RENFEI
  • HUANG GANG

Assignees

  • 中国科学院长春应用化学研究所

Dates

Publication Date
20260508
Application Date
20260113

Claims (10)

  1. 1. A preparation method of a porous carbon fiber film electrode loaded with metal alloy nano particles for a lithium oxygen/air battery is characterized by comprising the following steps of, Dissolving a carbon-making agent in water, adding a pore-forming agent and a cross-linking agent, and uniformly mixing to obtain spinning solution slurry; Carrying out electrostatic spinning on the spinning solution slurry to obtain a spinning fiber film; Sintering the spinning fiber film in two steps to form a porous carbon fiber film electrode; preparing a mixed metal salt solution by using a metal precursor and a solvent; and (3) dropwise adding the mixed metal salt solution onto the porous carbon fiber film electrode, and thermally shocking carbon for 50-500 ms at 1600-2800 ℃ in a joule heating mode to obtain the porous carbon fiber film electrode loaded with metal alloy nano particles for the lithium oxygen/air battery.
  2. 2. The method of claim 1, wherein the carbon-producing agent comprises one or more of polyacrylonitrile PAN, polyvinylidene fluoride PVDF, polyvinyl alcohol PVA, polyether sulfone PES, polyurethane PU, polylactic acid PLA, polystyrene PS, polyimide PI, polyetherimide PEI, poly-m-phenylene terephthamide PMIA, collagen, silk fibroin, hyaluronic acid, chitosan and chitin, the pore-forming agent comprises one or more of polymer microspheres and inorganic non-metal simple substance particles, and the crosslinking agent comprises one or more of polyacids, polyalcohol and organic matters containing unsaturated double bonds.
  3. 3. The method of claim 2, wherein the mass ratio of the carbonaceous material to the pore-forming agent is 1:2-4, and the amount of the crosslinking agent added is 0.02-0.04 wt% based on the total mass of the carbonaceous material and the pore-forming agent.
  4. 4. The method of claim 1, wherein the metal precursor and the solvent are mixed to obtain a mixed metal salt solution, the metal precursor comprises a rare earth metal salt, a transition metal salt and an inorganic metal acid, and the concentration of each metal ion in the mixed metal salt solution is 0.01-0.1 mol.L -1 .
  5. 5. The method of claim 1, wherein the mixed metal salt solution is added dropwise to the porous carbon fiber membrane electrode in an amount of 10 to 100. Mu.L cm -2 .
  6. 6. The method of claim 1, wherein the spinning solution slurry is subjected to electrostatic spinning, wherein the voltage of the electrostatic spinning is 10-40 kV, the flow rate of the spinning solution of the electrostatic spinning is 0.3-5 mL.h -1 , the receiving distance of the electrostatic spinning is 15-30 cm, the environmental temperature of the electrostatic spinning is 20-30 ℃, and the environmental humidity of the electrostatic spinning is 25-40 RH%.
  7. 7. The preparation method of the fiber spinning film according to claim 1, wherein the two-step sintering comprises pre-oxidation sintering and carbonization sintering, wherein the pre-oxidation sintering temperature is 220-280 ℃, the pre-oxidation sintering time is 2-4 hours, the pre-oxidation sintering atmosphere is air, the carbonization sintering temperature is 600-1200 ℃, the carbonization sintering time is 1.5-4 hours, and the carbonization sintering atmosphere is one or more of argon, nitrogen and carbon dioxide.
  8. 8. The method of claim 7, wherein the drawing force is provided by pressing graphite plates during the two-step sintering process.
  9. 9. The porous carbon fiber membrane electrode loaded with metal alloy nano particles for the lithium oxygen/air battery, which is prepared by the preparation method according to any one of claims 1-8.
  10. 10. The metal alloy nanoparticle-supported porous carbon fiber membrane electrode for a lithium oxygen/air battery of claim 9, wherein the electrode is of a porous structure, the porous structure comprises a microporous structure, a mesoporous structure and a macroporous structure, the pore diameter of the microporous structure is 0-3 nm, the pore diameter of the mesoporous structure is 3-50 nm, and the pore diameter of the macroporous structure is >50nm.

Description

Porous carbon fiber film electrode loaded with metal alloy nano particles for lithium oxygen/air battery and preparation method thereof Technical Field The invention belongs to the technical field of lithium oxygen/air batteries, and particularly relates to a porous carbon fiber membrane electrode loaded with metal alloy nano particles for a lithium oxygen/air battery and a preparation method thereof. Background A lithium oxygen/air cell is a metal fuel cell with ultra-high theoretical capacity density. The lithium metal is used as a negative electrode during operation, and oxygen which is ubiquitous in air is used for reacting with the positive electrode. The energy density of the fuel oil has theoretical energy density comparable to that of gasoline, and has great potential in the fields of electric automobiles and energy storage. In order to realize better catalytic capability and performance of the lithium oxygen/air battery, the prior researches respectively carry out research layout in the aspects of electrode structural design and high catalytic activity electrode materials. In the electrode structure design, the size of particles can be reduced to increase the length of three-phase interfaces (ion conductors, electron conductors and reaction gases), and the specific surface area and the pore volume of the electrode can be increased to provide a larger growth space for discharge products. However, the battery has a large overpotential, so that the material is unstable in charge and discharge, and the electrode material with high catalytic activity is required to be matched. The rare earth-containing high-entropy alloy material has rich active sites and a tuned electronic structure, and has excellent catalytic activity. Therefore, finding a suitable method for synthesizing the electrode material with the porous structure containing the rare earth high-entropy alloy has important significance. Disclosure of Invention This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the invention and in the title of the invention, which may not be used to limit the scope of the invention. The present invention has been made in view of the above and/or problems occurring in the prior art. Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of a porous carbon fiber membrane electrode loaded with metal alloy nano particles for a lithium oxygen/air battery. In order to solve the technical problems, the invention provides the following technical proposal that comprises, Dissolving a carbon-making agent in water, adding a pore-forming agent and a cross-linking agent, and uniformly mixing to obtain spinning solution slurry; Carrying out electrostatic spinning on the spinning solution slurry to obtain a spinning fiber film; Sintering the spinning fiber film in two steps to form a porous carbon fiber film electrode; preparing a mixed metal salt solution by using a metal precursor and a solvent; and (3) dropwise adding the mixed metal salt solution onto the porous carbon fiber film electrode, and thermally shocking carbon for 50-500 ms at 1600-2800 ℃ in a joule heating mode to obtain the porous carbon fiber film electrode loaded with metal alloy nano particles for the lithium oxygen/air battery. The preparation method is characterized in that the carbon-making agent comprises one or more of polyacrylonitrile PAN, polyvinylidene fluoride PVDF, polyvinyl alcohol PVA, polyether sulfone PES, polyurethane PU, polylactic acid PLA, polystyrene PS, polyimide PI, polyether imide PEI, poly-m-phenylene terephthamide PMIA, collagen, silk fibroin, hyaluronic acid, chitosan and chitin, the pore-forming agent comprises one or more of polymer microspheres and inorganic non-metal simple substance particles, and the crosslinking agent comprises one or more of polybasic acid, polyalcohol and organic matters containing unsaturated double bonds. As a preferable scheme of the preparation method, the mass ratio of the carbon making agent to the pore-forming agent is 1:2-4, and the addition amount of the cross-linking agent is 0.02-0.04 wt% compared with the total mass of the carbon making agent and the pore-forming agent. The preparation method is characterized in that a metal precursor and a solvent are used for preparing a mixed metal salt solution, wherein the metal precursor comprises rare earth metal element metal salt, transition metal element metal salt and inorganic metal acid, and the concentration of each metal ion in the mixed metal salt solution is 0.01-0.1 mol.L -1. The preparation method is characterized in that the mixed metal salt solution is dripped onto the porous carbon fiber film electrode, wherein the dripping amount of the mixed metal salt solution is 10-100 mu L cm -2. As a preferable scheme of the pre