Search

CN-122025672-A - Non-noble metal amorphous high-entropy alloy catalyst for lithium air battery and preparation method thereof

CN122025672ACN 122025672 ACN122025672 ACN 122025672ACN-122025672-A

Abstract

The invention discloses a non-noble metal amorphous high-entropy alloy catalyst for lithium air batteries and a preparation method thereof, comprising the steps of dissolving sodium citrate and non-noble metal transition metal salt in deionized water to obtain a homogeneous aqueous solution, adding sodium borohydride to perform reduction reaction, adding ammonium chloride to stir uniformly, standing for gelation to obtain a precipitate, washing the precipitate, centrifuging, and freeze-drying to obtain the non-noble metal amorphous high-entropy alloy catalyst. The method adopts a normal temperature liquid phase reduction method, has simple process and convenient operation, does not need complex equipment and severe reaction conditions, and is suitable for large-scale production. The prepared non-noble metal amorphous high-entropy alloy catalyst has a nano porous structure, has high specific surface area and high electrochemical activity area, and shows excellent catalytic activity in a lithium air battery.

Inventors

  • ZHANG XINBO
  • FAN YINGQI
  • DI YIFAN
  • LIU DONGXUE
  • LIU TONG
  • HUANG GANG

Assignees

  • 中国科学院长春应用化学研究所

Dates

Publication Date
20260512
Application Date
20260107

Claims (10)

  1. 1. A preparation method of a non-noble metal amorphous high-entropy alloy catalyst for a lithium air battery is characterized by comprising the steps of, Dissolving sodium citrate and non-noble metal transition metal salt in deionized water to obtain a homogeneous aqueous solution, adding sodium borohydride, carrying out reduction reaction, adding ammonium chloride, stirring uniformly, standing for gelation to obtain a precipitate, washing the precipitate, centrifuging, and freeze-drying to obtain the non-noble metal amorphous high-entropy alloy catalyst; Wherein the temperature of the reduction reaction is 5-40 ℃ and the time is 2-8 h.
  2. 2. The method of claim 1, wherein the non-noble metal transition metal salt comprises a manganese salt, an iron salt, a cobalt salt, a nickel salt, a copper salt, a tin salt, a zinc salt, or a chromium salt.
  3. 3. The method of claim 2, wherein the molar ratio of manganese salt, iron salt, cobalt salt, nickel salt, and copper salt is 0.3-1:0.3-1.
  4. 4. The method of claim 2, wherein the manganese salt is manganese chloride, the iron salt is ferric chloride, the cobalt salt is cobalt chloride, the nickel salt is nickel chloride, and the copper salt is copper chloride.
  5. 5. The method of claim 1, wherein the molar ratio of sodium citrate, non-noble metal transition metal salt, sodium borohydride, and ammonium chloride is 15-20:1-1.5:15-20:1-1.5.
  6. 6. The method of claim 1, wherein the precipitate is washed, centrifuged and freeze-dried at a rotational speed of 5000-12000 rpm.
  7. 7. The method of claim 6, wherein the freeze-drying temperature is-10 to-70 ℃ and the freeze-drying time is 10 to 50 hours.
  8. 8. The non-noble metal amorphous high-entropy alloy catalyst prepared by the preparation method according to any one of claims 1-7.
  9. 9. The amorphous high-entropy alloy catalyst of claim 8, wherein the general formula of the amorphous high-entropy alloy catalyst is Mn a Fe b Co c Ni d Cu e , the molar ratio of a to b to c to d to e is 0.3-1:0.3-1, and the amorphous high-entropy alloy catalyst of the amorphous phase structure.
  10. 10. The use of the non-noble metal amorphous high-entropy alloy catalyst according to claim 9 in lithium-air batteries, wherein the use comprises, Mixing the high-entropy alloy catalyst with a conductive carbon material according to the mass ratio of (0.5-3) to obtain an active substance, mixing the active substance with a binder according to the mass ratio of (4-9): 1, adding an NMP solvent, uniformly stirring, spraying the obtained slurry on the surface of carbon paper, and drying to form an anode; Wherein the conductive carbon material comprises one of KB, SP, CNT and the binder material comprises one of PVDF and PTFE.

Description

Non-noble metal amorphous high-entropy alloy catalyst for lithium air battery and preparation method thereof Technical Field The invention belongs to the technical field of catalysts, and particularly relates to a non-noble metal amorphous high-entropy alloy catalyst for a lithium air battery and a preparation method thereof. Background The lithium air battery has theoretical energy of about 3500 Wh/kg, which is ten times that of the current lithium ion battery. In practical use, exertion of energy density of lithium air batteries is limited, and the use of noble metal catalysts of noble metals in most lithium air batteries makes the batteries have extremely high cost, so that preparation of large-capacity batteries is difficult, and practical use needs cannot be met. Therefore, a low-cost and high-efficiency catalyst without noble metal is developed, which can effectively promote the practical application of lithium air batteries. The alloy catalyst with more catalytic reactivity is developed on the basis of the multielement synergistic effect of the high-entropy alloy, so that the performance of the battery can be effectively improved. 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 non-noble metal amorphous high-entropy alloy catalyst for a lithium air battery. In order to solve the technical problems, the invention provides the following technical proposal that comprises, Dissolving sodium citrate and non-noble metal transition metal salt in deionized water to obtain a homogeneous aqueous solution, adding sodium borohydride, carrying out reduction reaction, adding ammonium chloride, stirring uniformly, standing for gelation to obtain a precipitate, washing the precipitate, centrifuging, and freeze-drying to obtain the non-noble metal amorphous high-entropy alloy catalyst; Wherein the temperature of the reduction reaction is 5-40 ℃ and the time is 2-8 h. As a preferable scheme of the preparation method, the non-noble metal transition metal salt comprises manganese salt, ferric salt, cobalt salt, nickel salt, copper salt, tin salt, zinc salt and chromium salt. As a preferable scheme of the preparation method, the molar ratio of the manganese salt, the ferric salt, the cobalt salt, the nickel salt and the copper salt is 0.3-1:0.3-1. As a preferable scheme of the preparation method, the manganese salt is manganese chloride, the ferric salt is ferric chloride, the cobalt salt is cobalt chloride, the nickel salt is nickel chloride, and the copper salt is copper chloride. As a preferable scheme of the preparation method, the molar ratio of the sodium citrate to the non-noble metal transition metal salt to the sodium borohydride to the ammonium chloride is 15-20:1-1.5:15-20:1-1.5. The preparation method is characterized by comprising the steps of washing the precipitate, centrifuging and freeze-drying, wherein the rotating speed of the centrifuging is 5000-12000 rpm. As a preferable scheme of the preparation method, the freeze-drying temperature is-10 to-70 ℃, and the freeze-drying time is 10-50 hours. The invention aims to overcome the defects in the prior art and provide the non-noble metal amorphous high-entropy alloy catalyst prepared by the preparation method of the non-noble metal amorphous high-entropy alloy catalyst for the lithium air battery. In order to solve the technical problems, the general formula of the non-noble metal amorphous high-entropy alloy catalyst is Mn aFebCocNidCue, wherein the molar ratio of a to b to c to d to e is 0.3-1:0.3-1, and the non-noble metal amorphous high-entropy alloy catalyst is of an amorphous phase structure. The invention further aims to overcome the defects in the prior art and provide the application of the non-noble metal amorphous high-entropy alloy catalyst in a lithium air battery. In order to solve the technical problems, the invention provides the following technical proposal that the application comprises, Mixing the high-entropy alloy catalyst with a conductive carbon material according to the mass ratio of (0.5-3) to obtain an active substance, mixing the active substance with a binder according to the mass ratio of (4-9): 1, adding an NMP solvent, stirring uniformly, spraying the obtained slurry on the surface of carbon paper, and drying to form an anode, wherein the conductive carbon material comprises one of KB, SP, CNT, and the binder material comprises one of PVDF and PTFE. The invention has the beneficial effects that: (1) The preparati