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CN-120581605-B - Mg-CO2Preparation method of battery catalyst material

CN120581605BCN 120581605 BCN120581605 BCN 120581605BCN-120581605-B

Abstract

The invention discloses a preparation method of a catalyst material for a Mg-CO 2 battery, which comprises the steps of firstly carrying out intercalation treatment on MBenes nano sheets and COFs nano sheets modified by alkali metal ions to tightly combine the MBenes nano sheets and the COFs nano sheets to form a composite carrier, and then compounding the composite carrier with Ga-In-Sn alloy obtained by a laser melting technology.

Inventors

  • ZHANG HENGYUAN
  • ZOU GUODONG
  • GUO JING
  • Song Menghan
  • LI SEN
  • ZHANG YU
  • KANG QIJIA
  • LI YAXUAN
  • FANG ZHONGCHEN

Assignees

  • 燕山大学
  • 东北大学秦皇岛分校

Dates

Publication Date
20260508
Application Date
20250527

Claims (8)

  1. 1. The preparation method of the Mg-CO 2 battery catalyst material is characterized by sequentially carrying out the following steps: S1, uniformly mixing MAB precursor powder, liF and HCl, centrifuging for 1-2 hours at a rotating speed of 2000-4000rpm, filtering, and drying for 10-12 hours at 80-100 ℃ to obtain MBenes; S2, adding acetic acid into an aldehyde monomer solution, reacting for 1-3 hours, adding an amino monomer solution into the mixture, and reacting for 24-48 hours to obtain a COFs nanosheet mixed solution; s3, uniformly mixing the COFs nanosheet mixed solution and an alkali metal solution, heating in a water bath at 75-95 ℃ for 10-12 hours, filtering, and drying at 80-100 ℃ for 10-12 hours to obtain alkali metal@COFs powder; S4, uniformly mixing Ga, in and Sn according to the mass ratio of 70:24.5:5.5, placing the mixture In a reactor protected by inert atmosphere, scanning molten metal by using femtosecond laser, cooling the mixture to room temperature at the speed of 500-3000 ℃ per minute, and performing ultrasonic treatment for 3-10 hours to obtain Ga 70 In 24.5 Sn 5.5 alloy solution; S5, soaking the products obtained in the steps S1 and S3 in the alloy solution obtained in the step S4, carrying out pressurizing reaction under argon atmosphere, and then carrying out suction filtration and drying to obtain MBenes-SA@COFs/Ga 70 In 24.5 Sn 5.5 , namely the Mg-CO 2 battery catalyst material.
  2. 2. The method for preparing the catalyst material for the Mg-CO 2 battery according to claim 1, wherein in the step S1, the MAB precursor is (Mo 2/3 Y 1/3 ) 2 AlB 2 、Cr 3 AlB 4 、Fe 2 AlB 2 、Mn 2 AlB 2 , and the molar ratio of the MAB precursor to LiF and HCl is 1 (2-6): 2.
  3. 3. The method for preparing a catalyst material for a Mg-CO 2 battery according to claim 1, wherein in step S2, the aldehyde group monomer is trimethylphloroglucinol or 2, 5-dihydroxyterephthalaldehyde, and the amino group monomer is 2, 5-diaminobenzenesulfonic acid or aminoguanidine hydrochloride.
  4. 4. The method for preparing the catalyst material for the Mg-CO 2 battery according to claim 1, wherein in the step S2, the molar ratio of the acetic acid to the aldehyde group monomer to the amino group monomer is (2-4): 1 (1-2).
  5. 5. The preparation method of the Mg-CO 2 battery catalyst material according to claim 1, wherein in the step S3, the alkali metal solution is one or more of Na 2 CO 3 、NaCl、NaNO 3 、Na 3 PO 4 、NaSO 4 、Li 2 CO 3 、LiCl、LiNO 3 、Li 3 PO 4 、LiSO 4 、K 2 CO 3 、KCl、KNO 3 、K 3 PO 4 、K 2 SO 4 , and the molar ratio of the mixed solution of the COFs nano-sheets to the alkali metal solution is 1 (0.5-1.5).
  6. 6. The method for preparing a catalyst material for a Mg-CO 2 battery according to claim 1, wherein in step S4, the laser power is 400W and the laser time is 2-10min.
  7. 7. The method for preparing a catalyst material for Mg-CO 2 cells according to claim 1, wherein in step S5, the pressurizing reaction is performed by pressurizing from normal pressure to 0.1-0.5MPa for 5min, then heating to 150 ℃ under normal pressure, and then maintaining the temperature for 14h.
  8. 8. The method for preparing a catalyst material for Mg-CO 2 cells according to claim 1, wherein in step S5, the drying temperature is 80-100 ℃ and the time is 10-12 hours.

Description

Preparation method of Mg-CO 2 battery catalyst material Technical Field The invention belongs to the field of magnesium-carbon dioxide batteries, and relates to a preparation method of a catalyst material for a Mg-CO 2 battery. Background Meeting the increasing energy demands of the human society and solving the environmental problems caused by excessive consumption of fossil fuel is one of the key problems to be solved in order to realize the sustainable development of the human society. In general, excessive consumption of fossil fuels may lead to excessive emission of carbon dioxide gas, accelerating the trend of global warming. Therefore, in recent years, new energy systems have been vigorously developed in both academia and industry to reduce carbon dioxide emissions and convert carbon dioxide into valuable chemicals. Currently, rechargeable metal-carbon dioxide batteries offer a great advantage in terms of efficient emission reduction, CO 2 value-added conversion, and high-performance energy storage in exploring systems for carbon dioxide emission reduction and utilization. Therefore, rechargeable Mg-CO 2 batteries are considered a strategy of "one-stone-two-bird" and are a research hotspot in the fields of CO 2 emission reduction and electrochemical energy storage. However, alkali metals have high reactivity and are prone to dendrite formation during cycling, resulting in serious battery safety problems, which shorten the cycle life of the battery and limit practical applications of the battery. Therefore, research into magnesium, which is relatively low in activity and free of dendrites, as a negative electrode of Mg-CO 2 battery is critical to Mg-CO 2 battery. Chinese patent application number 201410500300.6 discloses a graphene-FeOF positive electrode composite material and a preparation method thereof, wherein a solid-liquid mixture is formed by water bath reaction after mixing, feOF is synthesized by ferric fluoride and graphene oxide for the first time, and the graphene oxide is used as a reactant and a conductive agent at the same time, so that the conductivity is increased to a certain extent. However, the active site of the composite material is uneven, the coordination degree is low, and the raw material ferric fluoride has certain toxicity and is easy to pollute the environment. Chinese patent No. 201610951729.6 discloses a two-dimensional transition group metal carbo/nitride and nano sulfur particle composite material, its preparation and application. The composite material consists of MXene nano-sheets and nano-sulfur particles. The preparation method comprises the steps of taking formic acid as a reducing agent, enabling nano sulfur generated by the reaction to uniformly grow on the surface of an MXene nano sheet, and obtaining the MXene and nano sulfur particle composite material through neutralization, washing and centrifugation. The composite material has high composite degree, no need of introducing adhesive and conductive agent, and simple process. However, the thermal stability is poor, sulfur is easy to run off at high temperature, the material performance is affected, side reactions are easy to occur, and the selectivity is poor. Document JOURNAL OF ELECTROCHEMISTRY 2019,25 (2): 280 discloses preparation of a two-dimensional multi-layer Ti 3C2Tx -MXene/polypyrrole nanowire composite material and research on capacitance performance, and the one-dimensional polypyrrole nanowire is loaded on the two-dimensional surface of Ti 3C2Tx -MXene, so that the self-stacking phenomenon of MXene is effectively improved, and the capacitance performance is improved. But the material has smaller specific surface area, low surface activity and poor catalytic efficiency. In summary, the main drawbacks of current metal-carbon dioxide batteries are: first, the catalyst material is unevenly compounded, and the catalyst activity is poor; secondly, the catalyst has poor stability and is sensitive to external conditions such as chemical reaction temperature, pH value and the like; Thirdly, the utilization rate of catalyst atoms is low, and the catalytic activity is poor; Fourth, the preparation process is too complicated, the cost is high, and the large-scale application is difficult. Based on this, the present invention aims to provide a catalyst material having a high specific surface area, good electrical conductivity, chemical and thermal stability. Disclosure of Invention Aiming at the technical problems, the invention aims to provide a preparation method of a catalyst material for a Mg-CO 2 battery, which comprises the steps of firstly carrying out intercalation treatment on MBenes nano sheets and COFs nano sheets modified by alkali metal ions to enable the MBenes nano sheets and the COFs nano sheets to be tightly combined to form a composite carrier, and then compounding the composite carrier with Ga-In-Sn alloy obtained by a laser melting technology. In order to achieve the above purpose, the tec