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CN-121974325-A - Preparation method and application of lignin supermolecule derived carbonaceous bimetallic compound

CN121974325ACN 121974325 ACN121974325 ACN 121974325ACN-121974325-A

Abstract

The invention discloses a preparation method of lignin supermolecule derived carbonaceous bimetallic complex, which comprises the steps of modifying lignin by ethylenediamine and formaldehyde through Mannich reaction to synthesize aminated lignin; adding boric acid into the lignin supermolecule precursor for boron doping, adding vanadium-manganese compound, and obtaining the lignin supermolecule derived carbonaceous bimetallic compound through hydrothermal and carbonization. The invention realizes supermolecule synthesis, nonmetal doping and metal loading, optimizes the electronic structure and pore structure of the material, can effectively reduce ion diffusion resistance, improves ion transmission efficiency, and improves the comprehensive electrochemical performance of lignin derived carbon materials in a water system zinc ion energy storage system.

Inventors

  • XU JIKUN
  • LIU SIHAN
  • GUO JUN
  • ZHU YUANCHEN
  • CHEN SHIMAN

Assignees

  • 武汉科技大学

Dates

Publication Date
20260505
Application Date
20260116

Claims (10)

  1. 1. A preparation method of a lignin supermolecule derived carbonaceous bimetallic compound is characterized by firstly modifying lignin by using ethylenediamine and formaldehyde through a Mannich reaction to synthesize aminated lignin, forming a lignin supermolecule precursor by the aminated lignin, melamine and cyanuric acid, adding boric acid to carry out boron doping, uniformly mixing the boric acid doped lignin supermolecule precursor with a vanadium-manganese compound in a solution, and carrying out hydrothermal and carbonization treatment to obtain the lignin supermolecule derived carbonaceous bimetallic compound.
  2. 2. The method for preparing the lignin supermolecule derived carbonaceous bimetallic composite according to claim 1, comprising the steps of: (1) Dissolving lignin in a sodium hydroxide solution, adding ethylenediamine and formaldehyde solution, performing heat preservation treatment, dialyzing to clarify, and freeze-drying the obtained dialysate to obtain aminated lignin; (2) Uniformly mixing melamine and cyanuric acid in water, adding the aminated lignin obtained in the step (1), uniformly mixing, and then adding boric acid for fully mixing to obtain a boric acid doped lignin supermolecule precursor solution; (3) Adding ammonium metavanadate and oxalic acid into water, heating and stirring uniformly, then adding manganese chloride and urea, and continuing heating and stirring until the urea is dissolved to obtain a vanadium-manganese compound solution; (4) Adding the vanadium-manganese compound solution obtained in the step (3) into the boric acid doped lignin supermolecule precursor solution obtained in the step (2), uniformly mixing, performing a hydrothermal reaction, collecting a solid product after the hydrothermal reaction is finished, and performing carbonization treatment to obtain the lignin supermolecule derived carbonaceous bimetallic compound.
  3. 3. The preparation method of the lignin supermolecule derived carbonaceous bimetallic compound according to claim 2 is characterized in that in the step (1), the concentration of sodium hydroxide solution is 5-10wt%, the mass ratio of lignin to sodium hydroxide solution is 1 (8-12), the mass ratio of lignin to ethylenediamine to formaldehyde solution is 1 (0.5-2), and the mass ratio of lignin to ethylenediamine to formaldehyde solution is 1-3; After dissolving lignin in a sodium hydroxide solution, heating to 30-60 ℃, adding ethylenediamine and formaldehyde solution, after adding ethylenediamine and formaldehyde solution, magnetically stirring for 2-5 hours in a water bath at a constant temperature of 30-60 ℃, heating to 60-90 ℃ and preserving heat for 2-5 hours, wherein the concentration of formaldehyde solution is 20-40 wt%.
  4. 4. The method for preparing a lignin supermolecule derived carbonaceous bimetallic complex according to claim 2, wherein in the step (1), dialysis is performed for 120-480 hours by using a dialysis bag with a molecular weight of 2000-4000; In the step (2), the mass ratio of melamine to cyanuric acid is 1 (0.3-0.8), the mass ratio of aminated lignin to the total mass of melamine and cyanuric acid is 1 (5-15), and the mass ratio of boric acid to the total mass of melamine and cyanuric acid is 1 (0.8-1.2).
  5. 5. The preparation method of the lignin supermolecule derived carbonaceous bimetallic compound according to claim 2, wherein in the step (3), ammonium metavanadate and oxalic acid are added into water according to a mass ratio of 1 (0.4-1), and are heated and stirred for 8-14 h at a temperature of 50-90 ℃; The mass ratio of the ammonium metavanadate to the manganese chloride is 1 (1-2), the mass ratio of the ammonium metavanadate to the urea is 1 (0.6-1), the manganese chloride is added, then the mixture is heated and stirred for 0.5-3 hours at 50-90 ℃, and the urea is added and stirred until the mixture is completely dissolved under the premise that the water bath temperature is kept unchanged.
  6. 6. The preparation method of the lignin supermolecule derived carbonaceous bimetallic compound according to claim 2, wherein in the step (4), when the solution of the lignin supermolecule precursor doped with boric acid and the solution of the vanadium-manganese compound are mixed, the stirring time is 6-10 h, the temperature of the hydrothermal reaction is 160-220 ℃ and the reaction time is 8-14 h, wherein the ratio of the aminated lignin in the lignin supermolecule precursor to the total mass of ammonium metavanadate and oxalic acid in the step (3) is 1 (2.8-4).
  7. 7. The method for preparing the lignin supermolecule derived carbonaceous bimetallic composite according to claim 2, wherein in the step (4), a solid product is collected by adopting a water system micro-pore filtration membrane for filtration, the filtration pore diameter is 0.4-0.5 μm, the carbonization temperature is 700-900 ℃, and the carbonization time is 1-3 hours.
  8. 8. A lignin supramolecular derived carbonaceous bimetallic complex prepared according to the method of any one of claims 1-7.
  9. 9. The use of the lignin supermolecule derived carbonaceous bimetallic composite of claim 8 as a positive electrode material for zinc ion batteries.
  10. 10. The application of the lignin supermolecule derived carbonaceous bimetallic compound in the aspect of capacitance deionization is characterized in that the lignin supermolecule derived carbonaceous bimetallic compound is uniformly mixed with a conductive agent, a binder and a solvent, and then respectively coated on two titanium plates for drying to be used as an anode and a cathode of a capacitance deionization device.

Description

Preparation method and application of lignin supermolecule derived carbonaceous bimetallic compound Technical Field The invention relates to the field of biomass materials, in particular to a preparation method and application of a lignin supermolecule derived carbonaceous bimetallic compound. Background Lignin is used as an aromatic natural high molecular compound with the content inferior to that of cellulose in the nature, and has the advantages of wide sources, no toxicity, low price, rich aromatic structure and higher carbon content. However, as a by-product, most of industrial lignin is directly incinerated, causing environmental pollution and resource waste. One key strategy for lignin proliferation is the conversion of lignin to advanced carbonaceous materials. In recent years, lignin supermolecules have been widely focused on due to their regular, stable three-dimensional network structure and controllability. In the prior art, after dissolving lignin by using ammonia water, preparing lignin supermolecule, and then applying the lignin supermolecule to a zinc ion battery, wherein the power density is not more than 150Wh/kg, and the performance of the lignin supermolecule serving as a battery anode material needs to be improved. In addition, the lignin is partially ring-opened for oxidative ammonolysis modification, then a proper amount of amide is introduced as a coordination group, and then the coordination group is self-assembled with metal ions to form a lignin-metal supermolecular framework material, and the lignin-metal supermolecular framework material is carbonized at high temperature and then is used for water electrolysis, but the lignin-metal supermolecular framework material has poor effect as an electrode material. The lignin is dissolved in the dimethyl nitrosamine, and then the crosslinking agent such as glutaraldehyde and the like are added into the lignin to be subjected to heat treatment to form lignin supermolecules, but the method has high requirements on experimental conditions, different crosslinking agents, pH, temperature and reaction time have great influence on the performance of the product, and the energy consumption is high in the process of selecting proper reaction conditions, and the crosslinking agents are mostly toxic organic matters, so that certain influence is caused on the environment. Disclosure of Invention The invention aims to solve the technical problems of providing a preparation method of a lignin supermolecule derived carbonaceous bimetallic compound aiming at the defects of the prior art, and the preparation method realizes supermolecule synthesis, nonmetal doping and metal loading, thereby remarkably improving the electrochemical performance, having mild reaction conditions and small environmental pollution. The invention adopts the technical proposal for solving the problems that: According to the invention, lignin is modified by ethylenediamine and formaldehyde through a Mannich reaction to synthesize aminated lignin, the aminated lignin, melamine and cyanuric acid form a lignin supermolecule precursor, boric acid is added into the lignin supermolecule precursor to carry out boron doping, then vanadium-manganese compound is added, and then the vanadium-manganese loaded boron-nitrogen doped lignin supermolecule derivative carbon material is obtained through hydrothermal and carbonization, namely the lignin supermolecule derivative carbon bimetallic compound. Further, the preparation method of the lignin supermolecule derived carbonaceous bimetallic compound specifically comprises the following steps: (1) Dissolving lignin in a sodium hydroxide solution, adding ethylenediamine and formaldehyde solution, then preserving heat for 2-5 hours at 60-90 ℃, naturally cooling to room temperature, and then dialyzing until dialysate is clear; (2) Stirring melamine and cyanuric acid in water, mixing uniformly, adding the aminated lignin obtained in the step (1), stirring thoroughly, adding boric acid, and mixing thoroughly to obtain a boric acid doped lignin supermolecule precursor solution; (3) Adding ammonium metavanadate and oxalic acid into water, heating and stirring in a water bath, then adding manganese chloride and urea into the mixture, and continuing heating and stirring in the water bath until the urea is dissolved to obtain a vanadium-manganese compound solution; (4) Adding the vanadium-manganese compound solution obtained in the step (3) into the boric acid doped lignin supermolecule precursor solution obtained in the step (2), uniformly mixing, performing hydrothermal reaction, and collecting a solid product after the reaction is finished; (5) And (3) drying the solid product obtained in the step (4) and then carbonizing to obtain the vanadium-manganese-loaded boron-nitrogen-doped lignin supermolecule derived carbon material, namely the lignin supermolecule derived carbonaceous bimetallic composite. According to the scheme, in the step (1), the concen