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CN-119552329-B - Metal-doped three-dimensional covalent organic framework material, preparation method thereof, negative electrode with material and secondary battery with negative electrode

CN119552329BCN 119552329 BCN119552329 BCN 119552329BCN-119552329-B

Abstract

The invention relates to a metal-doped three-dimensional covalent organic framework material, which is formed by connecting a 9, 10-dihydro-9, 10- [1,2] benzanthracene framework and a metal-doped beta-tetraR-group porphyrin framework through nitrogen atoms, wherein the 9, 10-dihydro-9, 10- [1,2] benzanthracene framework comprises two first dimension connecting sites, two second dimension connecting sites and two third dimension connecting sites, for any 9, 10-dihydro-9, 10- [1,2] benzanthracene framework, at least one first dimension connecting site is connected with the nitrogen atoms through double bonds, at least one second dimension connecting site is connected with the nitrogen atoms through double bonds, at least one third dimension connecting site is connected with the nitrogen atoms through double bonds, and four R groups of the metal-doped beta-tetraR-group porphyrin framework are respectively connected with one nitrogen atom through single bonds, and the metal comprises one of cerium, iridium, platinum and gold. The material provided by the invention can shorten the mass transfer path, reduce charge retardation, improve the conductivity and catalytic activity of the material, accelerate proton conduction, strengthen the kinetics of mass transfer reaction and provide an efficient catalytic platform for electrochemical reaction.

Inventors

  • TAN WEI
  • WEI SUQING
  • SHI KAIXIANG
  • LIU QUANBING
  • CHEN ZIKANG
  • LIANG JIEHAO

Assignees

  • 广东工业大学
  • 化学与精细化工广东省实验室揭阳分中心

Dates

Publication Date
20260505
Application Date
20241017

Claims (9)

  1. 1. The metal-doped three-dimensional covalent organic framework material is characterized in that the metal-doped three-dimensional covalent organic framework material is formed by connecting a 9, 10-dihydro-9, 10- [1,2] benzanthracene framework and a metal-doped beta-tetraR-based porphyrin framework through nitrogen atoms, wherein the 9, 10-dihydro-9, 10- [1,2] benzanthracene framework comprises two first dimension connecting sites, two second dimension connecting sites and two third dimension connecting sites, and for any 9, 10-dihydro-9, 10- [1,2] benzanthracene framework, at least one first dimension connecting site is connected with the nitrogen atoms through double bonds, at least one second dimension connecting site is connected with the nitrogen atoms through double bonds, at least one third dimension connecting site is connected with the nitrogen atoms through double bonds, and four R groups of the metal-doped beta-tetraR-based porphyrin framework are respectively connected with one nitrogen atom through single bonds; The structural formula of the metal doped three-dimensional covalent organic framework material is as follows: Wherein M is one of cerium, iridium, platinum and gold.
  2. 2. A method for preparing the metal-doped three-dimensional covalent organic framework material is characterized by comprising the following steps of uniformly mixing metal-doped 5,10,15, 20-tetra (4-aminophenyl) porphyrin with a three-dimensional ketone compound, glacial acetic acid solution and a first solvent, carrying out a reaction at 100-150 ℃ for 72-120 hours after degassing, and carrying out suction filtration, washing and drying to obtain the metal-doped three-dimensional covalent organic framework material; The three-dimensional ketone-based compound is formed by connecting the 9, 10-dihydro-9, 10- [1,2] benzanthracene skeleton and at least three oxygen atoms through double bonds, wherein at least one first-dimensional connecting site is connected with the oxygen atoms, at least one second-dimensional connecting site is connected with the oxygen atoms, at least one third-dimensional connecting site is connected with the oxygen atoms, and the first solvent comprises one or more of methanol, pyridine, N-methylpyrrolidone, o-dichlorobenzene, N-butanol, mesitylene and 1, 4-dioxane.
  3. 3. The method for preparing a metal-doped three-dimensional covalent organic framework material according to claim 2, wherein the three-dimensional ketone-based compound is 9,10- [1,2] benzanthracene-2,3,6,7,14,15 (9 h,10 h) -hexanone.
  4. 4. The method for preparing a metal-doped three-dimensional covalent organic framework material according to claim 2, wherein the molar ratio of ketocarbonyl groups in the three-dimensional ketone-based compound to amino groups in the metal-doped 5,10,15, 20-tetra (4-aminophenyl) porphyrin is 1 (1-1.2).
  5. 5. The preparation method of the metal-doped three-dimensional covalent organic framework material according to claim 2, wherein the sum of the mass of the three-dimensional ketone-based compound and the mass of the metal-doped 5,10,15, 20-tetra (4-aminophenyl) porphyrin is that the volume of the first solvent is=20 mg (1-2) ml, the volume ratio of the first solvent to the glacial acetic acid solution is 1 (0.1-0.2), and the concentration of the glacial acetic acid solution is 6-12mol/L.
  6. 6. A negative electrode comprising an active metal and the metal-doped three-dimensional covalent organic framework material of claim 1, wherein the active metal comprises one or more of lithium, sodium, potassium, and zinc.
  7. 7. The method for preparing the negative electrode according to claim 6, wherein the method comprises the steps of uniformly dispersing the metal-doped three-dimensional covalent organic framework material in a second solvent to obtain a mixed solution, uniformly dripping the mixed solution on the surface of the active metal, and heating the active metal until the second solvent on the surface of the active metal is completely volatilized to obtain the negative electrode; The mass of the metal-doped three-dimensional covalent organic framework material is that the volume of the second solvent is=1 mg (1-3) mL; The mixed solution is dripped on the surface of the active metal with the dosage of 0.17-0.28 mu L/mm 2 .
  8. 8. The negative electrode according to claim 7, wherein the method for producing a negative electrode further comprises the step of heating the active metal at a temperature of 40-80 ℃ for a time of 4-12 hours.
  9. 9. A secondary battery comprising a battery case, the negative electrode of any one of claims 6 to 8, a lithium iron phosphate positive electrode, a separator, and an electrolyte, wherein the separator is located between the positive electrode and the negative electrode.

Description

Metal-doped three-dimensional covalent organic framework material, preparation method thereof, negative electrode with material and secondary battery with negative electrode Technical Field The invention relates to the field of chemical functional composite materials, in particular to a metal-doped three-dimensional covalent organic framework material, a preparation method thereof, a negative electrode with the material and a secondary battery with the negative electrode. Background Covalent Organic Framework (COFs) materials are porous framework compounds formed by connecting organic micromolecular framework molecules through strong covalent bonds, and in recent years, the covalent organic framework materials (COFs) gradually become research hot spots of novel battery materials due to the advantages of designable pore parameters, strong thermochemical stability, designability area electron enrichment properties and the like. With the deep research of three-dimensional framework molecules, research branches of three-dimensional COFs materials appear, and compared with the two-dimensional COFs materials, the three-dimensional COFs materials can establish a unique three-dimensional pore structure, so that higher mass transfer efficiency and more catalytic sites are brought to a heterogeneous catalytic process, and the three-dimensional COFs materials have optimistic research prospects. However, the three-dimensional COFs materials are relatively less studied at present, and no related study on three-dimensional COFs materials formed by connecting cerium, iridium, platinum and gold doped porphyrin molecules with 9, 10-dihydro-9, 10- [1,2] benzanthracene and the electrode performance and the battery performance of the three-dimensional COFs materials is available. Disclosure of Invention Based on the above, the invention aims to provide a metal doped three-dimensional covalent organic framework material, which is formed by directly connecting 9, 10-dihydro-9, 10- [1,2] benzanthracene with beta-tetra-substituted porphyrin doped with a third transition metal cerium, iridium, platinum and gold through nitrogen atoms, so that the mass transfer path between two molecules is shortened, the charge retardation is reduced, the unique advantages of 4f orbitals and 5d orbitals peculiar to cerium, iridium, platinum and gold are fully utilized, the conductivity and catalytic activity of the material are improved, the proton conduction is accelerated, the mass transfer reaction kinetics is enhanced, and a high-efficiency catalytic platform is provided for electrochemical reaction. The three-dimensional COF material constructs a penetrating porous network structure, and the network structure not only provides a stable mass transfer path, but also effectively promotes multi-scale ion transmission through a dotted line conveying mechanism. The ordered pore canal design makes the transmission of protons, lithium ions and the like in an electrochemical system more efficient, reduces charge blocking, and enhances the dynamic performance of the whole mass transfer reaction. The invention synthesizes Covalent Organic Frameworks (COFs) by using beta-tetrar-based porphyrin doped with cerium (Ce), iridium (Ir), platinum (Pt) or gold (Au) and 9, 10-dihydro-9, 10- [1,2] benzanthracene as monomers, which has remarkable advantages, in particular in mass transfer coupling and proton hybridization. The Ce, ir, pt, au is doped into the beta-tetraR-based porphyrin framework to form the COF material, so that the conductivity and the electrochemical activity of the COF material can be further enhanced. The metal doped COF materials are modified on the lithium metal cathode, so that lithium ion deposition can be uniformly distributed, and growth of lithium dendrites can be effectively inhibited, thereby improving cycle performance and safety of the lithium metal battery. Under the action of the 5d and 4f orbitals, ce, ir, pt, au and other metals have remarkable advantages in proton coupling electron transfer reaction and also have outstanding performance in catalytic dynamics. Ce, ir, pt, au is doped into the beta-tetra R-porphyrin skeleton to form a COF material, so that not only can the conductivity and catalytic activity of the material be effectively improved, but also proton conduction can be obviously accelerated, and the mass transfer reaction kinetics can be enhanced. In particular, the 4f orbitals of cerium (Ce) have a highly localized electron structure, exhibiting significant electron transfer capability during proton coupling. The redox cycling of Ce 3+ and Ce 4+ provides a stable charge transfer channel, further enhancing proton transport and coupling efficiency. The iridium partially filled 5d orbitals exhibit excellent catalytic properties during proton hybridization enhancing charge transfer and proton coupling. The semi-filled 5d orbitals of platinum can provide a stable and efficient proton transport path suitable for kinetic ac