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CN-118324119-B - Petroleum asphalt-based high-crystallization soft carbon material and preparation method thereof

CN118324119BCN 118324119 BCN118324119 BCN 118324119BCN-118324119-B

Abstract

The invention provides a petroleum asphalt-based high-crystallization soft carbon material and a preparation method thereof, which belong to the technical fields of new energy sources, new materials and the like. Firstly, petroleum asphalt and aromatic phenol organic matters are melt-blended, then the mixture is subjected to condensation reaction with aromatic aldehyde under the catalysis of organic base to prepare in-situ phenolic resin modified petroleum asphalt, low-boiling point fractions are removed through reduced pressure distillation, the high-softening point phenolic resin modified petroleum asphalt can be controllably prepared, and lamellar graphite-like soft carbon materials with high crystallinity and controllable structure are prepared through carbonization. The invention solves the technical problems of poor controllability and poor crystallization performance of the carbon material in the carbonization preparation process of the petroleum asphalt, and provides a new path for the application of the petroleum asphalt in the fields of high-performance green energy sources such as environment-friendly batteries, energy storage materials and the like.

Inventors

  • SHEN KAIHUA
  • LI CHUNLEI

Assignees

  • 大连理工大学

Dates

Publication Date
20260505
Application Date
20240418

Claims (9)

  1. 1. A preparation method of a petroleum asphalt-based high-crystallization soft carbon material is characterized by comprising the steps of firstly, carrying out melt blending on petroleum asphalt, an aromatic phenol monomer, an aromatic aldehyde monomer and an organic base, and carrying out condensation reaction on the aromatic phenol monomer and the aromatic aldehyde monomer under the catalysis of the organic base to obtain in-situ phenolic resin modified petroleum asphalt; The crystallization degree and the structural dimension of the petroleum asphalt in the whole processes of modification and carbonization can be regulated and controlled by selecting and proportioning the petroleum asphalt, the aromatic phenol monomer, the aromatic aldehyde monomer and the catalyst, controlling the conditions of polymerization reaction and reduced pressure distillation, setting the final carbonization temperature and controlling the heating rate.
  2. 2. The method for preparing the petroleum asphalt-based high-crystalline soft carbon material according to claim 1, which is characterized by comprising the following steps: 1) Adding petroleum asphalt, aromatic phenol monomers, aromatic aldehyde monomers and an organic base catalyst into a reaction kettle, wherein the amount of the aromatic aldehyde monomers is 5-10wt% of the mass of the asphalt, the amount of the aromatic phenol monomers is 5-10wt% of the mass of the asphalt, and the amount of the organic base is 1-10wt% of the mass of the aromatic aldehyde monomers; 2) Slowly heating until materials in the kettle are fully dissolved and mixed, and then carrying out polycondensation reaction for 2-8 hours in a range of 140-200 ℃ to obtain in-situ phenolic resin modified petroleum asphalt; 3) Performing reduced pressure distillation on the in-situ phenolic resin modified petroleum asphalt obtained in the step 2) for 1-6 hours at the temperature of 250-350 ℃ and in the range of 10-50 kPa to obtain phenolic resin modified petroleum asphalt with the softening point of 170-270 ℃; 4) And (3) under the protection of inert gas, carrying out carbonization reaction for 2-5 hours at 1000-1500 ℃ on the phenolic resin in-situ modified asphalt obtained in the step (3), and cooling to obtain the lamellar graphite-like soft carbon material with high crystallinity and controllable structure.
  3. 3. The method for preparing a petroleum asphalt-based high-crystalline soft carbon material according to claim 2, wherein the petroleum asphalt is one or two of oxidized petroleum asphalt, solvent-deoiled petroleum asphalt and blended petroleum asphalt.
  4. 4. The method for preparing the petroleum pitch-based high-crystalline soft carbon material according to claim 2, wherein the aromatic phenol monomer comprises one or more of phenol, methyl phenol, dimethyl phenol, ethyl phenol, propyl phenol, tertiary butyl phenol, amyl phenol, hexyl phenol, nonyl phenol, cardanol, bisphenol a, bisphenol F, bisphenol S, phenyl phenol, catechol, resorcinol, hydroquinone, naphthol or naphthalene diphenol.
  5. 5. The method for preparing the petroleum asphalt-based high-crystalline soft carbon material according to claim 2, wherein the aromatic aldehyde monomer comprises one or more of furfural, benzaldehyde, naphthalene aldehyde, o-phthalaldehyde, m-phthalaldehyde, p-phthalaldehyde, trimellitic aldehyde, naphthalene dialdehyde and derivatives thereof.
  6. 6. The method for preparing the petroleum pitch-based high crystalline soft carbon material according to claim 2, wherein the organic base catalyst comprises one or more than two of cyclohexylamine, quinoline, indoline, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD), 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), mono-alkyl substituted imidazole, mono-alkyl substituted imidazoline, poly-alkyl substituted imidazole or poly-alkyl substituted imidazoline.
  7. 7. The method for preparing a petroleum pitch-based high crystalline soft carbon material according to claim 2, wherein the inert protective atmosphere is nitrogen or argon.
  8. 8. A petroleum pitch-based highly crystalline soft carbon material, characterized in that said highly crystalline soft carbon material is obtained by the production method according to any one of claims 1 to 7.
  9. 9. The application of the petroleum asphalt-based high-crystallization soft carbon material as claimed in claim 8, which is characterized in that the petroleum asphalt-based high-crystallization soft carbon material can be used as a cathode material of environment-friendly batteries and energy storage devices.

Description

Petroleum asphalt-based high-crystallization soft carbon material and preparation method thereof Technical Field The invention belongs to the industrial fields of energy chemical industry, petrochemical industry, material chemical industry, high polymer chemical industry and the like, and relates to a cathode material which can be used for environment-friendly batteries and energy storage devices, and is a high-crystallization petroleum asphalt-based soft carbon material and a preparation method thereof. Background With the rapid increase of the electrochemical energy storage demand, the performance requirement and the dosage scale of green energy materials in the market are continuously increased, and the cathode material is one of key materials. Because of the limitation of the perfection of the industrial production technology, the negative electrode material used in the lithium ion battery in the market at present still takes artificial graphite as a main material, wherein coal pitch and a small part of high-quality petroleum pitch are used as initial raw materials. Because of high pollution in the coal chemical industry, the overall development is limited, the coal pitch yield is gradually reduced, and the requirement of high-performance energy materials cannot be met. The petroleum asphalt which is an important product in the oil refining industry has huge yield, but has low aromatic content, high H/C ratio, low direct carbonization carbon residue rate and poor crystallinity, can not meet the performance requirement of functional carbon for a negative electrode material, and how to regulate and prepare the high-performance petroleum asphalt and meet the requirement of a green energy carbon material becomes an important scientific and technical problem. While petroleum pitch is considered as a potential precursor for preparing carbon materials, it is challenging to 1) dislocation or even overlap between sheets of petroleum pitch-based carbonized materials, with a disordered, disordered structural distribution, and 2) a high H/C ratio of petroleum pitch, which can easily cause structural defects during carbonization, affecting the electrochemical performance of the carbon materials. In order to solve the problems, patent CN102723492A proposes a preparation method of adding petroleum asphalt into an epoxy group-containing organic polymer solution, uniformly mixing the petroleum asphalt with the epoxy group-containing organic polymer solution, drying the mixture to obtain a precursor, carbonizing the precursor to form hard carbon, patent CN116216693A proposes a method of preparing a hard carbon negative electrode material by ball milling and mixing the pre-oxidized and modified petroleum asphalt with ammonium phosphate salt and then directly carbonizing the mixture, patent CN115974065A proposes a preparation method of dispersing ball-milled petroleum asphalt powder and a chemical modifier 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone into acetic acid, ball milling and mixing the slurry and carbonizing the mixture to obtain a hard carbon material, patent CN117185285A proposes a preparation method of dissolving petroleum asphalt into an organic solvent, adding template agents such as silicate cement and iron, distilling and recovering the organic solvent, carbonizing the asphalt mixture at a high temperature, removing acid washing cement and the iron template agent, and drying the mixture in vacuum to obtain graphene. However, the method has the defects of poor compatibility of petroleum asphalt, modifier and template agent, high cost and difficulty in meeting the requirements of industrial production, and the mixing depends on a large amount of organic solvents and special mechanical equipment. Disclosure of Invention Aiming at the problems existing in the prior art, the invention provides the petroleum asphalt-based high-crystallization soft carbon material and the preparation method thereof, wherein the in-situ polymerization of the aromatic phenol monomer and the aromatic aldehyde monomer in the liquid asphalt solution is adopted to obtain the in-situ phenolic resin modified petroleum asphalt, so that the fine dispersion of the phenolic resin in the petroleum asphalt is realized, the pyrolysis and polymerization of the polycyclic aromatic hydrocarbon in the asphalt and the growth of the carbon material can be effectively regulated and controlled, and the lamellar high-crystallization graphite-like soft carbon material can be controlled. In order to achieve the above purpose, the invention adopts the following technical scheme: The method is characterized in that firstly, petroleum asphalt, aromatic phenol monomers, aromatic aldehyde monomers and organic base are added into a reaction kettle to be melt blended, and the aromatic phenol monomers and the aromatic aldehyde monomers undergo condensation reaction under the catalysis of the organic base to prepare the in-situ phenolic resin modified petroleum as