CN-118083948-B - Resin-based coated asphalt-based hard carbon composite material and preparation method thereof

CN118083948BCN 118083948 BCN118083948 BCN 118083948BCN-118083948-B

Abstract

The invention relates to the technical field of secondary battery material preparation, and provides a preparation method of a resin-based coated asphalt-based hard carbon composite material, which comprises the following steps of S1, uniformly mixing asphalt, sodium nitrite, 1, 4-p-phenylenediamine and a catalyst, and carrying out diazotization reaction to obtain aminated asphalt; S2, uniformly mixing the aminated asphalt with an aldehyde solution, adding a graphene oxide solution and a nitrogen source, uniformly mixing again, adding a phenol solution, performing oxidation-reduction reaction, forming a heteroatom doped resin-based hard carbon composite shell outside the aminated asphalt-based hard carbon, and obtaining a hard carbon precursor material, and S3, carbonizing the hard carbon precursor material, thereby obtaining the hard carbon composite material. Through the technical scheme, the problem that the balance among the first discharge specific capacity, the compaction density and the quick charge performance of the hard carbon material in the prior art cannot be achieved is solved, and therefore the comprehensive performance of the hard carbon material is improved.

Inventors

SONG ZHITAO
CHEN ZUOCHUAN
SONG FAN
CHEN FEI
REN RONG

Assignees

河北坤天新能源股份有限公司

Dates

Publication Date: 20260508
Application Date: 20240226

Claims (8)

1. The preparation method of the resin-based coated asphalt-based hard carbon composite material is characterized by comprising the following steps of: s1, uniformly mixing asphalt, sodium nitrite, 1, 4-p-phenylenediamine and a catalyst, and carrying out diazotization reaction to obtain aminated asphalt; s2, uniformly mixing the aminated asphalt with an aldehyde solution, adding a graphene oxide solution and a nitrogen source, uniformly mixing again, adding a phenol solution, performing redox reaction, and forming a heteroatom doped resin-based hard carbon composite shell outside the aminated asphalt-based hard carbon to obtain a hard carbon precursor material; s3, carbonizing the hard carbon precursor material to obtain a hard carbon composite material; In the step S2, the mass ratio of the aminated asphalt to the aldehyde solution to the graphene oxide solution to the nitrogen source to the phenol solution is 100:50-150:50-200:1-5:5-20; the mass fraction of the graphene oxide solution is 1% -5%; In the step S2, the temperature of the oxidation-reduction reaction is 60-100 ℃, the pressure of the oxidation-reduction reaction is 1-5 mpa, and the time of the oxidation-reduction reaction is 3-12 h.
2. The preparation method of the resin-based coated asphalt-based hard carbon composite material according to claim 1, wherein in the step S1, the mass ratio of asphalt, sodium nitrite, 1, 4-p-phenylenediamine and catalyst is 100:20-50:40-80:10-50.
3. The method for preparing the resin-based coated asphalt-based hard carbon composite material according to claim 1, wherein in the step S3, the carbonization temperature is 1200-1500 ℃, and the carbonization time is 1-6 hours.
4. The method for preparing a resin-based coated asphalt-based hard carbon composite material according to claim 1, wherein the aldehyde solution comprises one of formaldehyde solution, acetaldehyde solution, propionaldehyde solution, valeraldehyde solution, caproaldehyde solution and furfural solution.
5. The method for preparing a resin-based coated asphalt-based hard carbon composite material according to claim 1, wherein the phenolic solution comprises one of a phenol solution, a cresol solution, a xylenol solution, an aminophenol solution, a nitrophenol solution, and a naphthol solution.
6. The method for preparing a resin-based coated pitch-based hard carbon composite material according to claim 1, wherein the step S3 is to carbonize a hard carbon precursor material in a reducing gas atmosphere to obtain a hard carbon composite material.
7. The method for preparing a resin-based coated pitch-based hard carbon composite material according to claim 6, wherein the reducing gas comprises one of hydrogen, carbon monoxide, and hydrogen sulfide.
8. The application of the hard carbon composite material prepared by the preparation method of the resin-based coated asphalt-based hard carbon composite material according to any one of claims 1-7 in sodium ion batteries.

Description

Resin-based coated asphalt-based hard carbon composite material and preparation method thereof Technical Field The invention relates to the technical field of preparation of secondary battery materials, in particular to a resin-based coated asphalt-based hard carbon composite material and a preparation method thereof. Background The negative electrode material used for the sodium ion battery mainly comprises hard carbon materials, wherein the hard carbon materials are classified into biomass hard carbon, resin-based hard carbon and coal-based hard carbon according to different raw materials, each hard carbon material has different aspects such as precursor, pore-forming temperature, orientation of carbon-based materials and the like, so that the specific capacity, compaction density and charging capacity of the material are obviously different, and the cost is also greatly different, for example, the specific capacity of the biomass hard carbon material is moderate (300-330 mAh/g), the compaction density is moderate (0.9-1.0 g/cm 3), the primary efficiency is high (92%), the specific capacity of the resin-based hard carbon material is high (320-360mAh/g), the compaction density is moderate (0.95-1.05 g/cm 3), the primary efficiency is high (90%), the specific capacity of the coal-based hard carbon material is low (220-250 mAh/g), the compaction density is high (1.0-1.1 g/cm 3), the primary efficiency is low (86-89%), and the cost is low. The sodium ion battery requires that the anode material used achieve balance among the specific capacity of initial discharge, compaction density and quick charge performance, but the current hard carbon material can not meet the requirement, and has lower comprehensive performance. Disclosure of Invention The invention provides a resin-based coated asphalt-based hard carbon composite material and a preparation method thereof, which solve the problem that the hard carbon material in the related art cannot reach balance among initial discharge specific capacity, compaction density and quick charge performance, so that the comprehensive performance of the hard carbon material is low. The technical scheme of the invention is as follows: the invention provides a preparation method of a resin-based coated asphalt-based hard carbon composite material, which comprises the following steps: s1, uniformly mixing asphalt, sodium nitrite, 1, 4-p-phenylenediamine and a catalyst, and carrying out diazotization reaction to obtain aminated asphalt; s2, uniformly mixing the aminated asphalt with an aldehyde solution, adding a graphene oxide solution and a nitrogen source, uniformly mixing again, adding a phenol solution, performing redox reaction, and forming a heteroatom doped resin-based hard carbon composite shell outside the aminated asphalt-based hard carbon to obtain a hard carbon precursor material; and S3, carbonizing the hard carbon precursor material to obtain the hard carbon composite material. In the invention, in order to improve the compaction density and the first efficiency of the hard carbon material, the surface of the pitch-based precursor is coated with a resin-based material through phenolic reaction, and the hard carbon composite material is obtained after carbonization. And the electron conductivity and the multiplying power performance of the hard carbon composite material can be improved by carrying out nitrogen doping on the hard carbon composite material. As a further technical scheme, the mass ratio of the asphalt to the sodium nitrite to the 1, 4-p-phenylenediamine to the catalyst is 100:20-50:40-80:10-50. As a further technical scheme, the catalyst is sulfuric acid aqueous solution with the mass fraction of 70%. As a further technical scheme, the mass ratio of the aminated asphalt to the aldehyde solution to the graphene oxide solution to the nitrogen source to the phenol solution is 100:50-150:50-200:1-5:5-20. As a further technical scheme, the mass fraction of the aldehyde solution is 35%. As a further technical scheme, the graphene oxide solution is 1% -5% in mass fraction. As a further technical scheme, the mass fraction of the phenolic solution is 5%. As a further technical scheme, the temperature of the diazotization reaction is 50 ℃, and the time of the diazotization reaction is 24 hours. As a further technical scheme, the temperature of the oxidation-reduction reaction is 60-100 ℃, the pressure of the oxidation-reduction reaction is 1-5 mpa, and the time of the oxidation-reduction reaction is 3-12 h. As a further technical scheme, the carbonization temperature is 1200-1500 ℃, and the carbonization time is 1-6 h. As a further technical scheme, the aldehyde solution comprises one of formaldehyde solution, acetaldehyde solution, propionaldehyde solution, valeraldehyde solution, hexanal solution and furfural solution. As a further technical scheme, the phenolic solution comprises one of phenol solution, cresol solution, xylenol solution, aminophenol solutio