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Modification method of artificial graphite

An artificial graphite, modified technology, applied in electrical components, battery electrodes, circuits, etc., can solve the problems of insufficient oxidation degree, complex process, high industrialization cost, and achieve increased coating uniformity, uniform particle size distribution, and the first time. Efficiency improvement effect

Active Publication Date: 2015-02-11
CNOOC TIANJIN CHEM RES & DESIGN INST +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Japanese patent JP11246209 immerses and coats graphite in medium and low temperature asphalt, but it is difficult to form a uniform coating layer on the surface
However, JP200397357 directly mixes graphite and pitch, and then heat-treats it at high temperature. The pulverization of the post-treatment affects the particle size distribution of the product and also affects the coating effect.
Shanshan patent CN200410018079.7 is coated with a solvent, and then the solvent is removed in a vacuum and then thermally polymerized at 350-500°C. The performance of the obtained product is good, but the industrialization cost of high temperature and high pressure reaction is relatively high
And CN200510029448.7 improves the previous patent by adding reaction aids to improve the coating performance, but it does not solve the high temperature and high pressure problem
BAK patent CN200710072974.0 is oxidized by hydrogen peroxide or concentrated nitric acid, and then coated in asphalt solution. It can react at low temperature or even normal temperature, but the degree of oxidation is not enough, which makes the coating performance unsatisfactory. The cost of selected solvents such as pyridine and tetrahydrofuran is relatively low. High, difficult to meet industrial standards
[0005] Judging from the current situation, the existing technologies have not achieved satisfactory results from the perspective of industrialization, and there are generally disadvantages such as complex processes, high raw material costs, harsh reaction conditions, and unstable product quality.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] The artificial graphite was oxidized with 0.1 M potassium permanganate in an ice-water bath for 1 hour, and then dried. Then add it to the asphalt washing oil solution for coating treatment, wherein the mass ratio of asphalt to washing oil is 0.01, the mass ratio of graphite to asphalt is 100, the reaction temperature is 120°C, the reaction time is 2 hours, and then centrifugally filtered. Finally, it was carbonized under the condition of 800° C. and kept for 2 hours.

[0017] The obtained artificial graphite modified material has a tested reversible capacity of 348mAh / g, an increase of 8mAh / g, and an initial efficiency of 92.41%.

Embodiment 2

[0019] The artificial graphite was oxidized with 5M potassium permanganate in an ice-water bath for 10 hours, and then dried. Then add it to the asphalt washing oil solution for coating treatment, wherein the mass ratio of asphalt to washing oil is 0.4, the mass ratio of graphite to asphalt is 10, the reaction temperature is 200 ° C, the reaction time is 10 hours, and then centrifugally filtered. Finally, it was carbonized under the condition of 1500°C and kept for 12 hours.

[0020] The obtained artificial graphite modified material has a tested reversible capacity of 350mAh / g, an increase of 10mAh / g, and an initial efficiency of 93.1%.

Embodiment 3

[0022] The artificial graphite was oxidized with 12M concentrated sulfuric acid in an ice-water bath for 3 hours, and then dried. Then add it to the asphalt washing oil solution for coating treatment, wherein the mass ratio of asphalt to washing oil is 0.05, the mass ratio of graphite to asphalt is 20, the reaction temperature is 150 ° C, the reaction time is 8 hours, and then centrifugally filtered. Finally, it was carbonized under the condition of 900° C. and kept warm for 6 hours.

[0023] The obtained artificial graphite modified material has a tested reversible capacity of 353mAh / g, an increase of 13mAh / g, and an initial efficiency of 93.22%.

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Abstract

The invention provides a modification method of artificial graphite. The modification method is characterized in that the process comprises the following steps of: step 1, crushing and sieving the artificial graphite; carrying out pre-oxidization treatment in an ice water bath, wherein an oxidant can be potassium permanganate, concentrated sulfuric acid or a mixed solution of potassium permanganate and concentrated sulfuric acid; the concentration of potassium permanganate is 0.1-5 M, the concentration of concentrated sulfuric acid is 12-18 M, the solute mol ratio ranges from 10: 1 to 1: 10 when the potassium permanganate and the concentrated sulfuric acid are mixed, and the pre-oxidization time is 1-10 hours; step 2, dissolving the product of the step 1 into a washing oil solution of asphalt; heating and agitating to carry out in-situ covering treatment; centrifuging and filtering, wherein the mass ratio of asphalt to washing oil is 0.01-0.4; the mass ratio of artificial graphite to asphalt is 10-100; the covering temperature is 120-200 DEG C; and the reaction time is 2-10 hours; and step 3, carbonizing the product of the step 2, wherein the carbonizing temperature is 800-1500 DEG C and the heat-preservation time is 2-12 hours.

Description

technical field [0001] The invention relates to the field of lithium-ion secondary batteries, in particular to a method for modifying artificial graphite in lithium-ion battery negative electrode materials. Background technique [0002] As one of the most commonly used negative electrode materials in the lithium battery industry, artificial graphite has the advantages of good crystal morphology, high specific capacity, and good conductivity; however, due to problems such as poor high-current performance, unsatisfactory cycle performance, and severe solvation of artificial graphite, So that the general graphite needs proper treatment to achieve the best results. [0003] Because pyrolytic carbon such as pitch has good cycle stability and good stability to organic electrolytes, it can make up for the defects of graphite in this respect. Therefore, many pyrolytic carbons coated with organic polymers on the surface of graphite form carbon-carbon composite material. In addition...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/38
CPCY02E60/10
Inventor 刘庆华刘红光叶学海张波宫毓鹏孙国娟
Owner CNOOC TIANJIN CHEM RES & DESIGN INST
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