CN108258242B - Preparation method of high-performance artificial graphite anode material precursor - Google Patents
Preparation method of high-performance artificial graphite anode material precursor Download PDFInfo
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- CN108258242B CN108258242B CN201611235211.9A CN201611235211A CN108258242B CN 108258242 B CN108258242 B CN 108258242B CN 201611235211 A CN201611235211 A CN 201611235211A CN 108258242 B CN108258242 B CN 108258242B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a high-performance artificial graphite anode material precursor, which is mainly characterized by comprising the following steps of: a. selecting refined coal pitch with quinoline insoluble matter content not more than 0.5 wt% and residual carbon content of 10-40 wt% as material; b. the raw materials are put into a carbonization device for carbonization, and the specific carbonization conditions are as follows: and (3) carbonizing time: 6-8 hours; carbonization temperature: 450-490 ℃; carbonization pressure: 0.20 to 0.6 MPa; nitrogen flow rate: 0.01 to 0.20m3H; c. the carbonized material obtained under the carbonization condition is subjected to heat treatment under nitrogen atmosphere to obtain the prepared precursor, and the specific heat treatment conditions are as follows: the heat treatment temperature is as follows: 600 ℃ and 1000 ℃; nitrogen flow rate: 0.30-1m3H; and (3) heat treatment time: 20min-2 h.
Description
Technical Field
The invention relates to a technology for preparing a high-quality artificial graphite type lithium ion battery anode material precursor.
Background
In the early development stage of the lithium ion battery, the cathode material mainly comprises natural graphite and MCMB. With the development of the lithium ion battery industry, especially the explosive growth of power batteries, the requirements on the capacity, the cyclicity and the rate of the negative electrode material are continuously improved, and the price is continuously reduced. Therefore, artificial graphite-based negative electrode materials have been produced and have become the mainstream of negative electrode materials for power batteries. At present, the raw materials for preparing the artificial graphite type lithium ion battery cathode material mainly comprise: needle coke, petroleum coke, pitch coke. Traditionally, needle coke has been used primarily for the production of ultra-high power graphite electrodes; the pitch coke is mainly applied to the fields of carburant, aluminum anode, special carbon and the like. Because of different application fields and different required performances, the development of a precursor technology meeting the requirements of the negative electrode material for the power battery is imperative. At present, no preparation technology of the precursor specially used for the lithium ion battery anode material is seen in relevant documents and reports.
Disclosure of Invention
The invention aims to provide a method for preparing a precursor of a lithium ion battery cathode material, and the cathode material prepared by using the precursor prepared by the method as a raw material has better particle shape and electrochemical performance.
The technical problem to be solved can be implemented by the following technical scheme.
A preparation method of a high-performance artificial graphite anode material precursor is characterized by comprising the following steps:
a. selecting refined coal pitch with quinoline insoluble matter content not more than 0.5 wt% and residual carbon content of 10-40 wt% as material;
b. the raw materials are put into a carbonization device for carbonization, and the specific carbonization conditions are as follows:
and (3) carbonizing time: 6-8 hours;
carbonization temperature: 450-490 ℃;
carbonization pressure: 0.20 to 0.6 MPa;
nitrogen flow rate: 0.01 to 0.20m3/h；
c. And (2) carrying out heat treatment on the carbide obtained under the carbonization condition in a nitrogen atmosphere to obtain the prepared precursor, wherein the specific heat treatment conditions are as follows:
the heat treatment temperature is as follows: 600 ℃ and 1000 ℃;
nitrogen flow rate: 0.30-1m3/h；
And (3) heat treatment time: 20min-2 h.
As one of the preferable embodiments of the invention, the mass percent of quinoline insoluble substances in the raw material is less than or equal to 0.4 percent, and the mass percent of carbon residue is 15-40 percent.
As a further improvement of the technical scheme, when the raw material is carbonized in the carbonization device, the specific carbonization conditions are as follows:
and (3) carbonizing time: 6-8 hours;
carbonization temperature: 460 to 480 ℃;
carbonization pressure: 0.20 to 0.4 MPa;
nitrogen flow rate: 0.02-0.20 m3/h。
As a further improvement of the present technical solution, the specific heat treatment conditions of the heat treatment are as follows:
the heat treatment temperature is 700 ℃ and 1000 ℃;
nitrogen flow rate: 0.30-1m3/h；
And (3) heat treatment time: 20min-1 h.
Also as a preferred embodiment of the present invention, the method employs the following specific process conditions:
a. selecting refined coal pitch with quinoline insoluble content of 0.05 percent by mass and residual carbon content of 15.1 percent by mass as a raw material;
b. the raw materials are put into a carbonization device for carbonization, and the specific carbonization conditions are as follows:
and (3) carbonizing time: 7 hours;
carbonization temperature: 465 ℃;
carbonization pressure: 0.25 MPa;
nitrogen flow rate: 0.05m3/h；
c. And (2) carrying out heat treatment on the carbide obtained under the carbonization condition in a nitrogen atmosphere to obtain the prepared precursor, wherein the specific heat treatment conditions are as follows:
the heat treatment temperature is as follows: 800 ℃;
nitrogen flow rate: 0.45m3/h；
And (3) heat treatment time: and (4) 40 min.
As a preferred embodiment of the present invention, the method employs the following specific process conditions:
a. selecting refined coal pitch with quinoline insoluble matter content of 0.03 wt% and carbon residue content of 35.6 wt% as raw material;
b. the raw materials are put into a carbonization device for carbonization, and the specific carbonization conditions are as follows:
and (3) carbonizing time: 8 hours;
carbonization temperature: 460 ℃;
carbonization pressure: 0.30 MPa;
nitrogen flow rate: 0.04m3/h；
c. And (2) carrying out heat treatment on the carbide obtained under the carbonization condition in a nitrogen atmosphere to obtain the prepared precursor, wherein the specific heat treatment conditions are as follows:
the heat treatment temperature is as follows: 900 ℃;
nitrogen flow rate: 0.55m3/h；
And (3) heat treatment time: and (3) 30 min.
As a preferred embodiment of the present invention, the method employs the following specific process conditions:
a. selecting refined coal pitch with quinoline insoluble content of 0.35 percent by mass and residual carbon content of 27.4 percent by mass as a raw material;
b. the raw materials are put into a carbonization device for carbonization, and the specific carbonization conditions are as follows:
and (3) carbonizing time: 7 hours;
carbonization temperature: 470 ℃;
carbonization pressure: 0.40 MPa;
nitrogen flow rate: 0.03m3/h；
c. And (2) carrying out heat treatment on the carbide obtained under the carbonization condition in a nitrogen atmosphere to obtain the prepared precursor, wherein the specific heat treatment conditions are as follows:
the heat treatment temperature is as follows: 1000 ℃;
nitrogen flow rate: 0.60m3/h；
And (3) heat treatment time: and 20 min.
According to the preparation method of the high-performance artificial graphite cathode material precursor, low Quinoline Insoluble (QI) pitch is used as a raw material, carbonization is carried out under a specific carbonization condition, and heat treatment is carried out under normal pressure, so that the precursor for preparing the lithium ion battery cathode material is obtained. The negative electrode material obtained by crushing and graphitizing the precursor has excellent performance, and particularly has very high charge-discharge capacity. The precursor prepared by the technology is a high-quality material for preparing a high-capacity and high-rate lithium ion battery cathode material.
Drawings
FIG. 1 is a schematic view of a carbonizing apparatus used in the production method of the present invention;
in the figure: 1-carbonization tube 2-heating furnace 3-tail gas purification system
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings.
The invention relates to a technology for preparing a high-quality artificial graphite type lithium ion battery anode material precursor, which mainly comprises the following differences compared with the prior art:
the method comprises the following steps: refined coal pitch is used as a raw material, the content of Quinoline Insoluble (QI) is less than or equal to 0.5 percent (mass percent), and the carbon residue is 10 to 40 percent (mass percent).
Secondly, carbonization: the refined coal pitch is put into a carbonization device and carbonized under specific carbonization conditions. The specific key carbonization conditions are as follows:
and (3) carbonizing time: 6-8 hours;
carbonization temperature: 450-490 ℃;
carbonization pressure: 0.20 to 0.6 MPa;
nitrogen flow rate: 0.01 to 0.20m3/h。
Thirdly, heat treatment: and heating the carbide at the temperature of 600-1000 ℃ and in the nitrogen atmosphere for a certain time to finally prepare the high-quality lithium ion battery cathode material precursor. The specific heat treatment conditions were as follows:
the heat treatment temperature is 600 ℃ and 1000 ℃;
nitrogen flow rate: 0.30-1m3/h；
Time: 20min-2 hours.
As shown in figure 1, the carbonization device used in the preparation method mainly comprises three parts: respectively a carbonization tube 1, a heating furnace 2 and a tail gas purification system 3.
The specific carbonization operation is as follows:
putting a carbonization tube 1 filled with the refined coal tar pitch raw material into a heating furnace 2;
opening a nitrogen valve to enable nitrogen to enter from the bottom of the furnace tube, and adjusting the flow of the nitrogen to a set value;
thirdly, adjusting the outlet valve of the furnace tube to stabilize the pressure at a set value;
fourthly, electrifying, heating to a set value according to a set program, and carbonizing according to a set carbonization time.
The following is a preferred form of the preparation method relative to the above process requirements: wherein the content of the first and second substances,
(1) and raw materials: refined coal pitch is used as a raw material, the content of Quinoline Insoluble (QI) is less than or equal to 0.4 percent (mass percent), and the carbon residue is 15-40 percent (mass percent).
(2) And carbonization conditions:
and (3) carbonizing time: 6-8 hours;
carbonization temperature: 460 to 480 ℃;
carbonization pressure: 0.20 to 0.4 MPa;
nitrogen flow rate: 0.02-0.20 m3/h
(3) And heat treatment conditions: the heat treatment temperature is 700 ℃ and 1000 ℃; nitrogen flow rate: 0.30-1m3H, time: 20min-1 hour.
Benefits of this preferred condition: the method is favorable for improving the first charge-discharge capacity and the first charge-discharge efficiency of the cathode material precursor.
In practice, the precursor prepared according to the procedures can be firstly crushed to prepare powder with a certain granularity; then graphitizing at 3000 ℃; and then the button cell is made. And carrying out electrochemical performance detection on the button cell. The result shows that the cathode material prepared by the precursor obtained by the technical scheme has excellent electrochemical performance, and compared with needle coke, the charge-discharge capacity is improved, and particularly the rate capability is obviously improved. The specific effects are shown in the following table 1:
table 1: the electrochemical performance of the common material (needle coke) is compared with that of the negative electrode material prepared by the precursor in the technology
The preparation of the precursor and the performance of the cell obtained after graphitization in the present production method will be described below with reference to several more specific examples.
Example 1:
refined coal juiceCyan, QI: 0.05% (mass percent), carbon residue: 15.1% (mass percent). Carbonization temperature: 465 ℃ and carbonization pressure: 0.25MPa, nitrogen flow: 0.05m3H, carbonization time: for 7 hours. Heat treatment temperature 800 ℃, heat treatment time 40min, nitrogen flow: 0.45m3H is used as the reference value. The anode material precursor prepared by the technology is crushed to D50 ═ 15.2 mu m, graphitized at 3000 ℃ and prepared into a button cell, the first lithium removal capacity is 359.6mAh/g, the first coulombic efficiency is 93.8 percent, and the button cell multiplying power (1C/0.2C) is 48.5 percent.
Example 2:
refined coal pitch, QI: 0.03% (mass percent), carbon residue: 35.6% (mass percent). Carbonization temperature: 460 ℃, carbonization pressure: 0.30MPa, nitrogen flow: 0.04m3H, carbonization time: for 8 hours. Heat treatment temperature 900 ℃, heat treatment time 30min, nitrogen flow: 0.55m3H is used as the reference value. The anode material precursor prepared by the technology is crushed to D50 ═ 16.3 mu m, graphitized at 3000 ℃ and made into a button cell, the first lithium removal capacity is 362.4mAh/g, the first coulombic efficiency is 94.6%, and the button cell multiplying power (1C/0.2C) is 46.8%.
Example 3:
refined coal pitch, QI: 0.35% (mass percent), carbon residue: 27.4% (mass percent). Carbonization temperature: 470 ℃, carbonization pressure: 0.40MPa, nitrogen flow: 0.03m3H, carbonization time: for 7 hours. Heat treatment temperature 1000 ℃, heat treatment time 20min, nitrogen flow: 0.60m3H is used as the reference value. The anode material precursor prepared by the technology is crushed to D50 ═ 14.8 mu m, graphitized at 3000 ℃ and prepared into a button cell, the first lithium removal capacity is 358.7mAh/g, the first coulombic efficiency is 95.6%, and the button cell multiplying power (1C/0.2C) is 57.7%.
Claims (1)
1. A preparation method of a high-performance artificial graphite anode material precursor is characterized by comprising the following steps:
a. selecting refined coal pitch with quinoline insoluble content of 0.35 percent by mass and residual carbon content of 27.4 percent by mass as a raw material;
b. the raw materials are put into a carbonization device for carbonization, and the specific carbonization conditions are as follows:
and (3) carbonizing time: 7 hours;
carbonization temperature: 470 ℃;
carbonization pressure: 0.40 MPa;
nitrogen flow rate: 0.03m3/h；
c. And (2) carrying out heat treatment on the carbide obtained under the carbonization condition in a nitrogen atmosphere to obtain the prepared precursor, wherein the specific heat treatment conditions are as follows:
the heat treatment temperature is as follows: 1000 ℃;
nitrogen flow rate: 0.60m3/h；
And (3) heat treatment time: and 20 min.
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| CN101289625A (en) * | 2008-06-03 | 2008-10-22 | 山西宏特煤化工有限公司 | Production process of dipping agent bitumen |
| CN102225755A (en) * | 2011-05-26 | 2011-10-26 | 淄博矿业集团有限责任公司 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
| CN103333706A (en) * | 2013-07-11 | 2013-10-02 | 太原理工大学 | Method for preparing ordered needle coke through using coal tar pitch |
| CN105256409A (en) * | 2015-11-17 | 2016-01-20 | 安徽弘昌新材料有限公司 | Mesophase-pitch-based carbon fiber and preparation method thereof |
| CN105958072A (en) * | 2016-06-20 | 2016-09-21 | 傅云峰 | Preparation method of natural flake graphite-based negative electrode material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289625A (en) * | 2008-06-03 | 2008-10-22 | 山西宏特煤化工有限公司 | Production process of dipping agent bitumen |
| CN102225755A (en) * | 2011-05-26 | 2011-10-26 | 淄博矿业集团有限责任公司 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
| CN103333706A (en) * | 2013-07-11 | 2013-10-02 | 太原理工大学 | Method for preparing ordered needle coke through using coal tar pitch |
| CN105256409A (en) * | 2015-11-17 | 2016-01-20 | 安徽弘昌新材料有限公司 | Mesophase-pitch-based carbon fiber and preparation method thereof |
| CN105958072A (en) * | 2016-06-20 | 2016-09-21 | 傅云峰 | Preparation method of natural flake graphite-based negative electrode material |
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Address after: 2004-2002 Weisan Road Chemical Office Building, Baoshan District, Shanghai Applicant after: Baowu Carbon Material Technology Co., Ltd. Address before: 2004-2002 Weisan Road Chemical Office Building, Baoshan District, Shanghai Applicant before: Chemical Co., Ltd. of Baoshan Iron and Steel Group, Shanghai |
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Address after: 200942 three chemical engineering office building, Baoshan Iron and steel factory, Shanghai, Baoshan District Patentee after: Baowu Carbon Technology Co.,Ltd. Address before: 200942 three chemical engineering office building, Baoshan Iron and steel factory, Shanghai, Baoshan District Patentee before: BAOWU CARBON MATERIAL TECHNOLOGY Co.,Ltd. |
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