CN111244453B - Artificial composite graphite negative electrode material, lithium ion battery, preparation method and application - Google Patents
Artificial composite graphite negative electrode material, lithium ion battery, preparation method and application Download PDFInfo
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Abstract
The invention discloses a man-madeA composite graphite cathode material, a lithium ion battery, a preparation method and application. The preparation method comprises the following steps: carrying out carbonization treatment on a blocky mixture containing anthracite powder, needle coke green coke powder, a graphitization catalyst and a graphitizable adhesive, and then carrying out catalytic graphitization high-temperature treatment; the mass ratio of the anthracite powder to the needle coke green coke powder is (2-5): (5-8); the anthracite powder has a particle size D50 of 12-40 μm. The button cell obtained by the invention has excellent comprehensive performance and the compaction density reaches 1.75g/cm3The above; the discharge capacity reaches more than 360 mAh/g; the cycle performance is good (the cycle capacity is kept more than or equal to 90 percent after 300 times); the safety is better (the explosion does not occur at 130 ℃/60 minutes); the adaptability to electrolyte and other additives is good; the product has stable properties, and the batches have almost no difference; the preparation method is simple and feasible and is suitable for industrial production.
Description
Technical Field
The invention relates to an artificial composite graphite negative electrode material, a lithium ion battery, a preparation method and application.
Background
In recent years, lithium ion batteries have been used in a large number of applications in mobile phones, notebook computers, digital video cameras, and portable electric appliances. The lithium ion battery has excellent performances of large energy density, high working voltage, small volume, light weight, no pollution, quick charge and discharge, long cycle life and the like, and is an ideal energy source developed in the 21 st century. With the increasing requirements of various products on small size, light weight, multifunction and long-time driving, the improvement of the capacity and the large-current discharge performance of the lithium ion battery still depends on the development and the perfection of the negative electrode material. Therefore, for a long time, it has been the key point of research and development to improve the specific capacity of the lithium ion battery negative electrode material, reduce the first irreversible capacity, improve the cycling stability and improve the rapid charge and discharge performance.
The negative electrode material of lithium ion secondary batteries is mainly graphite micropowder at present. Wherein the common artificial stone toner has irregular shapeLarge specific surface area (usually > 5 m)2/g) results in poor processability of the material, low first efficiency, relatively high ash content and difficulty in ensuring stable batches.
Therefore, in order to overcome the performance deficiency of the common artificial graphite, the prior art carries out modification treatment on the artificial graphite. In japanese patent JP10294111, the graphite carbon material is coated with pitch at a low temperature, and after coating, non-melting treatment and light pulverization are required, which makes uniform coating difficult. Japanese patent JP11246209 is a method of impregnating graphite and hard carbon particles in pitch or tar at a temperature of 10 to 300 ℃, followed by solvent separation and heat treatment, which makes it difficult to form a highly polymerized pitch layer having a certain thickness on the surface of graphite and hard carbon. JP2000003708 rounds graphite material mechanically, then impregnates it in heavy oil, tar or pitch, separates and washes it, just like JP11246209 in terms of coating method. JP2000243398 discloses a method for surface treatment of graphite material by utilizing the atmosphere generated by pyrolysis of pitch, which is unlikely to improve the morphology of the modified material, and thus the improvement of the electrical properties is limited. JP2002042816 uses aromatic hydrocarbon as raw material and uses CVD method to coat or uses pitch phenolic resin to coat, which is similar to JP2000182617 and JP2000283398 in effect. US2006001003 reports a method for catalytic graphitization of artificial graphite-based negative electrode materials, which can improve rapid charge and discharge performance and cycle performance. Patent application CN201310172581.2 discloses a mesophase negative electrode material and a preparation method thereof, wherein the product has a low compacted density and a relatively small discharge capacity.
The various improvements reported in the above documents have problems that they cannot effectively improve the low compacted density and low discharge capacity of the negative electrode material for artificial graphite-based batteries.
Disclosure of Invention
The invention provides an artificial composite graphite cathode material, a lithium ion battery, a preparation method and application thereof, and aims to overcome the defects of low compacted density, low discharge capacity and the like of the artificial graphite cathode material of the battery in the prior art. The artificial composite graphite cathode material has high compaction density, large discharge capacity and good cycle performance, and the button cell prepared by the artificial composite graphite cathode material has excellent comprehensive performance, stable product property and almost no difference between batches.
The inventor researches and discovers that when the anthracite powder is used for the lithium ion battery, the impurity content is high, so that the tap density of the used material is low, the processability is poor, and the requirement of high purity of the graphite for the lithium battery cannot be met. Through a great deal of research, when the anthracite powder and needle coke green coke powder composite raw material with the particle size D50 of 12-40 mu m is used for graphitization and high-temperature treatment, and the mass ratio of the anthracite powder to the needle coke green coke powder is (2-5): (5-8), the obtained graphitized crystal nucleus is small and has high graphitization degree, and the produced electrode material has higher discharge capacity and higher compaction density when being used for a battery.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of an artificial composite graphite cathode material, which comprises the following steps:
carrying out carbonization treatment on a blocky mixture containing anthracite powder, needle coke green coke powder, a graphitization catalyst and a graphitizable adhesive, and then carrying out catalytic graphitization high-temperature treatment;
wherein the mass ratio of the anthracite powder to the needle coke green coke powder is (2-5): (5-8); the particle size D50 of the anthracite powder is 12-40 mu m.
In the present invention, the anthracite powder may be anthracite powder conventionally used in the art, and for example, may be anthracite powder available from Ningxia Jiayue charcoal industry Co.
In the present invention, the anthracite coal powder may have a particle size D50 of 12-37 μm, or may have a particle size D50 of 12.2 μm, 15.4 μm, 18.5 μm, 19.1 μm, 19.5 μm, 20.1 μm, or 36.1 μm.
In the present invention, the particle size of the needle coke green powder may be conventional in the art for such materials, for example, the particle size D50 of the needle coke green powder may be 10-20 μm, may also be 10.5-19.8 μm, and may also be 15.4 μm.
In the present invention, the graphitization catalyst is preferably one or more of carbides and oxides of the following elements: silicon, iron, tin or boron, more preferably a carbide of silicon and/or an oxide of iron. For example, the graphitization catalyst may be SiO2、SiC、Fe2O3、B2O3And SnO2One or more of (a).
In the present invention, the amount of the graphitization catalyst is the amount of the graphitization catalyst which is conventional in the art, for example, the amount of the graphitization catalyst may be 1 to 10%, 3 to 8%, or 5% of the sum of the mass of the anthracite powder and the mass of the needle coke green coke powder.
In the present invention, the binder capable of graphitization refers to a binder capable of binding, which is commonly used in the field of graphite negative electrode materials, and capable of making artificial graphite after graphitization, and is preferably one or more of petroleum pitch, coal pitch and phenolic resin. The particle size of the petroleum pitch or coal pitch is preferably 0.1mm or less. The petroleum asphalt, the coal asphalt and the phenolic resin can be selected from petroleum asphalt, coal asphalt and phenolic resin with various specifications in the field.
In the present invention, the binder capable of graphitization may be used in an amount conventional in the art, for example, the binder capable of graphitization may be used in an amount of 10 to 30% by mass, and may be used in an amount of 15 to 25% by mass of the sum of the masses of the anthracite powder and the needle coke green powder.
In the present invention, the method for preparing the cake mixture may be a method conventional in the art, and may include the steps of: heating and kneading a mixture containing anthracite powder, needle coke green coke powder, a graphitization catalyst and a binder, tabletting, then crushing, and briquetting to obtain the high-performance coal tar.
The heat kneading treatment can improve the processability of the artificial graphite at a high compacted density, and the specific operation method can be carried out by the conventional method in the field, such as solid phase kneading or liquid phase kneading. The liquid phase kneading means that the binder capable of graphitization is heated to a liquid state and then is kneaded with anthracite powder, needle coke green coke powder and a graphitization catalyst. The solid kneading means that a graphitizable binder, anthracite powder, needle coke green coke powder and a graphitization catalyst are mixed together, heated and kneaded. Liquid-phase kneading is preferable because it can avoid volatilization and polycondensation of the graphitizable binder due to an excessively high heating temperature. The heating temperature for the heating kneading in the present invention may be selected according to a conventional method in the art, and is generally lower than the crosslinking temperature of the graphitizable binder and 10 to 80 ℃ above the softening point temperature of the graphitizable binder, and the heating temperature may be 160-180 ℃ or may be 170 ℃. Short kneading time with heating, preferably 1 to 2 hours, leads to caking of the material, uneven mixing, and long kneading time with heating, which leads to volatilization loss of the binder and failure to form a kneaded mass.
Wherein the pulverization may be carried out by various conventional pulverization processes in the art, and the pulverization is preferably carried out into particles having a particle size of 5 to 100 μm.
The tabletting is convenient for carrying, storage and metering, and the uniformity and the caking property of the mixing can be checked through tabletting, and the tabletting can be a tablet with the thickness of 2-5mm, and can also be 3-4 mm.
The briquetting is performed to facilitate the subsequent graphitization treatment, and various conventional methods in the art can be adopted, such as extrusion, die forming or cold isostatic pressing.
In the present invention, the carbonization treatment is preferably performed under the protection of an inert gas. The inert gas is preferably nitrogen.
In the present invention, the time for the carbonization treatment can be selected according to a method conventional in the art, and may be, for example, 2 to 6 hours. The temperature of the carbonization treatment can be the temperature of the conventional carbonization treatment in the field, for example, 800-.
In the present invention, the carbonization treatment is preferably followed by cooling to room temperature and then the catalytic graphitization high temperature treatment. The room temperature may be 5-40 ℃.
In the present invention, the catalytic graphitization high temperature treatment can be performed by a method conventional in the art, for example, in a graphitization furnace. The time for the catalytic graphitization high temperature treatment may be selected according to methods conventional in the art, and may be, for example, 24 to 48 hours. The temperature of the catalytic graphitization high-temperature treatment can be the temperature of the catalytic graphitization high-temperature treatment which is conventional in the field, and can be 2800-3200 ℃ and can also be 3000 ℃.
In the invention, the mass ratio of the anthracite powder to the needle coke green coke powder is preferably 3:7 to 2: 3.
The invention also provides an artificial composite graphite cathode material prepared by the preparation method, and the performance parameters are shown in the following table 1:
TABLE 1
The invention also provides an application of the artificial composite graphite cathode material prepared by the preparation method in a lithium ion battery.
The invention also provides a lithium ion battery, and the negative electrode material of the lithium ion battery is the artificial composite graphite negative electrode material.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the artificial composite graphite cathode material has high compaction density, large discharge capacity and good cycle performance, and the button cell prepared by the artificial composite graphite cathode material has excellent comprehensive performance and mainly has the following advantages: the compacted density is higher and can reach 1.75g/cm3The above; electrochemical performance is good, and the discharge capacity is more than 360 mAh/g; the discharge platform and the platform retention rate are high; the cycle performance is good (300 cycles, the capacity is kept more than or equal to 90%); fifth, the safety is better (130℃)60 minutes without explosion and expansion); sixthly, the adaptability to electrolyte and other additives is better; the product has stable property and almost no difference among batches.
2. The preparation method is simple and feasible, has low cost and is suitable for industrial production.
Drawings
Fig. 1 is a first charge-discharge curve of the artificial composite graphite anode material of example 2 of the present invention.
Fig. 2 is a cycle curve of the artificial composite graphite anode material of example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The materials used in the various examples and comparative examples of the present invention are specifically illustrated as follows:
the petroleum asphalt is MQ-100 medium temperature asphalt produced by Dalian reinforcement industrial materials GmbH;
the coal pitch is medium temperature pitch produced by Henan Bohai chemical Co., Ltd;
the phenolic resin is 2130 phenolic resin produced by No-Sn Alzhen chemical Co.
The anthracite powder has high impurity content, difficult purification and grading processing, low compacted density of the prepared material and poor processing performance, thereby limiting the application of the anthracite powder in preparing electrode materials. The invention uses anthracite powder and needle coke green coke powder to carry out composite catalytic graphitization and high temperature treatment, overcomes the difficulties and prepares the cathode material with good performances.
Example 1
Pulverizing petroleum asphalt to below 0.1mm, adding anthracite powder (D50 is 19.1 μm)60kg, needle coke green coke powder (D50 is 15.4 μm)140kg and graphitization catalyst (SiO) under stirring2) Mixing 16kg of the above materials, adding 60kg of asphalt powder into a kneading pot, kneading at 160 deg.C for 1 hr, and tablettingPressing into sheet (4mm), pulverizing into granules with diameter less than 100 μm, and briquetting. Under the protection of nitrogen, carbonizing at 1100 ℃ for 2 hours, cooling the reaction product to room temperature, and carrying out catalytic graphitization at 2800 ℃ for 36 hours to obtain the artificial composite graphite cathode material with the particle size D50 of 17.8 mu m, wherein the half-cell capacity of the artificial composite graphite cathode material is 362.5mAh/g, and the primary efficiency of the artificial composite graphite cathode material is 92.8%.
Research shows that the grain size of the anthracite powder has great influence on the compacted density and the discharge capacity, and the grain size distribution is wider due to too large and too small grain sizes, so that the compacted density and the electrical property are influenced finally.
Example 2
Pulverizing petroleum asphalt to below 0.1mm, alternately adding 80kg anthracite powder (D50 is 19.5 μm), 120kg needle coke powder (D50 is 15.4 μm) and 6kg graphitization catalyst (SiC) under stirring, mixing uniformly, mixing with 20kg asphalt powder in a kneading pot, kneading at 160 deg.C for 1 hr, pressing into sheet (3mm) in a tablet press, pulverizing into granules with diameter less than 100 μm, and briquetting. Under the protection of nitrogen, carbonizing at 800 ℃ for 6 hours, cooling the reaction product to room temperature, and carrying out catalytic graphitization at 3000 ℃ for 48 hours to obtain the artificial composite graphite cathode material with the particle size D50 of 18.3 mu m, wherein the half-cell capacity of the artificial composite graphite cathode material is 363.1mAh/g, and the primary efficiency of the artificial composite graphite cathode material is 93.2%.
Example 3
Pulverizing coal tar pitch to below 0.1mm, alternately adding anthracite powder (D50 is 20.1 μm)100kg, needle coke green coke powder (D50 is 19.8 μm)100kg and graphitization catalyst (SiO)2)10kg of the above-mentioned raw materials were mixed uniformly, and mixed with 40kg of asphalt powder in a kneading pot, and kneaded at 160 ℃ for 1 hour, and after kneading, the mixture was pressed into a sheet (5mm) in a tablet press, and pulverized into particles having a particle size of less than 100. mu.m, and briquetted and formed. Under the protection of nitrogen, carbonizing at 1500 ℃ for 3 hours, cooling the reaction product to room temperature, and then carrying out catalytic graphitization at 3200 ℃ for 48 hours to obtain the artificial composite graphite cathode material with the particle diameter D50 of 17.4 mu m, wherein the half-cell capacity of the artificial composite graphite cathode material is 365.0mAh/g, and the primary efficiency of the artificial composite graphite cathode material is 92.6%.
Example 4
Pulverizing coal tar pitch to below 0.1mm, alternately adding anthracite powder (D50 is 12.2 μm)40kg, needle coke green coke powder (D50 is 10.5 μm)160kg and graphitization catalyst (Fe)2O3)2kg of the above-mentioned raw materials were mixed uniformly, and mixed with 50kg of asphalt powder in a kneading pot, and kneaded at 160 ℃ for 2 hours, and after kneading, the mixture was pressed into a sheet (5mm) in a tablet press, and pulverized into particles having a particle size of less than 100. mu.m, and briquetted and formed. Under the protection of nitrogen, carbonizing at 1000 ℃ for 4 hours, cooling the reaction product to room temperature, and then carrying out catalytic graphitization at 2800 ℃ for 48 hours to obtain the artificial composite graphite cathode material with the particle diameter D50 of 10.6 mu m, the half-cell capacity of the artificial composite graphite cathode material is 366.7mAh/g, and the primary efficiency of the artificial composite graphite cathode material is 93.0%.
Example 5
Pulverizing petroleum asphalt to below 0.1mm, adding anthracite powder (D50 is 36.1 μm)60kg, needle coke green coke powder (D50 is 19.8 μm)140kg and graphitization catalyst (B) under stirring2O3)20kg of the above-mentioned raw materials were mixed uniformly, and mixed with 40kg of asphalt powder in a kneading pot, and kneaded at 170 ℃ for 1.5 hours, and after kneading, the mixture was pressed into a sheet form (2mm) in a tablet press, and pulverized into particles having a particle size of less than 100. mu.m, and briquetted and formed. Under the protection of nitrogen, carbonizing at 1100 ℃ for 2 hours, cooling the reaction product to room temperature, and then carrying out catalytic graphitization at 3200 ℃ for 24 hours to obtain the artificial composite graphite cathode material with the particle size D50 of 30.4 mu m, wherein the half-cell capacity of the artificial composite graphite cathode material is 362.4mAh/g, and the primary efficiency of the artificial composite graphite cathode material is 92.8%.
Example 6
Pulverizing petroleum asphalt to below 0.1mm, alternately adding 60kg anthracite powder (D50 is 18.5 μm), 140kg needle coke green coke powder (D50 is 15.4 μm) and 10kg graphitizing catalyst (SiC) under stirring, mixing with 30kg asphalt powder in a kneading pot, kneading at 180 deg.C for 1 hr, pressing into sheet (2mm) in a tablet press, pulverizing into granules with diameter less than 100 μm, and briquetting. Under the protection of nitrogen, carbonizing at 900 ℃ for 5 hours, cooling the reaction product to room temperature, and then carrying out catalytic graphitization at 3200 ℃ for 48 hours to obtain the artificial composite graphite cathode material with the particle diameter D50 of 16.8 mu m, wherein the half-cell capacity of the artificial composite graphite cathode material is 366.1mAh/g, and the primary efficiency of the artificial composite graphite cathode material is 92.4%.
Example 7
Pulverizing coal tar pitch to below 0.1mm, alternately adding anthracite powder (D50 is 19.1 μm)60kg, needle coke green coke powder (D50 is 15.4 μm)140kg and graphitization catalyst (SnO)2)6kg of the above-mentioned raw materials were mixed uniformly, and mixed with 20kg of asphalt powder in a kneading pot, and kneaded at 160 ℃ for 1 hour, and after kneading, the mixture was pressed into a sheet (5mm) in a tablet press, and pulverized into particles having a particle size of less than 100. mu.m, and briquetted and formed. Under the protection of nitrogen, carbonizing at 1100 ℃ for 2 hours, cooling the reaction product to room temperature, and then carrying out catalytic graphitization at 3200 ℃ for 48 hours to obtain the artificial composite graphite cathode material with the particle diameter D50 of 17.1 mu m, wherein the half-cell capacity of the artificial composite graphite cathode material is 363.6mAh/g, and the primary efficiency of the artificial composite graphite cathode material is 92.6%.
Example 8
60kg of anthracite powder (D50 is 19.5 mu m), 140kg of needle coke green coke powder (D50 is 15.4 mu m) and a graphitization catalyst (SiO) are alternately added under stirring2) Mixing 16kg of the above components uniformly, mixing with 50kg of phenolic resin powder in a kneading pot, kneading at 180 ℃ for 1 hour, pressing into sheets (5mm) in a tablet press after kneading, pulverizing into granules with a particle size of less than 100 μm, and briquetting. Under the protection of nitrogen, carbonizing at 1100 ℃ for 120 minutes, cooling the reaction product to room temperature, and performing catalytic graphitization at 2800 ℃ for 48 hours to obtain the artificial composite graphite cathode material with the particle size D50 of 17.9 mu m, the half-cell capacity of 362.7mAh/g and the primary efficiency of 92.3%.
Comparative example 1
Pulverizing petroleum asphalt to below 0.1mm, alternately adding 60kg anthracite powder (D50 is 16.5 μm), 140kg needle coke green coke powder (D50 is 15.4 μm) and 20kg asphalt powder into a reaction kettle under stirring, performing thermal coating treatment, carbonizing at 1100 deg.C for 2 hr under the protection of nitrogen after coating, cooling the reaction product to room temperature, and mixing with additive (SiO)2)10kg of the graphite powder is alternately added into a cantilever double-helix conical mixer to be mixed, and then the high-temperature treatment (3200 ℃) for catalytic graphitization is carried out for 48 hours. The prepared artificial composite graphite cathode material with the particle size D50 of 19.4 mu m has the half-cell capacity of 367.0mAh/g and the primary efficiency of 89.7 percent.
Comparative example 2
Pulverizing petroleum asphalt to below 0.1mm, alternately adding 200kg of needle coke green coke powder (D50 is 19.8 μm) and 20kg of asphalt powder into a kneading pot under stirring, kneading at 160 deg.C for 1 hr, pressing into sheet (2mm) in a tablet press, pulverizing into granules with diameter less than 100 μm, and briquetting. Under the protection of nitrogen, carbonizing at 1100 ℃ for 2 hours, cooling the reaction product to room temperature, and graphitizing at 2800 ℃ for 48 hours to obtain the artificial graphite cathode material with the particle diameter D50 of 19.2 mu m, the half-cell capacity of 345.2mAh/g and the primary efficiency of 91.3%.
Comparative example 3
Pulverizing coal tar pitch to below 0.1mm, alternately adding 60kg anthracite powder (D50 is 27.1 μm) and 140kg needle coke breeze (D50 is 15.4 μm) under stirring, mixing well, mixing with 20kg asphalt powder in a kneading pot, kneading at 160 deg.C for 1 hr, pressing into sheet (5mm) in a tablet press, pulverizing into granules with diameter less than 100 μm, and briquetting. Under the protection of nitrogen, carbonizing at 1100 ℃ for 2 hours, cooling the reaction product to room temperature, graphitizing at 2800 ℃ for 48 hours to obtain the artificial composite graphite cathode material with the particle diameter D50 of 25.6 mu m, the half-cell capacity of 365.3mAh/g and the primary efficiency of 87.6%.
Comparative example 4
Pulverizing petroleum asphalt to below 0.1mm, alternately adding 80kg anthracite powder (D50 is 19.5 μm), 40kg needle coke powder (D50 is 15.4 μm) and 6kg graphitization catalyst (SiC) under stirring, mixing uniformly, mixing with 20kg asphalt powder in a kneading pot, kneading at 160 deg.C for 1 hr, pressing into sheet (3mm) in a tablet press, pulverizing into granules with diameter less than 100 μm, and briquetting. Under the protection of nitrogen, carbonizing at 800 ℃ for 6 hours, cooling the reaction product to room temperature, and carrying out catalytic graphitization at 3000 ℃ for 48 hours to obtain the artificial composite graphite cathode material with the particle size D50 of 16.9 mu m, wherein the half-cell capacity of the artificial composite graphite cathode material is 353.7mAh/g, and the primary efficiency of the artificial composite graphite cathode material is 88.7%.
Comparative example 5
Pulverizing petroleum asphalt to below 0.1mm, alternately adding 80kg anthracite powder (D50 is 8.5 μm), 120kg needle coke powder (D50 is 15.4 μm) and 6kg graphitization catalyst (SiC) under stirring, mixing uniformly, mixing with 20kg asphalt powder in a kneading pot, kneading at 160 deg.C for 1 hr, pressing into sheet (3mm) in a tablet press, pulverizing into granules with diameter less than 100 μm, and briquetting. Under the protection of nitrogen, carbonizing at 800 ℃ for 6 hours, cooling the reaction product to room temperature, and carrying out catalytic graphitization at 3000 ℃ for 48 hours to obtain the artificial composite graphite cathode material with the particle size D50 of 15.2 mu m, wherein the half-cell capacity of the artificial composite graphite cathode material is 358.0mAh/g, and the primary efficiency of the artificial composite graphite cathode material is 87.9%.
Comparative example 6
(1) 60kg of spherical natural graphite (D50 of 19.1 mu m), 140kg of mesocarbon microbeads (D50 of 25.4 mu m) and graphitization catalyst (SiO 2) are alternately added under stirring2) Mixing 16kg of the raw materials uniformly to obtain a mixture;
(2) mixing the mixture with 60kg of petroleum asphalt powder (pulverized to 0.1mm or less) in a kneading pot, and kneading at 160 deg.C for 1 hr;
(3) after kneading, pressing into sheets (thickness of 4mm) in a tablet press, crushing into particles with average particle size less than 100 μm, and molding by pressing and briquetting;
(4) carbonizing at 1100 deg.C for 2 hr under nitrogen protection, and cooling to room temperature;
(5) and carrying out catalytic graphitization high-temperature treatment at 2800 ℃ for 36 hours to prepare a mesophase negative electrode material with the particle size D50 of 17.8 mu m, wherein the half-cell capacity is 352.5mAh/g, and the primary efficiency is 94.8%.
Comparative example 7
The comparative example does not contain a graphitizable binder, and the rest parameter conditions are the same as those of the example 1, so that the steps of briquetting, forming and the like cannot be completed, further the subsequent graphitization treatment is influenced, and the higher discharge capacity and the compacted density of the product are influenced.
Comparative example 8
In the comparative example, the mass ratio of the anthracite powder to the needle coke green coke powder is 1:6, and the rest conditions are the same as those in example 1.
Comparative example 9
The particle size of the anthracite coal powder in this comparative example was 50 μm, and the rest of the conditions were the same as in example 1.
Effect example 1
(1) The graphite negative electrode materials of examples 1 to 8 and comparative examples 1 to 9 were subjected to particle size, true density, compacted density, specific surface area, ash content and the like, respectively, and the results are shown in table 2. The name and model of the instrument used for the test are as follows: particle size, laser particle size distribution instrument MS 2000; a true density, super constant temperature water tank SC-15; ash content, high temperature electric furnace SX 2-2.5-12; compacting the density by a pole piece rolling mill JZL235X 35-B111; specific surface area, specific surface area meter NOVA 2000.
(2) The graphite negative electrode materials of examples 1 to 8 and comparative examples 1 to 9 were tested for discharge capacity and first efficiency using a half cell test method, and the results are shown in table 2.
The half cell test method comprises the following steps: graphite samples, N-methylpyrrolidone with 6-7% polyvinylidene fluoride and 2% conductive carbon black were mixed in a ratio of 91.6: 6.6: 1.8, coating the mixture on a copper foil, and putting the coated pole piece into a vacuum drying oven at the temperature of 110 ℃ for vacuum drying for 4 hours for later use. The simulated cell was assembled in an argon-filled German Braun glove box with electrolyte 1M-LiPF6 EC: DEC: DMC 1: 1 (volume ratio), a metallic lithium plate as counter electrode, and electrochemical performance testing was performed on an American ArbinBT2000 cell tester with a charge-discharge voltage range of 0.005 to 1.0V and a charge-discharge rate of 0.1C.
TABLE 2
(3) The artificial composite graphite negative electrode material for a lithium secondary battery of example 2 was tested by a full battery test method. The full battery test method comprises the following steps: the artificial composite graphite of example 2 was used as a negative electrode, lithium cobaltate was used as a positive electrode, and a solution of 1M-LiPF6 EC: DMC: EMC (volume ratio) 1: 1 was used as an electrolyte to assemble a full cell, and the capacity retention rate reached 93.65% after charging and discharging for 300 weeks under test 1C, indicating that the cycle performance was good, and the results are shown in fig. 2.
(4) The results of other related tests on finished batteries made of the artificial composite graphite anode material for lithium secondary batteries of examples 1 to 8 were: the discharge platform (3.6V) is more than or equal to 75 percent, and the platform is maintained to be more than or equal to 95 percent after 100 cycles; circulating for 300 times, and keeping the capacity more than or equal to 90 percent; safety performance tests such as overcharge, high-temperature short circuit, thermal shock and the like have good stability, and the safety performance tests are free from ignition and explosion, and the surface temperature is not more than 150 ℃; the adaptability to electrolyte and other additives is good, and lithium is not separated out; the product is stable, and the batches have almost no difference; the overcharge performance is better; the pole piece has good processability.
As can be seen from the above data, comparative example 1 is low in discharge efficiency, which is only 89.7%; comparative example 2 was low in discharge capacity of only 345.2mAh/g and low in compacted density; the compacted density of comparative example 3 was low. The artificial composite graphite cathode material for the lithium secondary battery prepared by the method has the specific surface area controlled within 3.0-4.0 m2The discharge capacity can reach more than 360mAh/g, and the compaction density is not less than 1.75g/cm3(ii) a The gram volume and the compaction density are higher, the loss of irreversible volume is reduced, the energy density is improved, and the using amount of the anode is reduced; the specific surface area is controlled in a proper range, so that the development of pores on the surface of particles can be ensured, the ballooning phenomenon generated by a lithium ion battery system can be favorably inhibited, and the safety performance of the battery is good; the overcharge performance is better; an ideal voltage platform, the discharge voltage can reach a steady state soon, as shown in fig. 1; the cycle performance is good, and the capacity retention rate can reach 93.65% after 300 cycles, as shown in FIG. 2.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (18)
1. The preparation method of the artificial composite graphite negative electrode material is characterized by comprising the following steps of:
carrying out carbonization treatment on a blocky mixture containing anthracite powder, needle coke green coke powder, a graphitization catalyst and a graphitizable adhesive, and then carrying out catalytic graphitization high-temperature treatment;
wherein the mass ratio of the anthracite powder to the needle coke green coke powder is (2-5) to (5-8); the grain diameter D50 of the anthracite powder is 12-40 mu m; the particle size D50 of the needle coke green coke powder is 10-20 μm; the graphitization catalyst is one or more of carbides and oxides of the following elements: silicon, iron, tin or boron;
the method for preparing the lumpy mixture comprises the following steps: heating and kneading a mixture containing anthracite powder, needle coke green coke powder, a graphitization catalyst and a binder, tabletting, then crushing, and briquetting to obtain the high-performance coal tar.
2. The method according to claim 1, wherein the anthracite coal powder has a particle size D50 ranging from 12 to 37 μm.
3. The method according to claim 2, wherein the anthracite coal powder has a particle size D50 of 12.2 μm, 15.4 μm, 18.5 μm, 19.1 μm, 19.5 μm, 20.1 μm, or 36.1 μm;
and/or the particle size D50 of the needle coke green powder is 10.5-19.8 μm.
4. The method of claim 2, wherein the needle coke breeze has a particle size D50 of 15.4 μm.
5. The production method according to claim 1, wherein the graphitization catalyst is a carbide of silicon and/or an oxide of iron;
and/or the graphitizable binder is one or more of petroleum asphalt, coal asphalt and phenolic resin.
6. The method according to claim 5, wherein the particle size of the petroleum pitch or coal pitch is 0.1mm or less.
7. The method according to claim 1, wherein the graphitization catalyst is used in an amount of 1-10% by mass of the sum of the mass of the anthracite powder and the mass of the needle coke green coke powder;
the amount of the binder capable of being graphitized is 10-30% of the mass sum of the anthracite powder and the needle coke green coke powder;
and/or the mass ratio of the anthracite powder to the needle coke green coke powder is 3:7-2: 3.
8. The method according to claim 7, wherein the graphitization catalyst is used in an amount of 3-8% by mass of the sum of the mass of the anthracite powder and the mass of the needle coke green coke powder;
the dosage of the binder capable of being graphitized is 15-25% of the mass sum of the anthracite powder and the needle coke green coke powder.
9. The method according to claim 7, wherein the graphitization catalyst is used in an amount of 5% by mass of the sum of the mass of the anthracite powder and the mass of the needle coke green coke powder.
10. The production method according to claim 1, wherein the heating temperature of the heat kneading is 10 to 80 ℃ above the softening point temperature of the graphitizable binder and below the crosslinking temperature of the graphitizable binder;
the heating kneading time is 1-2 hours;
the crushing is to be crushed into particles with the particle size of 5-100 mu m;
the pressing sheet is a sheet object pressed into a thickness of 2-5 mm;
and/or the pressed block is formed by extrusion, die forming or cold isostatic pressing.
11. The method as claimed in claim 10, wherein the heating temperature is 160-180 ℃;
the tablet is a tablet pressed into a thickness of 3-4 mm.
12. The method of claim 11, wherein the heating temperature is 170 ℃.
13. The method according to claim 1, wherein the carbonization treatment is performed under an inert gas atmosphere;
the carbonization treatment time is 2-6 hours;
the temperature of the carbonization treatment is 800-1500 ℃;
cooling to room temperature after the carbonization treatment, and then carrying out the catalytic graphitization high-temperature treatment;
the catalytic graphitization high-temperature treatment is carried out in a graphitization processing furnace;
the time of the catalytic graphitization high-temperature treatment is 24-48 hours;
and/or the temperature of the catalytic graphitization high-temperature treatment is 2800-3200 ℃.
14. The method of claim 13, wherein the inert gas is nitrogen;
the temperature of the carbonization treatment is 900-1100 ℃;
the room temperature is 5-40 ℃;
and/or the temperature of the catalytic graphitization high-temperature treatment is 3000 ℃.
15. The method of claim 14, wherein the carbonization treatment is performed at a temperature of 1000 ℃.
16. An artificial composite graphite negative electrode material produced by the production method as claimed in any one of claims 1 to 15.
17. Use of the artificial composite graphite anode material of claim 16 in a lithium ion battery.
18. A lithium ion battery, characterized in that its negative electrode material is the artificial composite graphite negative electrode material according to claim 17.
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