CN112713264A - Artificial graphite negative electrode material, preparation method, application and battery - Google Patents
Artificial graphite negative electrode material, preparation method, application and battery Download PDFInfo
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Abstract
The invention discloses an artificial graphite cathode material, a preparation method, application and a battery. The preparation method of the artificial graphite negative electrode material comprises the following steps: (1) electrically demagnetizing graphite fragments with the particle size D50 of 13.5-17.5 microns to obtain a precursor A; (2) modifying the precursor A and a coating agent to obtain a precursor B, wherein the curing temperature of the coating agent is 80-150 ℃; (3) and carrying out heat treatment on the precursor B to obtain the artificial graphite cathode material. The preparation method of the artificial graphite cathode material is simple, the time consumption of the working procedure is short, the mass production is easy, the raw materials are common industrial products, the cost of the raw material graphite fragments is low, and the source is stable; compared with the prior art, the artificial graphite cathode material prepared by using the graphite fragments can ensure higher tap density, first efficiency, rate capability and cycle capacity retention rate, and meets the use requirements of the artificial graphite cathode material.
Description
Technical Field
The invention particularly relates to an artificial graphite cathode material, a preparation method, application and a battery.
Background
In 1990, Sony corporation commercializes the lithium ion battery cathode carbon material for the first time, and the carbon material has the characteristics of high energy density, long circulation, no memory effect, green environmental protection and the like, and is widely applied to 3C electronic portable products, new energy automobiles and other social fields. The negative electrode material is used as a main component of the lithium ion battery, and systems such as natural graphite, artificial graphite, hard carbon, soft carbon, graphene, carbon nanotubes and the like exist at present. The artificial graphite is used as a negative electrode material, and has the advantages of good cycle performance and rate capability, good selectivity to electrolyte and the like. With the development of technology, the development direction of the negative electrode material is the improvement of the quick charging performance and the development of low-cost products, and the pressure of reducing the cost is obvious for the products on the market, so the development of the products with high performance and low cost is the most important factor.
The term "graphite particles" refers to a general term for a by-product produced by graphitizing a carbon product and a material obtained by cutting the graphitized product during processing. In various documents and literature, the definition of graphite particles is different, one is that graphite particles are not very large and are called graphite particles (such as graphite powder), and the other is that graphite particles have a certain size and form a block, namely graphite particles. At present, the graphite fragments are usually used as additives and conductive materials to be applied to the steel-making and casting industries and can also be used as the raw materials of the artificial graphite cathode, but the processing method is complex, the cost is higher, the waste of resources is caused, and the source limitation of the graphite fragments for preparing the raw materials is larger. If the crushed graphite can be recycled, the pressure of post-treatment can be reduced, and the high-efficiency utilization of resources can be realized.
Patent CN103346294B discloses a method for preparing artificial graphite cathode material, which uses ultra-high power graphite electrode fragments and ultra-high joint graphite fragments as coating matrix material after spheroidization, but the raw material is a by-product in the electrode manufacturing process, the source channel is single, and the method comprises a graphitization process, the process has high price (price of 1.2-1.6 ten thousand/ton) and long cycle (shortest 30 days).
Therefore, the technical problems to be solved in the field are to develop an artificial graphite cathode material and a preparation method thereof, wherein the artificial graphite cathode material has high tap density, good cycle performance, short processing period and low preparation cost, and the first efficiency meets the use requirements of the existing artificial graphite.
Disclosure of Invention
The invention aims to overcome the defects that the cost of artificial graphite is high, byproducts cannot be effectively utilized to cause waste and the like in the prior art, and provides an artificial graphite cathode material, a preparation method, application and a battery. The method for preparing the artificial graphite cathode material is simple and easy to operate, the graphite scraps which are byproducts of the artificial graphite are used as raw materials, the production cost is reduced, and meanwhile, the artificial graphite cathode material is high in tap density, small in specific surface area, large in discharge capacity, high in first-time efficiency and good in cycle performance, and can meet the use requirements of the artificial graphite cathode material.
The invention mainly solves the technical problems through the following technical scheme:
the invention provides a preparation method of an artificial graphite cathode material, which comprises the following steps:
(1) electrically demagnetizing graphite fragments with the particle size D50 of 13.5-17.5 microns to obtain a precursor A;
(2) modifying the precursor A and a coating agent to obtain a precursor B, wherein the curing temperature of the coating agent is 80-150 ℃;
(3) and carrying out heat treatment on the precursor B to obtain the artificial graphite cathode material.
In the step (1), the graphite fragments can be graphite fragments of artificial graphite cathode materials, preferably electrode graphite fragments and/or joint graphite fragments. The graphite particles are materials such as by-products generated after the carbon product is graphitized and the graphitized product is cut during processing.
In the step (1), the particle size D50 of the graphite particles can be realized by crushing and grading operations.
Wherein the pulverization can be carried out by a conventional method in the art, preferably by using a mechanical pulverizer.
The classification can be carried out using methods conventional in the art, preferably using a classifier.
In step (1), the electric demagnetization can be realized by using a conventional method in the field, and preferably by using an electromagnetic demagnetizer.
In the step (1), the particle diameter D50 of the precursor a may be 13.5 to 17.5 μm, preferably 15.5 to 17.5 μm.
In the step (1), the tap density of the precursor A can be 0.8-1.0 g/cm3。
In the step (1), the content of the magnetic substance in the precursor A can be 0.2-0.7 ppm.
In the step (2), the curing temperature of the coating agent can be 85-150 ℃.
In the step (2), the coating agent may be phenolic resin and/or epoxy resin, preferably epoxy resin.
In the step (2), the mass ratio of the precursor a to the coating agent may be 100: (8-12), preferably 100: (9-12).
In the step (2), the modification may include the steps of: and adding the precursor A and the coating agent into modification equipment.
In the step (2), the modification time may be 3-7 min, preferably 4 min.
In step (2), the temperature of the modification may be 15 to 25 ℃, preferably 20 ℃.
In step (2), the modification can be carried out using methods conventional in the art, preferably using a fusion machine.
In the step (2), the rotation speed of the fusion machine may be 600 to 800HZ, preferably 800 HZ.
In the step (3), the heat treatment may include the steps of: and calcining the precursor B, and keeping the temperature to obtain the catalyst.
Preferably, the calcination may be achieved using a roller kiln.
The calcination temperature may be 1100 to 1400 ℃, preferably 1200 to 1400 ℃.
The heating rate of the calcination may be 4-6 deg.C/min, preferably 3.0 deg.C/min.
The temperature of the heat preservation can be 1100-1400 ℃, preferably 1200-1400 ℃.
Preferably, the temperature of the heat preservation is the same as the temperature of the calcination.
The heat preservation time can be 4-7 h, preferably 5 h.
The invention also provides the artificial graphite cathode material prepared by the preparation method.
The invention also provides an application of the artificial graphite cathode material in a lithium ion battery.
The invention also provides a negative pole piece which comprises the artificial graphite negative pole material.
The preparation method of the negative pole piece can comprise the following steps: the artificial graphite negative electrode material, conductive carbon black SP, CMC and SBR are uniformly stirred in water to prepare negative electrode slurry, the negative electrode slurry is coated on two sides of a copper foil by using a coater, and the copper foil is pressed into sheets after vacuum drying.
The mass ratio of the artificial graphite negative electrode material, the conductive carbon black SP, the CMC, and the SBR may be 95.6: 1.0: 1.1: 2.3.
the temperature of the vacuum drying may be 110 ℃.
The vacuum drying time may be 4 hours.
The invention also provides a lithium ion battery which comprises an electrode prepared from the artificial graphite negative electrode material.
The preparation method of the lithium ion battery can comprise the following steps: 1mol/L LiPF6The solvent of the electrolyte is a three-component mixed solvent, ethyl carbonate, dimethyl carbonate and methyl ethyl carbonate are mixed according to the volume ratio of 1:1:1, a metal lithium sheet is used as a positive electrode, and the negative electrode sheet made of the artificial graphite negative electrode material is assembled in a glove box filled with argon.
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:
the artificial graphite cathode material prepared by using the graphite fragments can ensure higher tap density, first efficiency and cycle capacity retention rate; the surface of the material is modified by a coating agent, so that the rate capability of the material is improved, and the use requirement of the artificial graphite cathode material is met;
the method for preparing the artificial graphite cathode material is simple and easy to operate, short in process time consumption, easy for mass production, low in graphite crushing cost and stable in source, and raw materials are common industrial products.
Drawings
FIG. 1 is a scanning electron micrograph of powders of an artificial graphite negative electrode material of example 1;
FIG. 2 is a charge-discharge curve diagram of the artificial graphite anode material of example 1;
fig. 3 is an ac impedance diagram of the artificial graphite negative electrode material of example 1.
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 phenolic resin and the epoxy resin are purchased from Liaoning Xin De chemical Co., Ltd, the curing temperature of the phenolic resin is 90-145 ℃, and the curing temperature of the epoxy resin is 90-95 ℃.
In the following examples and comparative examples, the mechanical pulverizer LHJ-150 used was purchased from Weichaft Positive distal machines, Inc. The electromagnetic demagnetizer ZR0709 is purchased from Nikki electromechanical equipment Limited of Lin 26384. The high performance gravity-free blender WZ-H-10P was purchased from Shanghai silver shark machine, Inc. The fusion machine ZSJ-600 was purchased from Gengxin powder facilities, Inc. without Sn. The carbonization furnace is purchased from Foshan high sand industrial kiln Co.
Example 1
(1) Crushing electrode graphite fragments with the diameter of 20mm by a mechanical crusher LHJ-150, wherein the average particle size D50 after classification is 14.0 mu m, and removing magnetic substances in the graphite fragments by using an electromagnetic demagnetizer ZR0709 to obtain a precursor A with the magnetic substance content of 0.4 ppm;
(2) mixing the precursor A with epoxy resin according to the mass ratio of 100: 9, respectively putting the raw materials into a fusion machine ZSJ-600 for modification treatment at the rotation speed of 800HZ and the temperature of 20 ℃ for 4min to obtain a precursor B;
(3) and under the nitrogen atmosphere, putting the precursor B into a carbonization furnace for carbonization, heating to 1200 ℃, and then preserving the heat for 5 hours at the same temperature to obtain the artificial graphite cathode material.
The artificial graphite negative electrode material obtained in example 1 had a particle diameter D50 of 15.5. mu.m, and a tap density of 0.94g/cm3Specific surface area of 1.8m2The magnetic material content is 0.4ppm, the discharge capacity is 349.0mAh/g, the primary efficiency is 91.5%, and the cycle capacity retention rate of 1C/1C 500 cycles is 91.5%.
Example 2
(1) Same as example 1, step (1);
(2) mixing the precursor A with epoxy resin according to the mass ratio of 100: 12 are respectively put into a fusion machine ZSJ-600 for modification treatment, the rotating speed of the fusion machine is 800HZ, the temperature of the modification treatment is 20 ℃, and the time of the modification treatment is 4min, so as to obtain a precursor B;
(3) same as example 1, step (3).
The artificial graphite negative electrode material obtained in example 2 had a particle diameter D50 of 16.9. mu.m, and a tap density of 0.90g/cm3Specific surface area of 1.5m2The magnetic material content is 1.0ppm, the discharge capacity is 348.0mAh/g, the first efficiency is 92.3 percent, and the cycle capacity retention rate of 1C/1C 500 cycles is 92.0 percent.
Comparative example 1
Comparative example 1 differs from example 1 in that: the magnetic removing process of the step (1) is not carried out, and the rest steps are not changed.
The artificial graphite negative electrode material obtained in comparative example 1 had a particle diameter D50 of 15.2 μm and a tap density of 0.91g/cm3Specific surface area of 1.6m2The average value of the magnetic substance content is about 8.0ppm, the discharge capacity is 348.7mAh/g, the first efficiency is 90.4%, and the cycle capacity retention rate is 59.4% at 1C/1C 500 cycles.
Comparative example 2
Comparative example 2 differs from example 1 in that: the conventional artificial graphite is used as a raw material instead of graphite scraps, and the rest steps are unchanged.
The artificial graphite negative electrode material obtained in comparative example 2 had a particle diameter D50 of 15.4. mu.m, and a tap density of 0.95g/cm3Specific surface area of 1.6m2The average value of the magnetic substance content is about 0.3ppm, the discharge capacity is 349.4mAh/g, the first efficiency is 92.3 percent, and the cycle capacity retention rate of 1C/1C 500 cycles is 92.7 percent.
Comparative example 3
Comparative example 3 differs from example 1 in that: the particle diameter D50 of the precursor A in the step (1) is 12.5 μm, and the rest steps are unchanged.
The artificial graphite negative electrode material obtained in comparative example 3 had a particle diameter D50 of 13.2. mu.m, and a tap density of 0.75g/cm3Specific surface area of 2.6m2The average value of the magnetic substance content is about 0.5ppm, the discharge capacity is 345.7mAh/g, the first efficiency is 88.4 percent, and the cycle capacity retention rate of 1C/1C 500 cycles is 87.6 percent.
Effects of the embodiment
The artificial graphite anode materials obtained in examples 1 and 2 and comparative example 1 were respectively subjected to particle size, tap density and specific surface area tests, and the results are shown in table 1. The name and model of the instrument used for the test are as follows: the particle size is measured by using a laser particle size distribution instrument MS 2000; the tap density is measured by using a tap meter TF-100B; specific surface area measurement using a specific surface area meter NOVATouch 2000; test of compaction Density an FT-100F powder automated compaction densitometer was used.
The preparation method of the half cell comprises the following steps: the artificial graphite negative electrode material, conductive carbon black SP, CMC and SBR are mixed according to the mass ratio of 95.6: 1.0: 1.1: and 2.3, uniformly stirring in water to prepare negative electrode slurry, coating the negative electrode slurry on two sides of copper foil by using a coater, putting the two-side coated electrode piece into a vacuum drying box at the temperature of 110 ℃ for vacuum drying for 4 hours, and pressing the electrode piece to prepare the negative electrode piece. Wherein the compacted density is the surface density/(thickness of the rolled pole piece-current collector thickness). The CR-2430 button cell is assembled in a Mikenona glove box filled with argon and has 1mol/L LiPF electrolyte6The three components of the mixed solvent are mixed according to the volume ratio of ethyl carbonate to dimethyl carbonate to methyl ethyl carbonate of 1:1:1, and the metal lithium sheet is used as a counter electrode.
And performing charge and discharge tests on a blue-ray battery test cabinet, wherein the voltage interval is 0.005-1.0V, and the charge and discharge multiplying power is 0.1C. The multiplying power, direct current impedance and alternating current impedance tests are carried out on an ArbinBT2000 type battery tester in the United states, and the test voltage interval is 0.005-1.0V.
TABLE 1
As can be seen from Table 1, since comparative example 1 did not undergo the demagnetization step, the content of the magnetic substance was as high as about 8ppm, and the use requirement of the artificial graphite could not be satisfied. In the 500-cycle capacity retention rate result of 1C/1C, the capacity retention rate of the comparative example 1 is greatly attenuated to 59.4%, and the capacity is seriously jumped, so that a great safety problem exists.
On the other hand, compared with the example 1, the comparative example 2 uses the conventional artificial graphite as the anode material prepared by the raw material, and the two groups of test indexes are equivalent, which shows that the example 1 can meet the use requirement of the artificial graphite and simultaneously reduce the cost; while comparative example 3 is less efficient, the 1C/1C 500 cycle capacity retention is also lower than example 1.
As can be seen from the field emission scanning electron microscope image of example 1 in FIG. 1, the artificial graphite anode material prepared in example 1 has a smooth and flat surface and no burr on the particle surface, so that example 1 has a high tap density. FIG. 2 is a graph of the charge and discharge curves of example 1, showing the higher capacity of the material prepared in example 1. FIG. 3 is an AC impedance plot of example 1, showing the better rate capability of the material made in example 1, the specific data is shown in Table 2.
TABLE 2
| Serial number | 0.1C/0.1C | 0.2C/0.1C | 0.5C/0.1C | 1C/0.1C | 2C/0.1C | 3C/0.1C |
| Example 1 | 98.1％ | 95.3％ | 74.0％ | 59.1％ | 20.0％ | 10.5％ |
| Example 2 | 98.0％ | 94.6％ | 72.9％ | 56.8％ | 19.1％ | 9.91％ |
| Comparative example 1 | 97.1％ | 96.1％ | 73.1％ | 57.3％ | 19.4％ | 8.9％ |
| Comparative example 2 | 98.2％ | 95.5％ | 74.9％ | 60.0％ | 20.5％ | 10.3％ |
| Comparative example 3 | 94.3％ | 86.9％ | 67.1％ | 35.3％ | 9.4％ | 3.9％ |
Rate performance data for the artificial graphite anode materials prepared in examples 1-2 and comparative examples 1-3 are provided in table 2. As is apparent from the data in Table 2, the artificial graphite anode material prepared by crushing, classifying, demagnetizing, coating, modifying and carbonizing graphite scraps has good dynamic performance. The rate performance of the artificial graphite cathode material prepared in the comparative example 1 without demagnetization does not change obviously in a rate test of several weeks, but the test results in the table 1 show that although the demagnetization process has little influence on short-term rate, the capacity of the material without demagnetization is obvious in water jumping in a long cycle, so that the artificial graphite cathode material has a great safety problem and cannot meet the use requirement of the artificial graphite cathode material. In addition, in combination with the data in table 1, the rate performance of comparative example 3 is relatively poor, and does not meet the use requirements of the artificial graphite anode material.
Claims (10)
1. The preparation method of the artificial graphite negative electrode material is characterized by comprising the following steps of:
(1) electrically demagnetizing graphite fragments with the particle size D50 of 13.5-17.5 microns to obtain a precursor A;
(2) modifying the precursor A and a coating agent to obtain a precursor B, wherein the curing temperature of the coating agent is 80-150 ℃;
(3) and carrying out heat treatment on the precursor B to obtain the artificial graphite cathode material.
2. The method for preparing the artificial graphite negative electrode material according to claim 1, wherein in the step (1), the graphite particles are electrode graphite particles and/or joint graphite particles;
and/or the electric demagnetization is realized by using an electromagnetic demagnetizer.
3. The method for preparing the artificial graphite anode material of claim 1, wherein in the step (1), the particle size D50 of the precursor A is 13.5-17.5 μm, preferably 15.5-17.5 μm;
and/or the tap density of the precursor A is 0.8-1.0 g/cm3；
And/or the content of the magnetic substance in the precursor A is 0.2-0.7 ppm.
4. The method for preparing the artificial graphite anode material according to claim 1, wherein in the step (2), the curing temperature of the coating agent is 85-150 ℃; the coating agent is phenolic resin and/or epoxy resin, preferably epoxy resin;
and/or the mass ratio of the precursor A to the coating agent is 100: (8-12), preferably 100: (9-12).
5. The method for preparing the artificial graphite anode material according to claim 1, wherein in the step (2), the modification comprises the steps of: adding the precursor A and the coating agent into modification equipment;
and/or the modification time is 3-7 min, preferably 4 min;
and/or the temperature of the modification is 15-25 ℃, preferably 20 ℃;
and/or the modification is realized by using a fusion machine, wherein the rotating speed of the fusion machine is 600-800 HZ, preferably 800 HZ.
6. The method for preparing the artificial graphite anode material according to claim 1, wherein in the step (3), the heat treatment comprises the steps of: calcining the precursor B, and keeping the temperature to obtain the precursor B;
preferably, the calcination is effected using a roller kiln;
the calcination temperature is preferably 1100-1400 ℃, more preferably 1200-1400 ℃;
the heating rate of the calcination is preferably 3.0 ℃/min;
the temperature of the heat preservation is preferably 1100-1400 ℃, and more preferably 1200-1400 ℃;
preferably, the temperature of the heat preservation is the same as the temperature of the calcination;
the time for heat preservation is preferably 4-7 hours, more preferably 5 hours.
7. An artificial graphite negative electrode material, characterized in that it is produced by the method for producing an artificial graphite negative electrode material according to any one of claims 1 to 6.
8. Use of the artificial graphite negative electrode material of claim 7 in a lithium ion battery.
9. A negative electrode sheet comprising the artificial graphite negative electrode material according to claim 7;
preferably, the preparation method of the negative electrode plate comprises the following steps: uniformly stirring the artificial graphite negative electrode material, conductive carbon black SP, CMC and SBR in water to prepare negative electrode slurry, coating the negative electrode slurry on two sides of a copper foil by using a coater, and tabletting after vacuum drying;
preferably, the mass ratio of the artificial graphite negative electrode material, the conductive carbon black SP, the CMC, and the SBR is 95.6: 1.0: 1.1: 2.3;
preferably, the temperature of the vacuum drying is 110 ℃;
preferably, the vacuum drying time is 4 h.
10. A lithium ion battery comprising a negative electrode tab as claimed in claim 9;
preferably, the preparation method of the lithium ion battery comprises the following steps: 1mol/L LiPF6The solvent of the electrolyte is a three-component mixed solvent, the three-component mixed solvent is prepared by mixing ethyl carbonate, dimethyl carbonate and methyl ethyl carbonate according to the volume ratio of 1:1:1, and a metal lithium sheet is adopted as a positive electrode and is assembled with the negative electrode sheet in a glove box filled with argon.
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