CN111362260A - High-compaction graphite negative electrode material of lithium ion battery and preparation method of high-compaction graphite negative electrode material - Google Patents
High-compaction graphite negative electrode material of lithium ion battery and preparation method of high-compaction graphite negative electrode material Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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- H—ELECTRICITY
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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention discloses a high-compaction lithium ion battery graphite cathode material and a preparation method thereof, wherein the preparation method of the material comprises the following steps: (1) uniformly mixing needle-shaped coke powder, anthracite powder and a catalyst; the mass ratio of the needle-shaped coke powder to the anthracite powder is 80: 10-10: 85 parts by weight; (2) and (4) carrying out graphitization treatment. The high-compaction lithium ion battery graphite cathode material has the advantages of simple preparation process and low cost, and the compaction density is more than 1.80g/cm3(up to 1.89g/cm3) (ii) a The discharge capacity of the lithium ion battery prepared by the lithium ion battery is further improved to 369.5mAh/g, the first efficiency is more than 94%, and the capacity retention rate after 300 times of circulation can reach more than 90%.
Description
The invention relates to the technical field of lithium ion battery materials, in particular to a high-compaction lithium ion battery graphite negative electrode material and a preparation method thereof.
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. The mesocarbon microbead graphitized product is an excellent lithium ion battery cathode material, can be used as a cathode material of a lithium ion secondary battery, and has the characteristics of low potential, good flatness, high specific gravity, high initial charge-discharge efficiency, good processability and the like. Theoretically LiC6The reversible lithium storage capacity of the mesocarbon microbeads can reach 372mAh/g, but the reversible lithium storage capacity of the mesocarbon microbeads is only about 310mAh/g, and the energy density is low. The common artificial graphite powder has irregular shape and large specific surface area (usually more than 5 m)2/g) results in poor processability of the material, low first efficiency, relatively high ash content and difficulty in ensuring stable batches.
With the rapid development of the electronic information industry, the requirements of various products on miniaturization and light weight are continuously improved, and the requirements on high performance such as high capacity and rapid charging of lithium ion secondary batteries are increasingly urgent. The improvement of the capacity of the lithium ion battery mainly depends on the development and the perfection of a carbon negative electrode material, so that the improvement of the specific capacity of the negative electrode material of the lithium ion battery, the improvement of the compaction density of the material, the reduction of the first irreversible capacity and the improvement of the cycling stability are always the key points of research and development.
Therefore, in order to overcome the respective performance deficiencies of the mesocarbon microbeads and the common artificial graphite, the prior art modifies the mesocarbon microbeads or the artificial graphite. The literature: (1) the mesocarbon for the lithium ion battery is subjected to catalytic heat treatment and is reported in the Material research newspaper Vol.21 No.4P.404-408 (2007), so that the irreversible electrochemical reaction on the surface of the carbon is effectively relieved; (2) 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.
Chinese patent CN108550850A discloses a high-capacity high-compaction artificial graphite negative electrode material, a preparation method thereof, and a lithium ion battery, wherein the preparation method comprises: selecting at least two of asphalt coke, petroleum coke and needle coke as graphite raw materials, and uniformly mixing the graphite raw materials with a coating agent (the coating agent is petroleum asphalt or coal pitch) to obtain a mixture; and graphitizing the mixture at 3000-3300 ℃ in a protective atmosphere to obtain the composite material. The method uses two graphite raw materials, the required cost is high, the discharge capacity of the prepared product is not obviously improved, and the compaction density is low.
The method reported in the above documents has disadvantages that either the preparation process is complicated, or the added components are not easily obtained, or the product yield is not very significant, increasing the production cost.
Disclosure of Invention
The invention provides a high-compaction graphite cathode material for a lithium ion battery and a preparation method thereof, aiming at overcoming the defects of harsh preparation process conditions, high cost, low compaction density of prepared products, low electric capacity and poor cycle performance in the prior art.
The invention provides a preparation method of a high-compaction graphite cathode material of a lithium ion battery, which comprises the following steps:
(1) uniformly mixing needle-shaped coke powder, anthracite powder and a catalyst; the mass ratio of the needle-shaped coke powder to the anthracite powder is 80: 10-10: 85 parts by weight;
(2) and (4) carrying out graphitization treatment.
The anthracite powder in the step (2) can improve the capacity and the compaction density of the graphite cathode material, and improve the dynamic performance and the cycle performance; the catalyst can improve the graphitization degree of the raw material and catalyze the graphitization of the raw material.
Wherein the needle-like coke powder in the step (1) is oil-based needle-like coke powder or coal-based needle-like coke powder; the particle size D50 of the needle coke powder is 2-30 μm; the needle coke powder is obtained by crushing needle coke by a crusher.
Wherein the mixing in step (2) is performed in a mixer; adding half mass of needle coke powder into the mixer, adding half mass of anthracite powder while stirring, adding the other half mass of needle coke powder into the mixer while stirring, adding the other half mass of anthracite powder into the mixer while stirring, and finally adding the catalyst into the mixer while stirring;
the stirring temperature is normal temperature, and the normal temperature is 5-28 ℃; the stirring time is 1.5-2.5 h.
The mixer is a cantilever double-helix conical mixer.
The particle size D50 of the anthracite powder is 10-20 μm, preferably 15-20 μm.
The catalyst is one or the mixture of more than two of carbides of silicon, iron, tin or boron or oxides thereof.
The mass ratio of the needle coke powder to the anthracite powder to the catalyst is 80: 10: 10-10: 85: 5, preferably 50:10:10 to 10:80: 5.
The graphitization temperature is 2800-3200 ℃, and the graphitization time is 12-60 h.
The invention also provides a high-compaction lithium ion battery graphite cathode material prepared by the preparation method, and the performance parameters of the high-compaction lithium ion battery graphite cathode material are shown in the following table 1:
TABLE 1
The positive progress effects of the invention are as follows:
the preparation method of the invention can effectively solve the problems of the existing materials, wherein the processes of crushing, grading, mixing and graphitizing are simple and easy, and the raw materials have wide sources. The method of needle coke crushing pretreatment, anthracite powder mixing, catalyst adding catalytic graphitization high temperature treatment and the like is adopted, so that the prepared product has high compaction density, capacity exertion and good circulation.
It can be seen from this thatThe graphite cathode material of the invention effectively improves the compacted density and the discharge capacity, and the button cell prepared by the graphite cathode material has excellent comprehensive performance, mainly has the advantages of higher ① compacted density which can reach 1.80g/cm3The material has the advantages of good ② electrochemical performance, discharge capacity of more than 360mAh/g, high maintenance rate of a ③ discharge platform and the platform, good ④ high-current charge-discharge performance, good ⑤ cycle performance (300 cycles, capacity maintenance rate of more than or equal to 90%), good ⑥ safety (130 ℃/60 minutes, no explosion and no expansion), good adaptability of ⑦ to electrolyte and other additives, stable ⑧ product properties and almost no difference between batches.
Drawings
Fig. 1 is a first charge-discharge curve of the graphite negative electrode material of example 2 of the present invention.
Fig. 2 is a cycle curve of the graphite negative electrode material of example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto.
Example 1
Pulverizing needle coke in a pulverizing classifier to obtain needle coke powder F1 (D50 is 25.6 μm), mixing F1 material 20kg, anthracite powder (D50 is 15.2 μm)10kg, and catalyst (SiO 50 is 15.2 μm)2)1.6kg of graphite cathode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3000 ℃) treatment for 48 hours to prepare the graphite cathode material with half-cell capacity of 366.3mAh/g and first efficiency of 94.6 percent.
Example 2
Pulverizing needle coke in a pulverizing classifier to obtain needle coke powder F1 (D50 is 25.6 μm), mixing F1 material 15kg, anthracite powder (D50 is 19.9 μm)15kg, and catalyst (Fe)2O3)2.5kg of graphite cathode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is treated by catalytic graphitization (3200 ℃) for 48 hours, so that the graphite cathode material has the half-cell capacity of 367.1mAh/g and the primary efficiency of 94.4 percent.
Example 3
The needle coke is crushed and graded in a crushing and grading machine,needle-like coke powder F1 (D50 is 2.7 μm) is obtained, 10kg of F1, 20kg of anthracite powder (D50 is 15.2 μm) and catalyst (SnO)2)3.2kg of graphite cathode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is treated by catalytic graphitization (2800 ℃) for 48 hours, so that the graphite cathode material has the half-cell capacity of 365.9mAh/g and the primary efficiency of 94.7 percent.
Example 4
Pulverizing needle coke in a pulverizing classifier to obtain needle coke powder F1 (D50 is 29.7 μm), mixing F1 material 25kg, anthracite powder (D50 is 19.9 μm)5kg, and catalyst (B)2O3)3.2kg of graphite cathode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3000 ℃) treatment for 48 hours to prepare the graphite cathode material with half-cell capacity of 369.5mAh/g and first efficiency of 94.9 percent.
Example 5
Pulverizing needle coke in a pulverizing classifier to obtain needle coke powder F1 (D50 is 16.7 μm), mixing F1 3.3kg with anthracite powder (D50 is 10.4 μm)28kg, and catalyst (SiO 50 is 10.4 μm)2)3.2kg of graphite cathode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3000 ℃) treatment for 48 hours, so that the graphite cathode material is prepared, the half-cell capacity is 367.5mAh/g, and the primary efficiency is 94.9%.
Example 6
Pulverizing needle coke in a pulverizing classifier to obtain needle coke powder F1 (D50 is 25.6 μm), mixing F1 material 20kg, anthracite powder (D50 is 15.2 μm)10kg, and catalyst (SiO 50 is 15.2 μm)2)2kg of graphite anode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3000 ℃) treatment for 48 hours to prepare the graphite anode material, the half-cell capacity is 368.3mAh/g, and the first efficiency is 94.5%.
Example 7
Needle coke is crushed and graded in a crushing and grading machine to obtain needle coke powder F1 (D50 is 25.6 mu m), 20kg of F1 material, 10kg of anthracite (D50 is 10.4 mu m) and 2kg of catalyst (SiC) are alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then are subjected to catalytic graphitization (3000 ℃) for 48 hours to obtain the graphite cathode material, the capacity of a half cell is 360.7mAh/g, and the primary efficiency is 94.1%.
Example 8
Pulverizing needle coke in a pulverizing classifier to obtain needle coke powder F1 (D50 is 20.7 μm), mixing F1 material 28kg, anthracite powder (D50 is 19.9 μm)3.5kg, and catalyst (SiO 50 is 19.9 μm)2)2kg of graphite anode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3000 ℃) treatment for 48 hours to prepare the graphite anode material, the half-cell capacity is 369.1mAh/g, and the first efficiency is 94.6%.
Comparative example 1
Pulverizing needle coke in pulverizing classifier to obtain needle coke powder F1 (D50 is 20.7 μm), mixing F1 with catalyst (SiO 1 kg)2)2kg of the graphite powder is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3000 ℃) treatment for 48 hours to prepare the cathode material, the half-cell capacity is 335.0mAh/g, and the primary efficiency is 93.2%.
Comparative example 2
30kg of anthracite powder (D50 is 19.9 mu m) and 2kg of catalyst (SiC) are alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours, and then catalytic graphitization (3000 ℃) treatment is carried out for 48 hours to prepare the cathode material of the invention, the half-cell capacity is 356.3mAh/g, and the primary efficiency is 90.5%.
Comparative example 3
Needle coke is crushed and graded in a crushing and grading machine to obtain needle coke powder F1 (D50 is 25.6 mu m), 20kg of F1 material and 10kg of anthracite powder (D50 is 10.4 mu m) are alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then are subjected to conventional graphitization (2800 ℃) treatment for 48 hours to obtain the graphite cathode material, the capacity of a half cell is 343.2mAh/g, and the primary efficiency is 90.6%.
The raw materials in the above examples are all conventional commercial products.
The physical properties and electrochemical properties of the graphite anode materials of the above examples 1 to 8 and comparative examples 1 to 3 were measured by a conventional measurement method, wherein the electrochemical property measurement method comprises the following steps:
uniformly mixing a graphite sample, an N-methyl pyrrolidone solution containing 6-7% of polyvinylidene fluoride (PVDF) and 2% of conductive carbon black, 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 assembly was carried out in an argon-filled german braun glove box with an electrolyte of 1M LiPF6+ EC: DEC ═ 1: 1 (volume ratio), the metal lithium sheet is a counter electrode, the electrochemical performance test is carried out on a battery tester of ArbinBT2000 type U.S. the charging and discharging voltage range is 0.005-1.0V, and the charging and discharging rate is 0.1C.
The performance parameters of the examples and comparative examples are shown in table 2 below:
TABLE 2
As can be seen from the above data, comparative example 1 has a low discharge capacity of 335.0 mAh/g; comparative example 2 has a large specific surface area; comparative example 3 has a low discharge capacity of 343.2mAh/g and a low compacted density; the compacted density of the graphite cathode material prepared by the method is more than 1.80g/cm3The capacity can reach more than 360 mAh/g.
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 low specific surface area is beneficial to inhibiting the gas expansion phenomenon of the lithium ion battery system, and the safety performance of the battery is good; the overcharge performance is better; the pole piece has good processability; an ideal voltage platform, the discharge voltage can reach a steady state soon, as shown in fig. 1; the high-current performance is better; the cycle performance is good, and the capacity retention rate can reach more than 90% after 300 cycles, as shown in figure 2.
Claims (9)
1. A preparation method of a high-compaction lithium ion battery graphite cathode material is characterized by comprising the following steps:
(1) uniformly mixing needle-shaped coke powder, anthracite powder and a catalyst; the mass ratio of the needle-shaped coke powder to the anthracite powder is 80: 10-10: 85 parts by weight;
(2) and (4) carrying out graphitization treatment.
2. The method for preparing the highly compacted graphite anode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the needle-shaped coke powder is oil-based needle-shaped coke powder or coal-based needle-shaped coke powder; the particle size D50 of the needle coke powder is 2-30 μm.
3. The method for preparing the highly compacted graphite anode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the mixing is carried out in a mixer;
adding half mass of needle coke powder into the mixer, adding half mass of anthracite powder while stirring, adding the other half mass of needle coke powder into the mixer while stirring, adding the other half mass of anthracite powder into the mixer while stirring, and finally adding the catalyst into the mixer while stirring;
the stirring temperature is normal temperature, and the normal temperature is 5-28 ℃; the stirring time is 1.5-2.5 h.
4. The method for preparing the highly compacted graphite anode material for the lithium ion battery according to claim 3, wherein the method comprises the following steps: the mixer is a cantilever double-helix conical mixer.
5. The method for preparing the highly compacted graphite anode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the particle size D50 of the anthracite powder is 10-20 μm, preferably 15-20 μm.
6. The method for preparing the highly compacted graphite anode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the catalyst is one or the mixture of more than two of carbides of silicon, iron, tin or boron or oxides thereof.
7. The method for preparing the highly compacted graphite anode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the mass ratio of the needle coke powder to the anthracite powder to the catalyst is 80: 10: 10-10: 85: 5, preferably 50:10:10 to 10:80: 5.
8. The method for preparing the highly compacted graphite anode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the temperature of the graphitization treatment is 2800-3200 ℃, and the time of the graphitization treatment is 12-60 h.
9. The high-compaction lithium ion battery graphite negative electrode material prepared by the preparation method of any one of claims 1-8.
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