CN115806290A - Artificial graphite lithium ion battery cathode material and preparation method thereof - Google Patents
Artificial graphite lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
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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
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Abstract
The invention provides an artificial graphite lithium ion battery cathode material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Crushing petroleum coke or coal series coke to obtain a front end material; (2) Graphitizing the front-end material to obtain a graphitized material; (3) Mixing the graphitized material and the coating material, then carrying out carbonization treatment in an inert atmosphere, and then sieving to obtain a carbonized material; wherein, the coating material is at least one of resin or asphalt. In the preparation method, asphalt or resin is respectively used as a modifier to coat the surface of the artificial graphite in a carbonization stage, the asphalt or resin can coat a layer of amorphous carbon on the surface of the artificial graphite particles, the active end face of the graphite material is reduced, the graphite material is used as a negative electrode material of a lithium battery, solvent molecules and lithium ions can be prevented from being co-embedded between graphite layers, the structure of the inner layer graphite is protected, the electrochemical performance of the graphite material can be obviously improved, and the graphite material has the advantages of high initial discharge specific capacity, small specific surface area and smooth surface.
Description
Technical Field
The invention relates to the technical field of battery cathode materials, in particular to an artificial graphite lithium ion battery cathode material and a preparation method thereof.
Background
With the development of science and technology and the improvement of the living standard of human beings, fossil energy is largely consumed as a non-renewable resource; the rapid development of economy needs a large amount of energy as a support, and the use of fossil energy causes a series of problems such as greenhouse effect, air pollution and the like. Therefore, the consumption of searching and developing new renewable energy sources to replace non-renewable energy sources is urgent.
However, the lithium ion battery has the characteristics of high specific energy, good rate capability, high working voltage, good safety performance, environmental friendliness and the like, and is widely applied to electronic equipment (unmanned aerial vehicles and unmanned transport vehicles) and new energy vehicles. For a lithium ion battery, in the use process of the lithium ion battery, the expansion of a positive electrode material is small, and the expansion of a negative electrode material is large. The preparation of the cathode material is one of the very key technologies of the lithium ion battery, and the good and bad of the cathode material are directly related to the miniaturization and high capacity of the battery. Most of the current commercialized lithium ion batteries are made of graphite carbon materials; the artificial graphite occupies a large market share, but the artificial graphite used as the negative electrode material of the lithium ion battery has the following two problems: (1) The compatibility of the artificial graphite with the electrolyte is poor, organic solvents in the electrolyte can be embedded into the interlayer spacing of the graphite along with lithium ions, so that the graphite layer structure is peeled off, a new heterogeneous SEI film is continuously reformed and generated, an unstable situation occurs, and a large amount of lithium ions (Li) can be consumed by the thick SEI film + )，Resulting in poor coulombic efficiency, high impedance and fast capacity fade. (2) The artificial graphite has large Specific Surface Area (SSA), unsmooth surface, porosity and other factors, which cause the artificial graphite to form more electrolyte and solid electrolyte interface film (SEI film) during charging and discharging, which is also one of the key factors causing the loss of irreversible capacity and the deterioration of cycle performance of lithium batteries.
Therefore, in order to solve the problems of poor cycle performance, poor charge and discharge performance, easy detachment of graphite layers, and the like of artificial graphite, it is necessary to develop an artificial graphite lithium ion battery negative electrode material having good electrochemical performance.
Disclosure of Invention
In view of the above problems, the present invention aims to provide an artificial graphite lithium ion battery negative electrode material and a preparation method thereof, and the artificial graphite lithium ion battery negative electrode material has the advantages of high first discharge specific capacity, small specific surface area and smooth surface.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an artificial graphite lithium ion battery anode material, comprising the steps of:
(1) Crushing petroleum coke or coal series coke to obtain a front end material;
(2) Graphitizing the front-end material to obtain a graphitized material;
(3) Mixing the graphitized material with a coating material, then carrying out carbonization treatment in an inert atmosphere, and then sieving to obtain a carbonized material;
wherein, the coating material is at least one of resin or asphalt.
The artificial graphite lithium ion battery cathode material is prepared by taking petroleum coke or coal coke as a basic raw material, crushing the petroleum coke or coal coke as the basic raw material, graphitizing, carbonizing and sieving, wherein asphalt or resin is respectively used as a modifier to coat the surface of the artificial graphite in the carbonization stage, the asphalt or resin can coat a layer of amorphous carbon on the surface of artificial graphite particles to reduce the active end face of the graphite material, and the artificial graphite lithium ion battery cathode material can prevent solvent molecules and lithium ions from being co-embedded between graphite layers, has a protection effect on the structure of the inner graphite, can obviously improve the electrochemical performance of the artificial graphite lithium ion battery cathode material, and has the advantages of high first discharge specific capacity, small specific surface area and smooth surface.
In some embodiments, the method further comprises the step (4) of mixing the carbonized material with the lithium-containing polymer solution to obtain a liquid coating material, performing secondary carbonization treatment on the liquid coating material at 1000-1400 ℃ to obtain a secondary carbonized material, and mixing the lithium-containing polymer with water to obtain the lithium-containing polymer solution.
In some embodiments, the lithium-containing polymer is present in an amount of 1-6Wt% of both the graphitized material and the coating material mixture.
In some embodiments, the lithium-containing polymer is at least one of lithium polyacrylate, lithium polymethacrylate, lithium polymaleate, lithium polyfumarate.
In some embodiments of the present invention, the, the resin is at least one of epoxy resin, phenolic resin, amino phenolic resin, polyethylene resin, furan resin, polyamide resin and polystyrene.
In some embodiments, the mass ratio of the graphitized material to the cladding material is 98-70. .
In some embodiments, the graphitized material and the coating material mixture are heated at 400-1000 ℃ for 6-24 hours before being carbonized.
In some embodiments, the carbonization treatment is performed at a temperature of 600 ℃ to 1500 ℃ for 2 to 24 hours.
In some embodiments, the inert atmosphere is argon (Ar), nitrogen (N) 2 ) And helium (He).
Correspondingly, the invention also provides an artificial graphite lithium ion battery cathode material which is prepared by the preparation method of the artificial graphite lithium ion battery cathode material.
The invention has the following beneficial effects:
(1) The asphalt or resin can coat a layer of amorphous carbon on the surface of the artificial graphite particles, so that the active end faces of the graphite material are reduced, solvent molecules and lithium ions can be prevented from being co-embedded into the graphite layers, and the structure of the inner-layer graphite is protected;
(2) The coated amorphous carbon provides more lithium ion diffusion channels, the coating modification of the lithium-containing polymer can enhance the elastic artificial SEI film, and meanwhile, the lithium-containing polymer is an ion-conducting polymer and contains excessive lithium ions, so that the loss of lithium can be compensated to improve the first effect, and the electrochemical performance of the negative electrode can be effectively improved;
(3) The lithium-containing polymer coating layer can also inhibit the decomposition of electrolyte and prevent the attenuation of electrode capacity to a certain extent;
(4) The carbonization process reduces the specific surface area of the graphite, reduces pores, improves the tap density and enables the graphite surface to become smoother and more compact;
(5) The surface of the artificial graphite is modified to change the compatibility of the artificial graphite with electrolyte, so that a thin and compact SEI film is generated, and the stability of an electrode is ensured.
Drawings
FIG. 1 is an SEM photograph of a graphitized material in example 1 of the present invention.
FIG. 2 is an SEM photograph of a carbonized material in example 2 of the present invention.
FIG. 3 is an SEM photograph of a carbonized material in example 4 of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The preparation method of the artificial graphite lithium ion battery negative electrode material comprises the following steps:
(1) Crushing petroleum coke or coal series coke to obtain a front end material;
(2) Graphitizing the front-end material to obtain a graphitized material;
(3) Mixing the graphitized material and the coating material, then carrying out carbonization treatment in an inert atmosphere, and then sieving to obtain a carbonized material;
wherein, the coating material is at least one of resin or asphalt.
The artificial graphite lithium ion battery cathode material is prepared by taking petroleum coke or coal coke as a basic raw material, and performing crushing, graphitization treatment, carbonization treatment and sieving on the basic raw material. In the carbonization stage, asphalt or resin is respectively used as a modifier to coat the surface of the artificial graphite, the asphalt or the resin can coat a layer of amorphous carbon on the surface of the artificial graphite particles, the active end face of the graphite material is reduced, the graphite material is used as a negative electrode material of a lithium battery, solvent molecules and lithium ions can be prevented from being co-embedded into a graphite layer, the structure of the inner-layer graphite is protected, the electrochemical performance of the graphite material can be remarkably improved, and the graphite material has the advantages of high first discharge specific capacity, small specific surface area and smooth surface.
In some embodiments, the petroleum coke or coal-based coke is subjected to coarse crushing, and shaping to obtain a front end material. The coarse crushing, crushing and shaping treatment equipment can adopt one or more of but not limited to 150 type mechanical mill, 260 type mechanical mill, 500 type mechanical mill, crushing and shaping integrated machine and rolling mill. Further, the D50 of the front-end material is 5.5-10.5 μm; the D99 of the front-end material is less than or equal to 30 mu m.
In some embodiments, the graphitization treatment is performed using equipment including, but not limited to, a box furnace, an Acheson furnace, a continuous graphitization furnace. It should be understood that the graphitization treatment is performed in an inert gas, which may be, but is not limited to, argon (Ar), nitrogen (N) 2 ) And helium (He). Further, the temperature of the graphitization treatment is 2500 ℃ to 3500 ℃, and the graphitization treatment may be 2500 ℃, 2700 ℃, 2900 ℃, 3100 ℃, 3300 ℃, 3500 ℃, for example, but it is not limited to the numerical values listed, and other numerical values not listed in the above numerical value ranges are also applicable. Furthermore, the D50 of the graphitized material is 5.5-10.5 μm, and the D99 of the graphitized material is less than or equal to 20 μm.
In some embodiments, the mass ratio of the graphitized material to the coating material is 70-98, i.e. the mass ratio of the graphitized material to the coating material is 98-70. Further, the coating material is at least one of resin or asphalt. Specifically, the resin is at least one of an epoxy resin, a phenolic resin, an amino phenolic resin, a polyethylene resin, a furan resin, a polyamide resin, and polystyrene, but not limited thereto. In other embodiments, the asphalt is at least one of low-temperature coal-series asphalt, medium-temperature coal-series asphalt, high-temperature coal-series asphalt, and oil-series asphalt, but not limited thereto.
In some embodiments, the method further comprises the step (4) of mixing the carbonized material with the lithium-containing polymer solution to obtain a liquid coating material, and performing secondary carbonization treatment on the liquid coating material at 1000-1400 ℃ to obtain a secondary carbonized material, wherein the lithium-containing polymer is mixed with water to obtain the lithium-containing polymer solution. The lithium-containing polymer is an ion conductive polymer, contains excessive lithium ions, can make up for lithium loss to improve the first effect, and the coated amorphous carbon provides more lithium ion diffusion channels, the coating modification of the lithium-containing polymer can enhance the elastic artificial SEI film, thereby effectively improving the electrochemical performance of the negative electrode, and the lithium-containing polymer coating can also inhibit the decomposition of electrolyte and prevent the capacity attenuation of the electrode to a certain extent. In some embodiments, the carbonized material and the lithium-containing polymer solution are mixed and added into an evaporator for vacuum drying at 50-200 ℃ to prepare the liquid coating material. Further, the content of the lithium-containing polymer is 1 to 6Wt% of the two mixtures of the graphitized material and the coating material, and the content of the lithium-containing polymer may be, for example, 1Wt%, 2Wt%, 3Wt%, 4Wt%, 5Wt%, 6Wt%, but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable. Further, the lithium-containing polymer is at least one of lithium polyacrylate, lithium polymethacrylate, lithium polymaleate and lithium polyfumarate, and lithium polyacrylate is preferably used.
In some embodiments, the mixture of the graphitized material and the coating material is heated for 6-24 hours at 400-1000 ℃ before carbonization for discharging volatile components. Wherein, the heating treatment equipment can adopt but not limited to a horizontal kettle, a vertical kettle and a continuous kettle. Further, the heat treatment is performed in an inert atmosphere of argon (Ar) or nitrogen (N) 2 ) And helium (He).
In some embodiments, the carbonized material obtained by sieving has a D50 of 6-15 μm and Dmax ≦ 25 μm, and by way of example, but not limitation, a 500 mesh sieve may be used for sieving.
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific embodiments. It should be noted that the following implementation methods are further illustrative of the present invention and should not be construed as limiting the present invention.
Example 1
The method comprises the following steps of roughly crushing, crushing (mechanically grinding), shaping and graphitizing (continuously graphitizing furnace) 32 tons of petroleum coke raw materials, wherein the graphitizing temperature is 3000 ℃, a graphitized material is discharged from the furnace and screened by adopting a 500-mesh screen, and the screened material is marked as GMC. Wherein, the test results show that: the mean D50 value of the graphitized material GMC is 6.5 mu m, the mean Dmax value is 21.7 mu m, and the mean Tap value is 1.0g/cm 3 The Specific Surface Area (SSA) was 3.1m 2 G, compaction (PD) 1.7g/cm 3 。
And (3) electrochemical performance testing: the preparation method comprises the following steps of taking a graphitized material GMC as an active substance, carbon black (Super-P) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder, mixing and dispersing the three materials in deionized water according to a mass ratio of 91. The homogenate was uniformly coated on a copper foil using an automatic coater and placed in a forced air oven at 85 ℃ for drying for 2.0h. And taking out the dried pole piece, removing the position 3.0cm away from the tail part, cutting the pole piece with the length of 6.0cm, taking the middle part of the pole piece with the length of 2.5cm, and rolling the cut pole piece. The rolled pole pieces were cut into small disks with a microtome (Φ 12.0 mm). And weighing by using a one-tenth-ten-thousand balance, calculating the surface density of the rolled pole piece, and measuring the thickness of the cut pole piece by using a micrometer. And selecting the pole piece with the surface density and the compacted density meeting the requirements, and drying the pole piece in a forced air oven at 85 ℃ for 0.5h.
The invention is assembled with a button cell, the model is CR2430, and the button cell is assembled in a glove box in Ar atmosphere. Assembling a battery shell of the button cell CR2430, a lithium sheet, foam nickel, a diaphragm and the like in a certain sequence and standing for a period of time. Electrochemical performance of the button cell was tested using the wuhan blue electric test cabinet and the LAND cell test system, and the test results (specific capacity, first effect) are shown in table 1.
Example 2
2.0 tons of the graphitized material GMC prepared in example 1 and oil-based asphalt with a softening point of 200 ℃ (the average value of D50 is 3.0 μm, the coking value of the asphalt is 70%), are mixed and carbonized according to a mass ratio of 95.8. Wherein, the test results show that: the D50 mean value of the carbonized material TMC-1 is 8.3 mu m, the Dmax mean value is 56.5 mu m, and the Tap (Tap) mean value is 1.5g/cm 3 Specific Surface Area (SSA) of 1.0m 2 G, compaction (PD) 1.6g/cm 3 。
And (3) electrochemical performance testing: example 2 the procedure of the electrochemical performance test was identical to that of example 1, except that the active material GMC in example 1 was changed to TMC-1, and the electrochemical performance test of example 2 is shown in table 1.
Example 3
Mixing and carbonizing treatment are carried out on 2.0 tons of the graphitized material GMC prepared in the example 1 and phenolic resin with the softening point of 100 ℃ (the average value of D50 is 3.0 μm, the coking value of the phenolic resin is 10%) according to the mass ratio of 85 to 15 (the residual carbon content of the phenolic resin is about 1.5, the residual carbon content = the coking value multiplied by the asphalt adding proportion), the carbonized material is sieved by a 500-mesh sieve, and the sieved material is marked as TMC-2. Wherein, the test results show that: the D50 mean value of the carbonized material TMC-2 is 7.6 mu m, the Dmax mean value is 30.7 mu m, and the Tap mean value is 0.7g/cm 3 The Specific Surface Area (SSA) was 2.0m 2 G, compaction (PD) 1.7g/cm 3 。
And (3) electrochemical performance testing: example 3 the procedure for the electrochemical performance test was identical to that of example 1, except that the active material GMC in example 1 was changed to TMC-2, and the electrochemical performance test of example 3 is shown in table 1.
Example 4
2.0 tons of TMC-1 material obtained in example 2 and a solution containing 3Wt% of lithium polyacrylate were mechanically fused, and the fused material was added to an evaporator to be vacuum-dried at a temperature of 100 ℃ to obtain a liquid coating material. And (3) carrying out secondary carbonization treatment on the liquid coating material at 1200 ℃ to obtain a secondary carbonized material, sieving the secondary carbonized material by adopting a 500-mesh sieve, and marking the sieved material as TPMC-1. Wherein, the test results show that: the D50 mean value of the carbonized material TPMC-1 is 8.1 mu m, the Dmax mean value is 27.6 mu m, and the Tap mean value is 1.6g/cm 3 Specific Surface Area (SSA) of 1.1m 2 G, compaction (PD) 1.7g/cm 3 。
And (3) electrochemical performance testing: example 4 the procedure for the electrochemical performance test was identical to that of example 1, except that the active material TMC-1 in example 1 was changed to TPMC-1, and the electrochemical performance test of example 4 was as shown in table 1.
Example 5
Mixing and carbonizing treatment are carried out on 2.0 tons of graphite material GMC prepared in example 1 and phenolic resin with the softening point of 100 ℃ (the average value of D50 is 3.0 μm, the coking value of the phenolic resin is 10%) according to a mass ratio of 80. Wherein, the test results show that: the D50 mean value of the carbonized material TMC-3 is 8.3 mu m, the Dmax mean value is 31.1 mu m, and the Tap mean value is 0.8g/cm 3 Specific Surface Area (SSA) of 1.9m 2 G, compaction (PD) 1.7g/cm 3 。
And (3) electrochemical performance testing: example 5 the procedure of the electrochemical performance test was identical to that of example 1, except that the active material GMC in example 1 was changed to TMC-3, and the electrochemical performance test of example 5 is shown in table 1.
Example 6
2.0 tons of the graphite material GMC obtained in example 1 was mixed with a phenol resin having a softening point of 100 ℃ (the average value of D50 is 3.0 μm, and the coking value of the phenol resin is 10%) in a mass ratio of 75And (4) treating, sieving the carbonized material by using a 500-mesh sieve, and marking the sieved material as TMC-4. Wherein, the test results show that: the D50 mean value of the carbonized material TMC-4 is 9.1 mu m, the Dmax mean value is 31.3 mu m, and the Tap mean value is 0.9g/cm 3 Specific Surface Area (SSA) of 1.7m 2 G, compaction (PD) 1.6g/cm 3 。
And (3) electrochemical performance testing: the procedure of the electrochemical performance test of example 6 was identical to that of example 1, except that the active material GMC in example 1 was changed to TMC-4, and the electrochemical performance test of example 6 is shown in table 1.
Example 7
Mixing and carbonizing treatment are carried out on 2.0 tons of graphite material GMC prepared in example 1 and phenolic resin with the softening point of 100 ℃ (the average value of D50 is 3.0 μm, the coking value of the phenolic resin is 10%) according to a mass ratio of 70. Wherein, the test results show that: the D50 mean value of the carbonized material TMC-5 is 9.8 mu m, the Dmax mean value is 32.2 mu m, and the Tap (Tap) mean value is 1.0g/cm 3 Specific Surface Area (SSA) of 1.5m 2 G, compaction (PD) 1.6g/cm 3 。
And (3) electrochemical performance testing: example 6 the procedure of the electrochemical performance test was identical to that of example 1, except that the active material GMC in example 1 was changed to TMC-5, and the electrochemical performance test of example 6 is shown in table 1.
Example 8
2.0 tons of TMC-2 material prepared in example 3 and a solution containing 3.0Wt% of lithium polyacrylate were mechanically fused, and the fused material was added to an evaporator to be vacuum-dried at a temperature of 100 ℃ to obtain a liquid coating material. And (3) carrying out secondary carbonization treatment on the liquid coating material at 1200 ℃ to obtain a secondary carbonized material, sieving the secondary carbonized material by adopting a 500-mesh sieve, and marking the sieved material as TPMC-2. Wherein, the test results show that: the D50 mean value of the carbonized material TPMC-2 is 8.5 mu m, the Dmax mean value is 33.1 mu m, and the Tap mean value is 1.1g/cm 3 Specific Surface Area (SSA) of 1.7m 2 Per g, compaction (PD) 1.6g/cm 3 。
And (3) electrochemical performance testing: example 8 the procedure for the electrochemical performance test was identical to that of example 1, except that the active material TMC-1 in example 1 was changed to TPMC-2, and the electrochemical performance test of example 8 is shown in table 1.
Table 1 performance parameter test results
As can be seen from the data in Table 1, in the example 1 of the present invention, the petroleum coke is subjected to coarse crushing, shaping and graphitization, the first discharge specific capacity of the graphitization material is 348.7mAh/g, and the first efficiency (ICE) is 92.5%. Example 2 is TMC-1 which is the material obtained by carbonizing the graphitized material and the coating material oil-based asphalt in example 1. From comparison between example 2 and example 1, the first discharge specific capacity of the oil-based asphalt-coated carbonized graphitized material is increased from 348.7mAh/g to 354.0mAh/g, and the first efficiency (ICE) is increased from 92.5% to 93.5%; next, the Specific Surface Area (SSA) of the graphitized material of example 1 is from 3.1m 2 The/g is reduced to 1.0m 2 (ii)/g, tap density (Tap) from 1.0g/cm 3 Increased to 1.5g/cm 3 . Therefore, the surface of the graphitized material in the embodiment 1 is modified by carbonization coating with the asphalt, so that the electrochemical performance of the artificial graphite is well improved, and the specific surface area is small.
Example 3 is TMC-2 which is the material obtained by carbonizing the graphite material GMC and the coating material phenolic resin in example 1. From the comparison between the example 3 and the example 1, the first discharge specific capacity of the graphitized material coated and carbonized by the phenolic resin is increased from 348.7mAh/g to 350.2mAh/g, and the Specific Surface Area (SSA) is increased from 3.1m 2 The/g is reduced to 2.0m 2 The electrochemical performance of the artificial graphite is improved.
Comparing the data of examples 1-3, it can be seen that the electrochemical properties of the same raw material graphite material after carbonization coating modification by using oil-based asphalt and phenolic resin are slightly different, and the difference in physical index performance is large, mainly in terms of Specific Surface Area (SSA) and Tap density (Tap). Further, comparing example 2 and example 3, it is clear that the effect of the oil-based asphalt on the reduction of the Specific Surface Area (SSA) of the GMC material after coating modification is more significant. Similarly, the effect of the oil-based asphalt on increasing the Tap density (Tap) of the GMC material after coating and modification is obvious. The result may be related to the type of coating agent and the composition of the coating agent. Generally, there are many small molecular substances in the phenolic resin, and these small molecular substances will overflow from the surface of the artificial graphite in a large amount during carbonization and heating, so that the surface of the artificial graphite has a large number of pore structures, and therefore, the effect of reducing the specific surface area of the phenolic resin coated and modified artificial graphite may be inferior to that of the oil-based asphalt coated and modified artificial graphite.
Comparing the data of example 2 and example 4, it can be seen that the electrochemical performance of the coated lithium polyacrylate obtained from example 4 is significantly improved, the specific capacity is increased from 354mAh/g to 357.3mAh/g, and the Specific Surface Area (SSA) is not changed much. The reason may be that the lithium-containing polymer is an ion-conducting polymer, contains excessive lithium ions, can compensate for lithium loss to improve the first effect, and the coated amorphous carbon provides more lithium ion diffusion channels, and the coating modification of the lithium-containing polymer can enhance the elastic artificial SEI film, thereby effectively improving the electrochemical performance of the negative electrode.
As can be seen from the comparison between example 3 and examples 5 to 7, the Specific Surface Area (SSA) increased from 2.0m as the coating amount of the phenolic resin increased from 15% to 30% 2 The/g is reduced to 1.5m 2 (ii)/g, tap density (Tap) from 0.7g/cm 3 Increased to 1.0g/cm 3 The capacity increased from 350.2mAh/g to 353.3mAh/g.
In example 4, the same content of lithium polyacrylate was coated on different coated carbonized materials, and the first capacity was improved by coating a layer of lithium polyacrylate on graphite after coating and carbonizing asphalt (or phenolic resin) as compared with example 8. The effect of first capacity improvement of coating a layer of lithium polyacrylate on the graphite after asphalt coating carbonization is obvious, the first capacity is improved from 354mAh/g to 357.3mAh/g, the first effect is improved from 93.5% to 95.4%, and the specific surface area is basically unchanged. Therefore, the coating modification of the artificial graphite by the asphalt and the lithium polyacrylate is more beneficial to improving the electrochemical performance.
Fig. 1, 2 and 3 show Scanning Electron Micrographs (SEM) of the graphitized material in example 1, the carbonized material in example 2 and the secondary carbonized material in example 4, respectively. Comparing fig. 1 and fig. 2, it can be seen that the surface of the artificial graphite becomes smooth and the pores are reduced after the pitch-coated carbonization is performed on the surface of the graphitized material GMC. As can be seen from a comparison of fig. 2 and 3, the surface of the artificial graphite becomes smoother and the pores are greatly reduced after the secondary coating lithium polyacrylate is carbonized.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the artificial graphite lithium ion battery cathode material is characterized by comprising the following steps:
(1) Crushing petroleum coke or coal series coke to obtain a front end material;
(2) Graphitizing the front-end material to obtain a graphitized material;
(3) Mixing the graphitized material with a coating material, then carrying out carbonization treatment in an inert atmosphere, and then sieving to obtain a carbonized material;
wherein, the coating material is at least one of resin or asphalt.
2. The preparation method of the artificial graphite lithium ion battery negative electrode material according to claim 1, further comprising the step (4): mixing the carbonized material with the lithium-containing polymer solution to obtain a liquid-state coating material, carrying out secondary carbonization treatment on the liquid-state coating material at 1000-1400 ℃ to obtain a secondary carbonized material, and mixing the lithium-containing polymer with water to obtain the lithium-containing polymer solution.
3. The method for preparing artificial graphite lithium ion battery negative electrode material according to claim 2, wherein the content of the lithium-containing polymer is 1-6Wt% of the two mixtures of the graphitized material and the coating material.
4. The method for preparing artificial graphite lithium ion battery negative electrode material according to claim 2, wherein the lithium-containing polymer is at least one of lithium polyacrylate, lithium polymethacrylate, lithium polymaleate and lithium polyfumarate.
5. The method for preparing artificial graphite lithium ion battery negative electrode material according to claim 1, wherein the resin is at least one of epoxy resin, phenolic resin, amino phenolic resin, polyethylene resin, furan resin, polyamide resin and polystyrene.
6. The preparation method of the artificial graphite lithium ion battery negative electrode material as claimed in claim 1, wherein the mass ratio of the graphitized material to the coating material is 98-70.
7. The method for preparing artificial graphite lithium ion battery cathode material according to claim 1, wherein the graphitized material and the coating material mixture are heated at 400-1000 ℃ for 6-24h before the carbonization treatment.
8. The preparation method of the artificial graphite lithium ion battery cathode material as claimed in claim 1, wherein the carbonization treatment temperature is 600-1500 ℃ and the time is 2-24h.
9. The method for preparing artificial graphite lithium ion battery anode material according to claim 1, wherein the inert atmosphere is at least one of argon, nitrogen and helium.
10. The artificial graphite lithium ion battery negative electrode material is characterized by being prepared by the preparation method of the artificial graphite lithium ion battery negative electrode material as claimed in any one of claims 1 to 9.
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