CN109546099B - Graphite composite negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Graphite composite negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- 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
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- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention relates to a graphite composite negative electrode material, a preparation method thereof and a lithium ion battery, and belongs to the field of lithium ion battery materials. The preparation method of the graphite composite negative electrode material comprises the following steps: (1) reacting a solution containing titanium and tin, graphite and a nitrogen source at the temperature of 120-200 ℃ for 6-24 hours, then carrying out solid-liquid separation, and drying to obtain a titanium/tin-doped graphite composite material; the nitrogen source is one of aniline, thiophene, pyrrole and urea; (2) and (2) under the mixed atmosphere of carbon source gas and ammonia gas, preserving the heat of the titanium/tin-doped graphite composite material at the temperature of 400-500 ℃ for 1-3 h, then preserving the heat at the temperature of 800-900 ℃ for 1-3 h, and then cooling to obtain the graphite composite negative electrode material. When the graphite composite negative electrode material prepared by the invention is used for a lithium ion battery, the lithium ion battery has better quick charge performance and cycle performance.
Description
Technical Field
The invention relates to a graphite composite negative electrode material, a preparation method thereof and a lithium ion battery, and belongs to the field of lithium ion battery materials.
Background
In recent years, people have increasingly seen the demand for pure electric vehicles and hybrid electric vehicles, and the demand for power batteries is also increased. However, the current lithium ion battery cannot fully meet the requirements of new energy automobiles due to the long charging time and low energy density. Therefore, further improvement in power characteristics and energy density of lithium ion batteries is desired. Graphite is the most common cathode material of lithium ion batteries, and has the advantages of high energy density, low voltage, good conductivity, abundant resources, low price and the like. However, the layered structure of graphite causes a low diffusion rate of lithium ions and poor rate capability. And lithium ions are easy to deposit on the surface of graphite to form lithium dendrite during rapid charging, which causes serious potential safety hazard. At present, modification of graphite is a common method for improving the performance of graphite materials.
The application publication number of CN104282896A discloses a nitrogen-doped coated graphite cathode material and a preparation method thereof. The method comprises the steps of uniformly coating the ionic liquid on the outer surface of graphite to form a core-shell structure, and then carbonizing to obtain the nitrogen-doped coated graphite cathode material. The chinese patent application with application publication No. CN104966821A discloses a method for preparing a tin-nickel doped graphite negative electrode material. The modification methods do not influence the lattice structure of the graphite, so that the improvement range of the quick charging performance of the graphite material is limited.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a graphite composite negative electrode material, which can improve the quick charging performance of the graphite material.
The second object of the present invention is to provide a graphite composite anode material prepared by the above method for preparing a graphite composite anode material.
The third purpose of the invention is to provide a lithium ion battery, and the lithium ion battery negative electrode comprises the graphite composite negative electrode material. The lithium ion battery has the advantages of high charging speed and good cycle performance.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a graphite composite negative electrode material comprises the following steps:
(1) reacting a solution containing titanium and tin, graphite and a nitrogen source at the temperature of 120-200 ℃ for 6-24 hours, then carrying out solid-liquid separation, and drying to obtain a titanium/tin-doped graphite composite material; the nitrogen source is one of aniline, thiophene, pyrrole and urea;
(2) and (2) under the mixed atmosphere of carbon source gas and ammonia gas, preserving the heat of the titanium/tin-doped graphite composite material at the temperature of 400-500 ℃ for 1-3 h, then preserving the heat at the temperature of 800-900 ℃ for 1-3 h, and then cooling to obtain the graphite composite negative electrode material.
The solution containing titanium and tin in the step (1) is a mixed solution of titanium-containing turbid liquid and tin-containing solution, and the pH value of the mixed solution is 8-10.
The titanium-containing turbid liquid is obtained by dissolving tetrabutyl titanate in an ethylene glycol solution. Wherein the mass concentration of ethylene glycol in the ethylene glycol solution is 1-20%, and the ratio of the tetrabutyl titanate to the ethylene glycol solution is 1-2 g: 50-100 mL.
The tin-containing solution is obtained by adding tin dioxide into mixed acid of hydrochloric acid and ethylene diamine tetraacetic acid solution. The ratio of the tin dioxide to the hydrochloric acid to the ethylenediamine tetraacetic acid solution is 2-4 g: 50-100 mL: 150-300 mL. Wherein the concentration of the hydrochloric acid is 36 percent, and the concentration of the ethylene diamine tetraacetic acid solution is 0.1-0.5 g/L.
In the step (1), the mass ratio of the nitrogen source to the graphite is 5-10: 100.
the graphite used in the step (1) is one of natural graphite, artificial graphite and mesocarbon microbeads, and the particle size D50 is less than or equal to 5 mu m.
And (3) the carbon source gas in the step (2) is one of methane, ethane, acetylene and ethylene.
The volume ratio of the carbon source gas to the ammonia gas in the step (2) is 5-10: 1.
and (3) cooling in the step (2) to room temperature in an inert atmosphere.
According to the preparation method, the Ti element and the Sn element are doped in the graphite by a hydrothermal method, so that the interlayer spacing of the graphite material can be improved. Meanwhile, as the Ti element and the Sn element are doped in the graphite lattice structure, the diffusion channel of the lithium ions is expanded, and the diffusion resistance of the lithium ions is reduced, so that the diffusion speed of the lithium ions is improved, and the quick charge performance of the lithium ion battery is improved.
The titanium-doped graphite is used for catalyzing graphitization of the graphite material, improving the graphitization degree of the material, reducing the crystallinity and irreversible capacity of the material and improving the structural stability of the material; on the other hand, titanium carbide formed of titanium and carbon has a metal-like compound, and is low in resistivity, which contributes to improvement in conductivity of the material. Meanwhile, the titanium has high structural stability and is easy to embed lithium ions, so that the diffusion speed of the material is improved.
The surface of graphite in the graphite composite material prepared by the preparation method is coated with the nitrogen-doped carbon material, the coating layer is uniform and compact, the defects on the surface of the graphite material are reduced, and the growth of lithium dendrite is effectively avoided. The doping of nitrogen element makes the graphite material have higher electron conductivity compared with the pure carbon material.
The technical scheme adopted by the graphite composite negative electrode material is as follows:
a graphite composite negative electrode material prepared by the preparation method of the graphite composite negative electrode material.
The graphite composite negative electrode material has high conductivity.
The technical scheme adopted by the lithium ion battery is as follows:
a lithium ion battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the negative electrode comprises a graphite material, and the graphite material is the graphite composite negative electrode material.
The lithium ion battery has better quick charge performance and cycle performance.
Drawings
Fig. 1 is an SEM image of the graphite composite anode material of example 2.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The tetrabutyl titanate, the ethylene glycol, the tin dioxide, the hydrochloric acid and the like which are referred to in the following examples are all conventional products on the market.
Example 1
The preparation method of the graphite composite anode material of the embodiment comprises the following steps:
(1) dissolving 1.5g of tetrabutyl titanate in 80mL of ethylene glycol solution (the mass concentration of ethylene glycol is 10%) to form titanium-containing turbid solution; adding 3g of stannic oxide into a mixed acid of 80mL of hydrochloric acid (the concentration is 36%) and 200mL of ethylenediamine tetraacetic acid solution (the concentration of the ethylenediamine tetraacetic acid is 0.2g/L) to obtain a stannic solution; then adding the titanium-containing turbid solution into the tin-containing solution, uniformly stirring, and introducing ammonia gas to adjust the pH value of the solution to 9 to obtain a titanium-and tin-containing solution; then transferring the solution containing titanium and tin into a high-pressure reaction kettle, adding 8g of aniline and 100g of artificial graphite, reacting at 180 ℃ for 12 hours, filtering, and drying in vacuum to obtain the titanium/tin-doped graphite composite material;
(2) and then transferring the titanium/tin-doped graphite composite material into a tubular furnace, firstly introducing argon gas to exhaust air in the tube, then introducing methane gas and ammonia gas (the volume ratio is 8: 1), heating to 450 ℃, keeping the temperature for 2h, then heating to 850 ℃, keeping the temperature for 2h, then stopping introducing the methane gas and the ammonia gas, introducing the argon gas, and naturally cooling to room temperature to obtain the graphite composite negative electrode material.
Example 2
The graphite composite anode material of the present example was prepared by the preparation method of example 1. As can be seen from FIG. 1, the graphite composite negative electrode material of the present embodiment has a spherical structure, and the particle size is between 5 μm and 20 μm.
Example 3
The preparation method of the graphite composite anode material of the embodiment comprises the following steps:
(1) dissolving 1g of tetrabutyl titanate in 50mL of ethylene glycol solution (the mass concentration of ethylene glycol is 1%) to form titanium-containing turbid liquid; adding 2g of stannic oxide into a mixed acid of 50mL of hydrochloric acid (the concentration is 36%) and 150mL of ethylenediamine tetraacetic acid solution (the concentration of the ethylenediamine tetraacetic acid is 0.5g/L) to obtain a stannic solution; then adding the titanium-containing turbid solution into the tin-containing solution, uniformly stirring, and introducing ammonia gas to adjust the pH value of the solution to 10 to obtain a titanium-and tin-containing solution; then transferring the solution containing titanium and tin into a high-pressure reaction kettle, adding 5g of pyrrole and 100g of artificial graphite, reacting for 12 hours at the temperature of 120 ℃, filtering, and drying in vacuum to obtain the titanium/tin-doped graphite composite material;
(2) transferring the titanium/tin-doped graphite composite material into a tubular furnace, firstly introducing argon gas to exhaust air in the tube, then introducing methane gas and ammonia gas (the volume ratio is 5: 1), heating to 400 ℃, keeping the temperature for 3h, then heating to 800 ℃, keeping the temperature for 3h, then stopping introducing the methane gas and the ammonia gas, introducing the argon gas, and naturally cooling to room temperature to obtain the graphite composite negative electrode material.
Example 4
The graphite composite anode material of the present example was prepared by the preparation method of example 3.
Example 5
The preparation method of the graphite composite anode material of the embodiment comprises the following steps:
(1) dissolving 2g of tetrabutyl titanate in 100mL of ethylene glycol solution (the mass concentration of ethylene glycol is 20%) to form titanium-containing turbid solution; adding 4g of stannic oxide into a mixed acid of 100mL of hydrochloric acid (the concentration is 36%) and 300mL of ethylenediamine tetraacetic acid solution (the concentration of the ethylenediamine tetraacetic acid is 0.1g/L) to obtain a stannic solution; then adding the titanium-containing turbid solution into the tin-containing solution, uniformly stirring, and introducing ammonia gas to adjust the pH value of the solution to 10 to obtain a titanium-and tin-containing solution; then transferring the solution containing titanium and tin into a high-pressure reaction kettle, adding 10g of urea and 100g of artificial graphite, reacting for 6 hours at the temperature of 200 ℃, filtering and drying to obtain the titanium/tin-doped graphite composite material;
(2) transferring the titanium/tin-doped graphite composite material into a tubular furnace, firstly introducing argon gas to exhaust air in the tube, then introducing methane gas and ammonia gas (the volume ratio is 10: 1), heating to 500 ℃, keeping the temperature for 1h, then heating to 900 ℃, keeping the temperature for 1h, then stopping introducing the methane gas and the ammonia gas, introducing the argon gas, and naturally cooling to room temperature to obtain the graphite composite negative electrode material.
Example 6
The graphite composite anode material of the present example was prepared by the preparation method of example 5.
Example 7
The lithium ion battery of the embodiment is a button cell battery, comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, and is assembled in a hydrogen-filled glove box. The positive electrode is a metal lithium sheet, the diaphragm is a polyethylene and polypropylene composite film, and the electrolyte is LiPF6The volume ratio of EC to DEC is 1: 1, and the negative pole piece is a graphite negative pole piece.
The graphite negative pole piece is prepared by mixing the graphite composite negative pole material of the embodiment 2 as a negative pole material, a binder LA132, a conductive agent SP and secondary distilled water into slurry, coating the slurry on a copper foil, and drying and rolling the copper foil. Wherein the proportion of the graphite composite negative electrode material, LA132, SP and secondary distilled water is 95 g: 4 g: 1 g: 220 mL.
Example 8
The negative electrode plate of the present example was prepared according to the preparation method of the graphite negative electrode plate described in example 7, using the graphite composite negative electrode material of example 4 as a negative electrode material.
The lithium ion battery of this example was prepared according to the battery preparation method described in example 7, with the negative electrode sheet of this example as the negative electrode.
Example 9
The negative electrode plate of the present example was prepared according to the preparation method of the graphite negative electrode plate described in example 7, using the graphite composite negative electrode material of example 6 as a negative electrode material.
The lithium ion battery of this example was prepared according to the battery preparation method described in example 7, with the negative electrode sheet of this example as the negative electrode.
Example 10
The lithium ion battery of the embodiment is a 2Ah soft package battery and comprises a positive electrode, a negative electrode, electrolyte and a diaphragm. The anode is a ternary material LiNi1/3Co1/3Mn1/3O2The electrolyte is LiPF with the concentration of 1.3mol/L6A solution of/EC + DEC (EC to DEC volume ratio of 1: 1) with a membrane of celegard 2400. The negative electrode plates are respectively composed of
The graphite composite negative electrode materials of examples 2, 4 and 6, the binder LA132, the conductive agent SP and the secondary distilled water were mixed into a slurry, and then coated on a copper foil, and the slurry was prepared by drying and rolling. Wherein the proportion of the graphite negative electrode material, LA132, SP and secondary distilled water is 95 g: 4 g: 1 g: 220 mL.
Batteries prepared with the graphite composite negative electrode materials of examples 2, 4, and 6 as negative electrode sheets of the negative electrode materials are labeled C1, C2, C3, respectively.
Comparative example 1
The graphite cathode material of the comparative example is artificial graphite which is purchased in the market and has the model of FSN-1, and the manufacturer is Jiangxi purple light control science and technology company Limited.
Comparative example 2
The negative electrode plate of the present comparative example was prepared according to the preparation method of the graphite negative electrode plate described in example 7, using the artificial graphite in comparative example 1 as the negative electrode material.
The lithium ion battery of the comparative example was prepared according to the battery preparation method described in example 7, using the negative electrode sheet of the comparative example as the negative electrode.
Comparative example 3
In this comparative example, a soft-packed lithium ion battery, labeled D, was prepared according to the battery preparation method of example 10 using the artificial graphite of comparative example 1 as the negative electrode material.
Test example 1
Specific surface area tests were performed on the graphite composite anode materials of examples 2, 4 and 6 and the graphite anode material of comparative example 1. The test results are shown in table 1.
TABLE 1 specific surface area test results
| Item | Specific surface area (m)2/g) |
| Example 2 | 11.2 |
| Example 4 | 10.9 |
| Example 6 | 10.1 |
| Comparative example 1 | 1.5 |
As can be seen from Table 1, the graphite material prepared by the present invention has a large number of pore structures and large interlayer spacing.
Test example 2
And (3) carrying out liquid absorption and retention capability test on the graphite negative pole pieces in the examples 7-9 and the comparative example 2. The test results are shown in table 2.
The specific test method for the imbibition speed is as follows: in the glove box, 1cm by 1cm negative pole piece is selected, electrolyte is absorbed by a burette and titrated on the pole piece until the electrolyte does not have obvious electrolyte on the surface of the pole piece, time and the titration amount of the electrolyte are recorded, and the titration amount/time is the imbibing speed.
The specific test method of the liquid retention rate is as follows: and (3) calculating a theoretical liquid injection amount m1 according to the pole piece parameters, then placing the pole piece into the electrolyte with the theoretical amount m1, placing for 24 hours, weighing the electrolyte m2 absorbed by the pole piece, and finally obtaining the liquid retention rate which is (m2/m1) × 100%.
TABLE 2 liquid absorption and retention capability test results
| Item | Imbibition speed (mL/min) | Liquid retention rate |
| Example 7 | 7.8 | 94.1％ |
| Example 8 | 7.6 | 93.3％ |
| Example 9 | 7.5 | 93.2％ |
| Comparative example 2 | 4.2 | 83.1％ |
As can be seen from table 2, the liquid absorbing ability of the negative electrode sheet prepared from the graphite material of the present invention is significantly better than that of the artificial graphite in the comparative example, because the graphite material of the present invention has a porous structure and a high specific surface area, the liquid absorbing and retaining ability of the material is improved.
Test example 3
The lithium ion batteries prepared in examples 7 to 9 and comparative example 2 were subjected to an electrical property test. The electrical performance tester is a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.005V to 2.0V, and the charging and discharging speed is 0.1C. The test results are shown in table 3.
TABLE 3 Electrical Properties of lithium ion batteries
As can be seen from table 3, the lithium ion battery using the graphite negative electrode material of the present invention as the negative electrode has a high first discharge capacity and a good first charge-discharge efficiency.
Test example 4
Rate performance tests were performed on pouch cells C1, C2, and C3 of example 10 and pouch cell D of comparative example 3 under the following test conditions: the charging and discharging voltage range is 2.75-4.2V, the temperature is 25 +/-3.0 ℃, charging is carried out at 0.5C, 1.0C, 5.0C, 10.0C and 2.0C, and discharging is carried out at 0.5C. The test results are shown in table 4.
TABLE 4 Rate Performance test results
In the actual charging process, the charging time is influenced by factors such as the interlayer spacing of graphite, the speed of lithium ions entering the graphite interlayer, the surface structure of the negative electrode material and the like. As can be seen from table 4, compared with the comparative example, the soft-package battery using the negative electrode sheet prepared from the graphite negative electrode material of the present invention as the negative electrode has a good rate performance, a short charging time during high rate charging, and a good quick charging effect.
Test example 5
The pouch cells C1, C2 and C3 of example 10 and the pouch cell D prepared in comparative example 3 were subjected to a cycle performance test under the following test conditions: the charging and discharging current is 2C, and the voltage range is 3.0-4.2V. The test results are shown in table 5.
TABLE 5 results of the cycle performance test
As can be seen from table 5, the soft package battery using the negative electrode sheet prepared from the graphite negative electrode material of the present invention as the negative electrode has a good cycle performance, and the battery capacity retention rate is still maintained above 98% after 200 cycles.
Claims (10)
1. A preparation method of a graphite composite negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) carrying out hydrothermal reaction on a solution containing titanium and tin, graphite and a nitrogen source at the temperature of 120-200 ℃ for 6-24 h, then carrying out solid-liquid separation, and drying to obtain a titanium/tin-doped graphite composite material; the nitrogen source is one of aniline, thiophene, pyrrole and urea;
(2) and (2) under the mixed atmosphere of carbon source gas and ammonia gas, preserving the heat of the titanium/tin-doped graphite composite material at the temperature of 400-500 ℃ for 1-3 h, then preserving the heat at the temperature of 800-900 ℃ for 1-3 h, and then cooling to obtain the graphite composite negative electrode material.
2. The method for preparing the graphite composite anode material according to claim 1, characterized in that: the solution containing titanium and tin in the step (1) is a mixed solution of titanium-containing turbid liquid and tin-containing solution.
3. The method for preparing the graphite composite anode material according to claim 2, characterized in that: the titanium-containing turbid liquid is obtained by dissolving tetrabutyl titanate in an ethylene glycol solution.
4. The method for preparing the graphite composite anode material according to claim 3, characterized in that: the ratio of the tetrabutyl titanate to the glycol solution is 1-2 g: 50-100 mL.
5. The method for preparing the graphite composite anode material according to claim 2, characterized in that: the tin-containing solution is obtained by adding tin dioxide into mixed acid of hydrochloric acid and ethylene diamine tetraacetic acid solution.
6. The method for preparing the graphite composite anode material according to claim 5, characterized in that: the ratio of the tin dioxide to the hydrochloric acid to the ethylenediamine tetraacetic acid solution is 2-4 g: 50-100 mL: 150-300 mL.
7. The method for preparing the graphite composite anode material according to claim 1, characterized in that: in the step (2), the carbon source gas is one of methane, ethane, acetylene and ethylene.
8. The method for preparing the graphite composite anode material according to any one of claims 1 to 7, characterized in that: in the step (2), the volume ratio of the carbon source gas to the ammonia gas is 5-10: 1.
9. a graphite composite negative electrode material is characterized in that: the graphite composite negative electrode material is prepared by the preparation method of the graphite composite negative electrode material in claim 1.
10. A lithium ion battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, and is characterized in that: the negative electrode comprises a graphite material, and the graphite material is the graphite composite negative electrode material of claim 9.
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| CN114068886A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modified graphite material and preparation method and application thereof |
| CN114122392B (en) * | 2021-11-10 | 2024-03-29 | 云南中晟新材料有限责任公司 | High-capacity quick-charging graphite composite material and preparation method thereof |
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Effective date of registration: 20220111 Address after: No.1 Jiangdong Avenue, Jintan District, Changzhou City, Jiangsu Province Patentee after: Zhongchuangxin Aviation Technology Co.,Ltd. Address before: No.66, Binhe North Road, high tech Development Zone, Luoyang City, Henan Province Patentee before: CHINA AVIATION LITHIUM BATTERY Co.,Ltd. |