CN114920242B - Preparation method of high-capacity graphite composite material - Google Patents

Preparation method of high-capacity graphite composite material Download PDF

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CN114920242B
CN114920242B CN202210559845.9A CN202210559845A CN114920242B CN 114920242 B CN114920242 B CN 114920242B CN 202210559845 A CN202210559845 A CN 202210559845A CN 114920242 B CN114920242 B CN 114920242B
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韩松
周萨
要夏晖
游晨涛
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Gelong New Material Technology Changzhou Co ltd
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract

The invention discloses a preparation method of a high-capacity graphite composite material, which comprises the following steps: adding polystyrene, organosilane compound, needle coke and oily carbon nanotube conductive liquid into an organic solvent to prepare a uniform solution, preparing precursor microspheres through spray drying, adding the precursor microspheres into a coating agent, performing wet ball milling, and preparing the high-capacity graphite composite material through microwave heating polymerization and carbonization. The prepared graphite composite material reduces the expansion of the silicon material and the doped silicon thereof by utilizing micro holes left after the polystyrene is decomposed to improve the capacity, and simultaneously shortens the preparation period of the material by combining with microwave heating polymerization, reduces the cost, and the prepared material has the characteristics of high specific capacity, excellent cycle performance and the like.

Description

Preparation method of high-capacity graphite composite material
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a preparation method of a high-capacity graphite composite material.
Background
Along with the application expansion of the lithium ion battery to the fields of power batteries, energy storage and the like, the lithium ion battery has higher and higher requirements on the energy density, the power density and the cycle life of the lithium ion battery. The existing negative electrode material for the lithium ion battery mainly comprises graphite materials and silicon-carbon materials, but the existing silicon-carbon materials have the defects of high expansion rate, poor cycle times (less than or equal to 1500 times), high price and the like, and the existing market requirements on the cycle performance of the negative electrode material are difficult to meet, so that the specific capacity and the cycle life of the artificial graphite are improved only by modifying the artificial graphite which is low in cost, mature and stable and excellent in cycle performance. At present, the artificial graphite modification is mainly optimized through processes such as secondary granulation, surface coating modification and the like of materials, and has the defects of small capacity lifting amplitude, large cyclic deviation, large expansion rate and the like.
Patent application CN 107871859A discloses a preparation method of a high-cycle power lithium ion battery anode material, which comprises the following preparation processes: (1) crushing; (2) mixing materials; (3) low-temperature heat treatment; (4) medium-temperature or high-temperature treatment; (5) Cooling and grading, wherein the coating agent adopts a composition of asphalt and heavy oil, which is favorable for realizing uniform coating, and meanwhile, the material has higher energy density, and the prepared negative electrode material has obviously improved liquid absorption performance and peeling strength, high charge-discharge multiplying power and good cycle performance. However, the liquid absorption and the circulation performance of the SEI film are not ideal, and the main reason is that the SEI film stability deviation and the structural stability deviation of the SEI film formed by the SEI film stability deviation are not modified by a precursor process, so that the specific capacity improvement amplitude is not obvious, and the circulation performance is still to be improved.
Disclosure of Invention
In order to improve the specific capacity and the cycle performance of the graphite composite material, the structural stability of the graphite precursor material and the matching property of the graphite precursor material with electrolyte are improved by doping and modifying the graphite precursor material, so that the specific capacity and the cycle performance of the graphite precursor material are improved.
The invention provides a preparation method of a high-capacity graphite composite material, which comprises the following steps:
(1) Preparing precursor microsphere A:
adding polystyrene, an organosilane compound, needle coke and oily carbon nanotube conductive liquid into an organic solvent to prepare a uniform solution, and then preparing a precursor microsphere A through spray drying, wherein the mass ratio of the components is polystyrene to the organosilane compound to the needle coke to the oily carbon nanotube conductive liquid solid to the organic solvent= (1-5): (500-1000);
(2) Preparing a graphite precursor composite material B:
mixing the precursor microsphere A, asphalt and a thio-benzene compound to obtain a graphite precursor composite material B, wherein the mass ratio of each component is precursor microsphere A to asphalt to thio-benzene compound=100 (10-30) (50-200);
(3) Preparation of composite material C:
transferring the graphite precursor composite material B into a microwave oven, and heating and polymerizing by a microwave technology to obtain a composite material C;
(4) Preparation of composite material D:
and (3) carrying out heat treatment on the composite material C for 1-2 hours at the temperature of 1000-1200 ℃ under the protection of mixed gas, and then cooling, grading and demagnetizing the composite material C in an inert atmosphere to obtain the graphite composite material D.
In a preferred embodiment of the present invention, the organosilane compound in step (1) is one of dichlorodimethylsilane, hexamethyldisilazane, phenyltrichlorosilane, trimethylchlorosilane, hexamethyldisiloxane, octamethyltetrasiloxane, diphenyldihydroxysilane, diphenyldichlorosilane, methyltrichlorosilane, methyldichlorosilane, chloromethylsilane, chlorophenyl silane and trimethylchlorosilane.
In a preferred embodiment of the present invention, the thio-benzene compound in step (2) is one of thiobenzamide, phenyl thiochloroformate, 4-hydroxythiobenzamide, 2-acetyl-4-methylthiobenzene, phenyl thiobenzoate and 5-bromothio-benzene-2-aldoxime.
In a preferred embodiment of the invention, the mixed gas in the step (4) is mixed gas of argon and chlorine trifluoride, and the volume ratio of the mixed gas to the chlorine trifluoride is 100 (1-10).
In a preferred embodiment of the present invention, the time of the heating polymerization in step (3) is 5 to 20 minutes.
In a preferred embodiment of the present invention, the microwave power in step (3) is 500W.
The invention has the beneficial effects that:
the preparation method comprises the steps of preparing needle coke precursor microspheres containing silicon compounds by taking polystyrene as a template and doping organic silane compounds and graphite precursor material needle coke on the surface of the template, then heating the precursor microspheres to decompose the precursor microspheres and leave nano-micron holes, on one hand, reducing the expansion of silicon materials of the precursor microspheres, on the other hand, doping carbon nano tubes into the inner core to reduce the expansion of the inner core silicon materials and improve the conductivity of the inner core silicon materials, and obtaining the composite material with the inner core of the silicon compound and the graphite composite material and the outer surface of the composite material with the outer surface of the carbon nitride compound and the sulfur groups and benzene ring groups in the sulfur benzene compound and asphalt crosslinked to form a stable-structure carbon nitride substance coating layer. Finally, through surface modification of the chlorine trifluoride, the active points of the surface groups of the material are reduced, the side reaction of the material and electrolyte is reduced, and the cycle performance of the material is improved. Meanwhile, the microwave heating can greatly shorten the preparation process.
Drawings
The invention may be better understood by reference to the following description of an embodiment of the invention, taken in conjunction with the accompanying drawings in which:
fig. 1 is an SEM image of the graphite composite material prepared in example 1.
Detailed Description
Example 1
1) Preparing precursor microsphere A:
3g of polystyrene, 3g of dichlorodimethylsilane, 100g of needle coke and 60ml of oily carbon nanotube conductive liquid with the concentration of 5% are added into 800ml of N-methylpyrrolidone to prepare a uniform solution, and then precursor microspheres A are prepared through spray drying;
2) Preparing a graphite precursor composite material B:
weighing 100g of precursor microsphere A, 20g of asphalt and 100g of phenyl thio-chloroformate, and mixing to obtain a graphite precursor composite material B;
3) Preparation of composite material C:
transferring the graphite precursor composite material B into a microwave oven, and performing heating polymerization for 10min by a microwave technology (power 500W) to obtain a composite material C;
4) Preparation of composite material D:
and (3) carrying out medium-temperature heat treatment on the composite material C for 1.5 hours at the temperature of 1100 ℃ under the protection of mixed gas of argon and chlorine trifluoride (volume ratio, 100:5 and flow rate, 10 ml/min), and then cooling, grading and demagnetizing under the inert atmosphere of argon to obtain the graphite composite material D.
Example 2
1) Preparing precursor microsphere A:
adding 1g of polystyrene, 1g of hexamethyldisilazane, 100g of needle coke and 20ml of oily carbon nanotube conductive liquid with the concentration of 5% into 500ml of N-methylpyrrolidone to prepare a uniform solution, and then preparing precursor microspheres A by spray drying;
2) Preparing a graphite precursor composite material:
weighing 100g of precursor microsphere A,10g of asphalt and 50g of phenyl thiochloroformate, and mixing to obtain a graphite precursor composite material B;
3) Preparation of composite material C:
transferring the graphite precursor composite material B into a microwave oven, and heating and polymerizing for 5min by a microwave technology (power 500W) to obtain a composite material C;
4) Preparation of composite material D:
and (3) carrying out medium-temperature heat treatment on the composite material C for 2 hours at the temperature of 1000 ℃ under the protection of mixed gas (volume ratio, 100:1 and flow rate of 10 ml/min) of argon and chlorine trifluoride, and then cooling, grading and demagnetizing the composite material C under the inert atmosphere of argon to obtain the graphite composite material D.
Example 3
1) Preparing precursor microsphere A:
adding 5g of polystyrene, 5g of trimethylchlorosilane, 100g of needle coke and 100ml of oily carbon nanotube conductive liquid with the concentration of 5% into 1000ml of N-methylpyrrolidone organic solvent to prepare a uniform solution, and then preparing precursor microspheres A through spray drying;
2) Preparing a graphite precursor composite material:
weighing 100g of precursor microsphere A, 30g of asphalt and 200g of 4-hydroxy thiobenzamide, and mixing to obtain a graphite precursor composite material B;
3) Preparation of composite material C:
transferring the graphite precursor composite material B into a microwave oven, and heating and polymerizing for 20min by a microwave technology (power 500W) to obtain a composite material C;
4) Preparation of composite material D:
and (3) carrying out medium-temperature heat treatment on the composite material C for 1 hour at the temperature of 1200 ℃ under the protection of mixed gas of argon and chlorine trifluoride (volume ratio, 100:10 and flow rate, 10 ml/min), and then cooling, grading and demagnetizing under the inert atmosphere of argon to obtain the graphite composite material D.
Comparative example
And (3) uniformly mixing 100g of needle coke and 30g of asphalt, transferring into a tube furnace, sintering and preserving heat for 1h under the protection of argon atmosphere at 1200 ℃, naturally cooling to room temperature, grading, and demagnetizing to obtain the graphite composite material.
1) SEM test:
fig. 1 is an SEM image of the graphite composite material prepared in example 1, and it can be seen from the image that the material has a spheroid-like structure, the size distribution is reasonable, and the particle size is between 10 and 15 μm.
2) Physical and chemical properties and button cell testing:
the lithium ion battery anode materials obtained in examples 1 to 3 and comparative example were assembled into button cells A1, A2, A3, B1, respectively; the preparation method comprises the following steps: adding binder, conductive agent and solvent into the cathode material, stirring to slurry, coating on copper foil, oven drying, and rolling. The binder used is LA132 binder, conductive agent SP, the negative electrode materials are prepared in examples 1-3 and comparative example, the solvent is secondary distilled water, the proportion is: the anode material is SP 132, secondary distilled water=95 g:1g:4g:220mL, and an anode pole piece is prepared; the electrolyte is LiPF 6 And (3) the EC+DEC (volume ratio of 1:1) is used as a counter electrode, a diaphragm adopts a Polyethylene (PE), polypropylene (PP) or polyethylene propylene (PEP) composite film, the simulated battery is assembled in an argon-filled glove box, the electrochemical performance is carried out on a Wuhan blue electric CT2001A type battery tester, the charging and discharging voltage range is 0.005V to 2.0V, and the charging and discharging rate is 0.1C. The front electrode plate was also tested for compaction density and liquid absorption and retention capacity, and the cycling performance (0.1C/0.1C, 25 ℃,5 mV-2V) of its button cell. The test data are detailed in table 1.
Figure 315212DEST_PATH_IMAGE001
As can be seen from table 1, the discharge capacity of the coin cells using the negative electrode materials obtained in examples 1 to 3 and the first efficiency thereof were significantly higher than those of the comparative examples. Experimental results show that nanometer micron holes are reserved after carbonization by coating needle coke doped with organosilane compound and graphite precursor material on the surface of graphite, the expansion of the material can be controlled while the self capacity of the silicon material is high, and meanwhile, nanometer micron holes are reserved by decomposing polystyrene microspheres, so that the liquid absorption and retention capacity is high, and the cycle performance of the button cell in the embodiment is improved.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (6)

1. The preparation method of the high-capacity graphite composite material is characterized by comprising the following steps of:
(1) Preparing precursor microsphere A:
adding polystyrene, an organosilane compound, needle coke and oily carbon nanotube conductive liquid into an organic solvent to prepare a uniform solution, and then preparing a precursor microsphere A through spray drying, wherein the mass ratio of the components is polystyrene to the organosilane compound to the needle coke to the oily carbon nanotube conductive liquid solid to the organic solvent= (1-5): (500-1000);
(2) Preparing a graphite precursor composite material B:
mixing the precursor microsphere A, asphalt and a thiobenzene compound to obtain a graphite precursor composite material B, wherein the mass ratio of each component is (10-30) of the precursor microsphere A to (50-200) of the asphalt to the thiobenzene compound=100;
(3) Preparation of composite material C:
transferring the graphite precursor composite material B into a microwave oven, and heating and polymerizing by a microwave technology to obtain a composite material C;
(4) Preparation of composite material D:
and (3) carrying out heat treatment on the composite material C for 1-2 hours at the temperature of 1000-1200 ℃ under the protection of mixed gas, and then cooling, grading and demagnetizing the composite material C in an inert atmosphere to obtain the high-capacity graphite composite material D.
2. The production method according to claim 1, wherein the organosilane compound in step (1) is one of dichlorodimethylsilane, hexamethyldisilazane, phenyltrichlorosilane, trimethylchlorosilane, hexamethyldisiloxane, octamethyltetrasiloxane, diphenyldihydroxysilane, diphenyldichlorosilane, methyltrichlorosilane, methyldichlorosilane, chloromethylsilane, chlorophenyl silane and trimethylchlorosilane.
3. The production method according to claim 1, wherein the thio-benzene compound in the step (2) is one of thiobenzamide, phenyl thiochloroformate, 4-hydroxythiobenzamide, 2-acetyl-4-methylthiobenzene, phenyl thiobenzoate and 5-bromothio-benzene-2-aldoxime.
4. The preparation method according to claim 1, wherein the mixed gas in the step (4) is a mixed gas of argon and chlorine trifluoride, and the volume ratio is 100 (1-10).
5. The process according to claim 1, wherein the heating polymerization time in the step (3) is 5 to 20 minutes.
6. The method of claim 1, wherein the microwave power in step (3) is 500W.
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WO2010029135A2 (en) * 2008-09-12 2010-03-18 Commissariat A L'energie Atomique Method for producing a silicon/carbon composite material, material produced thereby, and electrode, especially negative electrode, comprising said material
CN114242987A (en) * 2021-12-22 2022-03-25 格龙新材料科技(常州)有限公司 Preparation method of three-dimensional porous silicon-carbon composite material
CN114400312A (en) * 2022-01-24 2022-04-26 格龙新材料科技(常州)有限公司 Low-expansion silicon-carbon composite negative electrode material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010029135A2 (en) * 2008-09-12 2010-03-18 Commissariat A L'energie Atomique Method for producing a silicon/carbon composite material, material produced thereby, and electrode, especially negative electrode, comprising said material
CN114242987A (en) * 2021-12-22 2022-03-25 格龙新材料科技(常州)有限公司 Preparation method of three-dimensional porous silicon-carbon composite material
CN114400312A (en) * 2022-01-24 2022-04-26 格龙新材料科技(常州)有限公司 Low-expansion silicon-carbon composite negative electrode material and preparation method thereof

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