CN110767892A - Preparation method of silicon-carbon material of lithium ion battery - Google Patents
Preparation method of silicon-carbon material of lithium ion battery Download PDFInfo
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- CN110767892A CN110767892A CN201911066857.2A CN201911066857A CN110767892A CN 110767892 A CN110767892 A CN 110767892A CN 201911066857 A CN201911066857 A CN 201911066857A CN 110767892 A CN110767892 A CN 110767892A
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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
- 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
- H01M4/386—Silicon or alloys based on silicon
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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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
Abstract
The invention provides a preparation method of a silicon-carbon material of a lithium ion battery, which comprises the following steps: and mechanically ball-milling a mixture at least containing a silicon-based material and a carbon material, and finally carrying out heat treatment in an inert atmosphere to obtain the silicon-carbon composite material. The preparation method of the silicon-carbon material for the lithium ion battery provided by the invention has the advantages that the silicon-based material is crushed into nano particles by utilizing mechanical ball milling, the carbon material is crushed into the thin-layer nano graphite flakes or graphene, the thin-layer nano graphite flakes or graphene are coated on the surface of the silicon-based material in the ball milling process, and finally the silicon-based composite material with stable structure and improved electrochemical performance is obtained by heat treatment.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a silicon-carbon material of a lithium ion battery.
Background
Silicon-based material with high energy density (3580 mAh/g at normal temperature) and low potential (<0.5V vs.Li/Li+) High safety, abundant reserves, no pollution, etc. have attracted the researchers' extensive attention, and are considered to be the most promising next-generation businessOne of the lithium ion battery cathode materials. However, the problems of SEI film rupture, limited lithium source continuous consumption and poor cycle performance caused by low first-turn coulombic efficiency and huge volume expansion (about 300%) during charging and discharging still need to be solved. Currently, modification of silicon-based materials is mainly focused on nanocrystallization, silicon-carbon compounding and presetting of expansion space. However, how to ensure the uniform dispersion of the nanoparticles after the nanocrystallization and effectively preset the expansion space around the Si particles to control the volume change of the whole electrode is still a scientific problem to be solved and improved.
The chinese patent nos. CN108023072A, CN108400307A, CN110148718A, etc. all compound silicon-based materials with carbon materials to improve the conductivity of the silicon-based materials and relieve the volume expansion during charging and discharging to improve the electrochemical properties of the silicon-based materials, but they use a lot of raw materials and have complex process procedures, and are difficult to implement industrial production. In the invention patent CN110021749A, the problem of expansion of silicon-based materials is solved by compounding nano-silicon and graphene, but the method is too high in cost and not beneficial to industrial production.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a silicon-carbon material of a lithium ion battery, which can effectively improve the conductivity of a silicon-based material and the stability of an SEI film, and simultaneously provides a buffer space for the volume expansion of the silicon-based material, thereby greatly improving the first effect and the cycle performance of the silicon-carbon material.
A preparation method of a silicon-carbon material of a lithium ion battery comprises the following steps:
and mechanically ball-milling a mixture at least containing a silicon-based material and a carbon material, and finally carrying out heat treatment in an inert atmosphere to obtain the silicon-carbon composite material.
Preferably, the mixture further comprises additives and/or a dispersion.
Preferably, the mass ratio of the silicon-based material, the carbon material and the additive is 1:1-20: 0-5.
Preferably, the mass ratio of the silicon-based material to the dispersion is 1:0 to 10.
Preferably, the silicon-based material is SiOx material, and x is more than or equal to 0 and less than or equal to 1.
Preferably, the carbon material is at least one of natural graphite, expanded graphite, and expandable graphite.
Preferably, the additive is at least one of sucrose, glucose, phenolic resin, epoxy resin, polyvinylpyrrolidone, polyethylene glycol and carbon nanotubes.
Preferably, the dispersion liquid is at least one of deionized water, ethanol and isopropanol.
Preferably, the mechanical ball milling step is as follows: firstly adding a carbon material for ball milling, and then adding a silicon-based material for ball milling; or directly mixing the silicon-based material with the carbon material and carrying out ball milling; or firstly ball-milling the silicon-based material, and then adding the carbon material for ball-milling.
Preferably, the ball-milling ball-material ratio is 1-100:1, the ball-milling time is 1-20h, and the median particle size of the silicon-based material after ball milling is 100nm-5 μm.
Preferably, the heat treatment temperature is 600-1100 ℃, the heat preservation time is 2-6h, and the inert atmosphere is nitrogen, argon or helium.
Compared with the prior art, the invention has the following advantages:
the preparation method of the silicon-carbon material for the lithium ion battery provided by the invention has the advantages that the silicon-based material is crushed into nano particles by utilizing mechanical ball milling, the carbon material is crushed into the thin-layer nano graphite flakes or graphene, the thin-layer nano graphite flakes or graphene are coated on the surface of the silicon-based material in the ball milling process, and finally the silicon-based composite material with stable structure and improved electrochemical performance is obtained by heat treatment.
In terms of product performance, the thin-layer nano graphite sheet or graphene of the silicon-based composite material prepared by the invention improves the conductivity of the silicon-based material, and meanwhile, a more complete and stable SEI film is formed on the surface of the material, so that the excessive consumption of electrolyte is inhibited; on the other hand, the thin-layer nano graphite sheet or graphene cross-linked structure also provides a buffer space for the volume expansion of the silicon-based material, ensures the integrity of the electrode and improves the electrochemical performance of the material.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1:
weighing 10g of Si particles, putting the Si particles into a ball milling tank, mechanically milling the Si particles for 4h according to the ball-to-material ratio of 10:1, adding 50g of expanded graphite into the ball milling tank, continuously milling the Si particles for 4h together, taking out the ball-milled material, and carrying out heat treatment on the ball-milled material for 2h in inert atmosphere nitrogen at the temperature of 700 ℃. After cooling to room temperature, the material was taken out for crushing and the final sample was obtained.
Example 2:
weighing 5g of Si particles, 50g of natural graphite and 10g of cane sugar, placing the Si particles, the natural graphite and the cane sugar into a ball milling tank, adding 25g of deionized water as a dispersing agent, ball milling for 10 hours according to a ball-to-material ratio of 8:1, taking out ball-milled slurry, drying, performing heat treatment for 2 hours in inert atmosphere nitrogen at the temperature of 800 ℃, taking out the material after cooling to room temperature, and crushing to obtain a final sample.
Example 3:
weighing 10g of Si particles, 80g of expanded graphite and 20g of phenolic resin, putting the Si particles, the 80g of expanded graphite and the 20g of phenolic resin into a ball milling tank, adding 100g of absolute ethyl alcohol as a dispersing agent, ball milling for 12 hours according to a ball-to-material ratio of 20:1, taking out ball-milled slurry, drying, carrying out heat treatment for 3 hours in argon atmosphere at 900 ℃, cooling to room temperature, taking out the material, and crushing to obtain a final sample.
Example 4:
weighing 10g of Si particles, 10g of natural graphite and 20g of glucose, placing the materials in a ball milling tank, adding 50g of deionized water as a dispersing agent, ball milling for 5 hours together according to a ball-to-material ratio of 50:1, wherein the median particle size of the Si particles is 100nm-5 mu m, finally taking out the ball-milled slurry, drying, carrying out heat treatment for 4 hours in argon atmosphere at 700 ℃, cooling to room temperature, taking out the material, crushing, and obtaining a final sample.
Example 5:
weighing 100g of expandable graphite, adding the expandable graphite into a ball milling tank, ball milling for 4h according to the ball-to-material ratio of 30:1, adding 50g of Si particles, 10g of epoxy resin and 15g of isopropanol serving as a dispersing agent into the ball milling tank, continuing to grind for 3h, taking out the ball-milled slurry, drying, carrying out heat treatment for 2h in helium in an inert atmosphere at the temperature of 1000 ℃, taking out the material after cooling to room temperature, and crushing to obtain a final sample.
Example 6:
weighing 10g of SiO particles, 100g of expandable graphite and 20g of carbon nanotubes, placing the SiO particles, 100g of expandable graphite and 20g of carbon nanotubes in a ball milling tank, adding 50g of absolute ethyl alcohol as a dispersing agent, ball milling for 8 hours according to the ball-to-material ratio of 10:1, taking out ball-milled slurry, drying, carrying out heat treatment for 2 hours in helium gas in an inert atmosphere at the temperature of 1100 ℃, cooling to room temperature, taking out the material, and crushing to obtain a final sample.
Example 7:
weighing 5g of SiO and Si particles, 30g of sucrose and 100g of deionized water as dispersing agents, mixing the materials in a ball milling tank, ball milling for 10 hours according to the ball-to-material ratio of 1:1, adding 70g of expanded graphite, and continuing ball milling for 10 hours. And at the moment, the median particle size of the SiO particles is between 100nm and 5 mu m, finally, taking out the ball-milled slurry, drying, preserving the heat for 3 hours at 800 ℃ in helium gas in an inert atmosphere, and taking out the material for crushing after cooling to the room temperature to obtain a final sample.
Example 8:
weighing SiO0.8Mixing 10g of materials, 100g of natural graphite and 20g of polyvinylpyrrolidone in a ball milling tank, adding 80g of isopropanol as a dispersing agent, grinding for 1h according to the ball-to-material ratio of 100:1, wherein the median particle diameter of SiO0.8 particles is 100nm-5 mu m, and finally taking out the ball-milled slurry for carrying outAnd (5) drying. And then keeping the temperature of the mixture at 700 ℃ for 4h in argon in an inert atmosphere, and taking out the material for crushing after the mixture is cooled to room temperature to obtain a final sample.
Example 9:
weighing 10g of SiO particles, 50g of expandable graphite and 50g of glucose, placing the mixture in a ball milling tank for mixing, adding 30g of ethanol as a dispersing agent, carrying out ball milling for 5 hours according to the ball-to-material ratio of 50:1, taking out the slurry after grinding, and drying. And then carrying out heat preservation treatment in helium gas in an inert atmosphere at the temperature of 600 ℃ for 6 hours, and taking out the material for crushing after cooling to the room temperature to obtain a final sample.
Comparative example 1:
weighing 10g of Si particles, putting the Si particles into a ball milling tank, carrying out mechanical ball milling for 8h according to the ball-material ratio of 10:1, and finally taking out the material for crushing to obtain a final sample.
Comparative example 2:
weighing 10g of Si particles, putting the Si particles into a ball milling tank, mechanically ball milling the Si particles for 4 hours according to the ball-to-material ratio of 10:1, adding 50g of acetylene black into the ball milling tank, continuously ball milling the Si particles for 4 hours together, taking out the ball-milled material, and carrying out heat treatment on the ball-milled material for 2 hours in inert atmosphere nitrogen at the temperature of 700 ℃. After cooling to room temperature, the material was taken out for crushing and the final sample was obtained.
Comparative example 3:
weighing 5g of Si particles, 50g of acetylene black and 10g of sucrose, placing the Si particles, the acetylene black and the sucrose into a ball milling tank, adding 25g of deionized water as a dispersing agent, ball milling for 10 hours according to a ball-to-material ratio of 8:1, taking out ball-milled slurry, drying, performing heat treatment for 2 hours in inert atmosphere nitrogen at the temperature of 800 ℃, taking out the material after cooling to room temperature, and crushing to obtain a final sample.
Respectively manufacturing the silicon-based lithium ion negative electrode materials prepared in the 9 embodiments and the silicon-based materials of the 3 comparative examples into pole pieces, using the pole pieces as working electrodes, and using LiPF6The solution of/DMC + EC + DEC (1: 1: 1) is used as electrolyte to assemble a button cell, and the charging and discharging cut-off voltage is0.01-1.5V, charging and discharging with a constant current of 100mA/g, measuring the first charging specific capacity, the first coulombic efficiency and the 50-week cycle retention rate, and the results are shown in Table 1:
TABLE 1 comparison of initial specific charge capacity, initial coulombic efficiency, 50 cycle retention
| Specific capacity for first charge (mAh/g) | First coulombic efficiency (%) | 50-week cycle maintenance (%) | |
| Example 1 | 726.7 | 73 | 89 |
| Example 2 | 513.6 | 80 | 95 |
| Example 3 | 523.2 | 85 | 95 |
| Example 4 | 946.5 | 63 | 87 |
| Example 5 | 973.3 | 68 | 87 |
| Example 6 | 407.4 | 82 | 96 |
| Example 7 | 463.8 | 79 | 94 |
| Example 8 | 416.0 | 81 | 97 |
| Example 9 | 395.9 | 88 | 99 |
| Comparative example 1 | 1861.1 | 50 | 13 |
| Comparative example 2 | 707.6 | 62 | 59 |
| Comparative example 3 | 500.7 | 67 | 65 |
As can be seen from table 1, both comparative example 2 and example 3 were coated with a carbon material, but acetylene black, due to its small particle size, achieved only an incomplete spot coating of the silicon material, and thus comparative example 2 and example 3 had lower first effect and inferior cycle performance compared to example 1 and example 2. In combination, example 3 has a relatively high capacity, a high first pass and good cycle performance, which is benefited by the addition of the expanded graphite and additives. Through the ball milling step, the expanded graphite is broken into a thin-layer nano graphite sheet or graphene structure by mechanical force, and the thin-layer nano graphite sheet or graphene structure forms complete surface coating on silicon particles, so that the conductivity of the silicon-based material is improved, a more complete and stable SEI film is formed on the surface of the material, and the excessive consumption of electrolyte is inhibited; meanwhile, the thin-layer nano graphite sheet or graphene cross-linked structure also provides a buffer space for the volume expansion of the silicon-based material, ensures the integrity of the electrode and improves the electrochemical performance of the material.
Comparative example 1 corresponds to all examples and is a blank control for all examples. Comparative example 1 is only ball milling of the silicon-based material without subsequent other processing steps, while examples 1-9 all carry out coating, additive addition, final heat treatment and other steps on the silicon-based material, the addition of the carbon-containing additive forms an amorphous carbon coating layer on the surfaces of the silicon, the thin-layer graphite nanoplatelets and the graphene after high-temperature pyrolysis, the conductivity and integrity of the material are further improved, and meanwhile, the amorphous carbon layer can prevent direct contact of silicon particles and electrolyte, and the stability of an SEI film is enhanced. The combined action of the carbon material and the additive enables the silicon carbon material to exhibit relatively excellent electrochemical performance, which is also reflected in all the examples. The treatment of the examples results in an increase in the electrochemical performance of the silicon-based material. By comparing comparative example 1 with examples 1-9, the beneficial effects of the graphitic carbon material and additives and the heat treatment process on the silicon-based material can be highlighted, and the advantages of the present invention are demonstrated.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (12)
1. A preparation method of a silicon-carbon material of a lithium ion battery is characterized by comprising the following steps: which comprises the following steps:
and mechanically ball-milling a mixture at least containing a silicon-based material and a carbon material, and finally carrying out heat treatment in an inert atmosphere to obtain the silicon-carbon composite material.
2. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 1, wherein: the mechanical ball milling specifically comprises: and mechanically ball-milling the mixture until the median particle size of the silicon-based material is in a range between 100 nanometers and 5 micrometers, and finishing ball milling.
3. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 2, wherein: the silicon-based material is SiOx material, and x is more than or equal to 0 and less than or equal to 1.
4. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 2, wherein: the carbon material is at least one of natural graphite, expanded graphite, and expandable graphite.
5. The method for preparing the silicon-carbon material for lithium ion batteries according to any one of claims 1 to 4, wherein:
the mixture also includes additives and/or dispersions.
6. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 5, wherein: wherein the mass ratio of the silicon-based material to the carbon material to the additive is 1:1-20: 0-5.
7. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 5, wherein: wherein the mass ratio of the silicon-based material to the dispersion liquid is 1: 0-10.
8. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 5, wherein: the additive is at least one of sucrose, glucose, phenolic resin, epoxy resin, polyvinylpyrrolidone, polyethylene glycol and carbon nano tubes.
9. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 5, wherein: the dispersion liquid is at least one of deionized water, ethanol and isopropanol.
10. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 1 or 2, wherein: the mechanical ball milling step comprises: firstly adding a carbon material for ball milling, and then adding a silicon-based material for ball milling; or directly mixing the silicon-based material with the carbon material and carrying out ball milling; or firstly ball-milling the silicon-based material, and then adding the carbon material for ball-milling.
11. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 10, wherein: the ball-milling ball material ratio is 1-100:1, and the ball-milling time is 1-20 h.
12. The method for preparing a silicon-carbon material for a lithium ion battery according to claim 1, wherein: the heat treatment temperature is 600-1100 ℃, the heat preservation time is 2-6h, and the inert atmosphere is nitrogen, argon or helium.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112133896A (en) * | 2020-09-15 | 2020-12-25 | 捷威动力工业嘉兴有限公司 | High-capacity graphite-silicon oxide composite material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104396064A (en) * | 2012-07-06 | 2015-03-04 | 东丽株式会社 | Negative electrode material for lithium ion secondary batteries, composite negative electrode material for lithium ion secondary batteries, resin composition for negative electrodes of lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery |
| CN105789594A (en) * | 2016-04-25 | 2016-07-20 | 中国科学院化学研究所 | Silicon/silicic oxide/carbon composite material as well as preparation method and application thereof |
| CN105958036A (en) * | 2016-07-07 | 2016-09-21 | 天津普兰能源科技有限公司 | Preparation method for carbon-coated silicon negative electrode material for lithium ion battery |
| CN106025218A (en) * | 2016-06-21 | 2016-10-12 | 中国科学院化学研究所 | Preparation method of high surface density silicon carbon negative material and application thereof |
| CN107785541A (en) * | 2016-08-29 | 2018-03-09 | 南京安普瑞斯有限公司 | A kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof |
-
2019
- 2019-11-04 CN CN201911066857.2A patent/CN110767892B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104396064A (en) * | 2012-07-06 | 2015-03-04 | 东丽株式会社 | Negative electrode material for lithium ion secondary batteries, composite negative electrode material for lithium ion secondary batteries, resin composition for negative electrodes of lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery |
| CN105789594A (en) * | 2016-04-25 | 2016-07-20 | 中国科学院化学研究所 | Silicon/silicic oxide/carbon composite material as well as preparation method and application thereof |
| CN106025218A (en) * | 2016-06-21 | 2016-10-12 | 中国科学院化学研究所 | Preparation method of high surface density silicon carbon negative material and application thereof |
| CN105958036A (en) * | 2016-07-07 | 2016-09-21 | 天津普兰能源科技有限公司 | Preparation method for carbon-coated silicon negative electrode material for lithium ion battery |
| CN107785541A (en) * | 2016-08-29 | 2018-03-09 | 南京安普瑞斯有限公司 | A kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112133896A (en) * | 2020-09-15 | 2020-12-25 | 捷威动力工业嘉兴有限公司 | High-capacity graphite-silicon oxide composite material and preparation method and application thereof |
| CN112133896B (en) * | 2020-09-15 | 2022-04-19 | 捷威动力工业嘉兴有限公司 | High-capacity graphite-silicon oxide composite material and preparation method and application thereof |
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