CN111342014A - Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof - Google Patents
Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN111342014A CN111342014A CN202010148266.6A CN202010148266A CN111342014A CN 111342014 A CN111342014 A CN 111342014A CN 202010148266 A CN202010148266 A CN 202010148266A CN 111342014 A CN111342014 A CN 111342014A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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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- 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 discloses a preparation method of a silicon-carbon cathode material of a lithium ion battery, which comprises the following steps: (1) putting the silicon monoxide in a corundum boat, and calcining in a tubular furnace to obtain disproportionated silicon monoxide; (2) mixing the disproportionated silicon monoxide, a carbon source and a nitrogen source according to a certain mass ratio, and adding a proper amount of deionized water to form a suspension; (3) heating the suspension in an open water bath and violently stirring until the water is evaporated to dryness to obtain residue; (4) and placing the residues in a corundum boat, preserving the temperature at low temperature in a tubular furnace, and calcining at high temperature to obtain the stable long-cycle lithium ion battery silicon-carbon cathode material. The invention also provides a silicon-carbon cathode material of the lithium ion battery, which has a core-shell structure, wherein the core is disproportionated silicon monoxide, and the shell is a nitrogen-doped carbon coating layer. The preparation method is simple and low in cost, and the provided negative electrode material is high in conductivity and excellent in cycle performance.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a silicon-carbon negative electrode material of a lithium ion battery and a preparation method thereof.
Background
In recent years, with the decrease of fossil energy and the increasing severity of environmental issues, lithium ion batteries have attracted more and more attention in the fields of electric vehicles and energy storage. Lithium ion batteries are currently considered to be the most promising electrical energy storage devices due to their higher energy and power densities relative to other types of batteries.
However, the energy density and power density of the existing lithium ion battery are still low, and the safety and cycle life of the existing lithium ion battery do not meet the requirements of future electric vehicles and energy storage system applications.
At present, the commercial lithium ion battery generally adopts graphite as a negative electrode material, but the theoretical specific capacity of the graphite is only 372mAh/g, and the demand of the field with higher energy density requirement cannot be met. Therefore, finding a negative electrode material with high specific capacity and long service life which can replace graphite is an important research direction of lithium ion batteries. Among a plurality of negative electrode materials, silicon materials have superior lithium intercalation capacity, are not easy to agglomerate in the electrochemical lithium intercalation and deintercalation process, have a discharge platform higher than that of the carbon-based materials widely used at present, are not easy to form lithium dendrites on the surface of an electrode, and the like, and are concerned. However, silicon suffers from 400% volume expansion and very low intrinsic conductivity during lithium ion intercalation/deintercalation. Meanwhile, silicon is not easy to generate a Solid Electrolyte Interface (SEI) film in a conventional electrolyte, which causes the problems of very low coulombic efficiency, short cycle life and the like of an initial battery.
CN106532010A in-situ coats nano-silicon with silicon nitride nanowires, and graphene is adopted to modify the surface of silicon nitride to form a silicon-silicon nitride-carbon composite material. The patent requires large energy consumption of 1200-1400 ℃ when the silicon nitride is synthesized to coat the nano silicon, the capacity of the coated silicon is greatly reduced due to the coating amount of the silicon nitride being more than 20%, the highest gram capacity of the coated silicon is only 512mAh/g, the graphene is difficult to disperse, the price is high, and the method is poor in economy.
The CN1075079792A patent adopts silicon alloy as raw material, obtains porous silicon by acid washing, and mixes and sinters the porous silicon and carbon source to prepare the silicon-carbon composite material. Acid washing is needed in the preparation process of the patent method, a large amount of waste water is generated, the environmental pollution is large, the highest capacity of the prepared silicon-based material is 1086mAh/g, and the capacity retention rate is only 83.4% after 20 cycles.
CN108390049A provides a composite negative electrode material with silicon powder as the innermost layer, silicon carbide as the middle coating layer and carbon material as the outermost coating layer. The silicon carbide produced by the patent needs high temperature (1000 ℃) and gas phase coating, has higher requirement on equipment and poor economic benefit, and is not beneficial to large-scale commercial popularization.
Therefore, in order to overcome the above problems in the prior art, it is necessary to provide a silicon carbon negative electrode material for a battery, which has good conductivity and excellent cycle performance, and has low preparation requirement, low cost and simple steps.
Disclosure of Invention
The invention provides a silicon-carbon cathode material of a lithium ion battery and a preparation method thereof, aiming at solving the problems in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of the silicon-carbon negative electrode material of the lithium ion battery, which comprises the following steps:
(1) putting the silicon monoxide in a corundum boat, and calcining in a tubular furnace to obtain disproportionated silicon monoxide;
(2) mixing the disproportionated silicon monoxide, the carbon source and the nitrogen source according to a certain mass ratio, and adding a proper amount of deionized water to form a suspension;
(3) heating the suspension in an open water bath and violently stirring until the water is evaporated to dryness to obtain residues;
(4) and placing the residues in a corundum boat, preserving the temperature at low temperature in a tubular furnace, and calcining at high temperature to obtain the silicon-carbon cathode material of the lithium ion battery.
Preferably, the nitrogen source in step (2) is selected from one or two of melamine and urea.
Preferably, the carbon source in step (2) is high softening point pitch.
Preferably, the calcination in step (1) is specifically: introducing argon gas as protective gas into the tubular furnace, heating the tubular furnace to 700-900 ℃ at the speed of 3 ℃/min, and keeping the temperature for 2-5 h.
Preferably, the mass ratio of the disproportionated silicon monoxide, the carbon source and the nitrogen source in the step (2) is 0.5-2:1-5: 0.5-2.
Preferably, the heating temperature of the water bath heating in the step (3) is 35-70 ℃, and the stirring speed is 500-600 rpm.
Preferably, the temperature of the low-temperature heat preservation in the step (4) is 250-400 ℃, and the time is 4-8 h; the high-temperature calcination temperature is 650-800 ℃, and the time is 0.5-3 h.
In a second aspect, the invention provides a silicon-carbon negative electrode material of a lithium ion battery, wherein the silicon-carbon negative electrode material of the lithium ion battery has a core-shell structure, the core is disproportionated silicon monoxide (d-SiO), and the shell is a nitrogen-doped carbon coating layer.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
the lithium ion battery silicon-carbon negative electrode material prepared by the invention has the advantages that as trivalent nitrogen is doped in the carbon coating layer, the carbon atom arrangement is defective, the conductivity of the coating layer is enhanced, the stress during the volume expansion of silicon is buffered, the lithium ion battery silicon-carbon negative electrode material has excellent cycle performance, the capacity retention rate is more than 80 percent when the lithium ion battery silicon-carbon negative electrode material is charged and discharged for 200 cycles under the current density of 1000mA/g, and the lithium ion battery silicon-carbon negative electrode material has simple preparation process, low requirement and low cost.
Detailed Description
The present invention will be described in detail and specifically with reference to the following examples to facilitate better understanding of the present invention, but the following examples do not limit the scope of the present invention.
Example 1
In this embodiment, a preparation method of a silicon-carbon negative electrode material of a lithium ion battery is provided, which includes the following steps:
(1) putting the silicon monoxide into a corundum boat, putting the corundum boat into a tube furnace, introducing argon as protective gas, heating to 900 ℃ at the speed of 3 ℃/min, and calcining for disproportionation for 3 hours to obtain disproportionated silicon monoxide;
(2) adding disproportionated silicon monoxide, asphalt and melamine into a beaker according to the mass ratio of 1:2:1, mixing, and adding a proper amount of deionized water to form a suspension;
(3) heating the obtained suspension in a water bath kettle with the opening and stirring vigorously until water is evaporated to dryness to obtain residue, wherein the water bath temperature is 50 ℃, and the stirring speed is 600 rpm;
(4) and transferring the residue obtained after evaporation to a corundum boat, putting the corundum boat into a tubular furnace, introducing argon gas as protective gas, preserving heat at 300 ℃ for 6 hours, heating to 700 ℃ for calcining for 2 hours, and naturally cooling to obtain the nitrogen-doped carbon-coated silicon carbon negative electrode material d-SiO @ NC-1.
Example 2
In this embodiment, a preparation method of a silicon-carbon negative electrode material of a lithium ion battery is provided, which includes the following steps:
(1) putting the silicon monoxide into a corundum boat, putting the corundum boat into a tube furnace, introducing argon as protective gas, heating to 900 ℃ at the speed of 3 ℃/min, and calcining for disproportionation for 3 hours to obtain disproportionated silicon monoxide;
(2) adding disproportionated silicon monoxide, asphalt and urea into a beaker according to the mass ratio of 1:2:1, mixing, and adding a proper amount of deionized water to form a suspension;
(3) heating the obtained suspension in a water bath kettle with the opening and stirring vigorously until water is evaporated to dryness to obtain residue, wherein the water bath temperature is 50 ℃, and the stirring speed is 500 rpm;
(4) and transferring the residue obtained after evaporation to a corundum boat, putting the corundum boat into a tubular furnace, introducing argon gas as protective gas, preserving heat at 300 ℃ for 6 hours, heating to 700 ℃ for calcining for 2 hours, and naturally cooling to obtain the nitrogen-doped carbon-coated silicon carbon negative electrode material d-SiO @ NC-1.
Example 3
Using the lithium ion battery silicon carbon negative electrode material prepared in examples 1-2, CR2032 type button cell batteries were prepared for battery testing experiments, and electrochemical experiments were performed on the batteries, respectively, with the following specific results:
TABLE 1 comparison of experimental data for CR2032 button cell
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of a silicon-carbon negative electrode material of a lithium ion battery is characterized by comprising the following steps:
(1) putting the silicon monoxide in a corundum boat, and calcining in a tubular furnace to obtain disproportionated silicon monoxide;
(2) mixing the disproportionated silicon monoxide, the carbon source and the nitrogen source according to a certain mass ratio, and adding a proper amount of deionized water to form a suspension;
(3) heating the suspension in an open water bath and violently stirring until the water is evaporated to dryness to obtain residues;
(4) and placing the residues in a corundum boat, preserving the temperature at low temperature in a tubular furnace, and calcining at high temperature to obtain the silicon-carbon cathode material of the lithium ion battery.
2. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the nitrogen source in the step (2) is one or two selected from melamine and urea.
3. The preparation method of the silicon-carbon anode material of the lithium ion battery as claimed in claim 1, wherein the carbon source in the step (2) is high-softening-point pitch.
4. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the calcination in the step (1) is specifically: introducing argon gas as protective gas into the tubular furnace, heating the tubular furnace to 700-900 ℃ at the speed of 3 ℃/min, and keeping the temperature for 2-5 h.
5. The preparation method of the silicon-carbon anode material of the lithium ion battery as claimed in claim 1, wherein the mass ratio of the disproportionated oxidized silicon monoxide to the carbon source to the nitrogen source in the step (2) is 0.5-2:1-5: 0.5-2.
6. The method for preparing the silicon-carbon anode material of the lithium ion battery as claimed in claim 1, wherein the heating temperature of the water bath heating in the step (3) is 35-70 ℃, and the stirring speed is 500-600 rpm.
7. The preparation method of the silicon-carbon anode material for the lithium ion battery as claimed in claim 1, wherein the low-temperature heat preservation temperature in the step (4) is 250-400 ℃, and the time is 4-8 h; the high-temperature calcination temperature is 650-800 ℃, and the time is 0.5-3 h.
8. The preparation method of the silicon-carbon anode material of the lithium ion battery according to claim 1,
and (4) keeping introducing argon into the tubular furnace as a protective gas all the time.
9. A silicon carbon negative electrode material of a lithium ion battery prepared by the method of any one of claims 1 to 8.
10. The silicon-carbon anode material for the lithium ion battery as claimed in claim 9, wherein the silicon-carbon anode material for the lithium ion battery has a core-shell structure, the core is disproportionated silicon monoxide, and the shell is a nitrogen-doped carbon coating layer.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747396A (en) * | 2020-07-10 | 2020-10-09 | 厦门大学 | Nitrogen-phosphorus-doped two-dimensional carbon/silicon compound and preparation method and application thereof |
| CN113346050A (en) * | 2021-04-21 | 2021-09-03 | 昆山聚创新能源科技有限公司 | Silicon-carbon negative pole piece and preparation method and application thereof |
| CN114229854A (en) * | 2021-12-17 | 2022-03-25 | 新疆晶硕新材料有限公司 | Preparation method of silicon-oxygen-carbon composite material, negative plate and battery |
| CN114613972A (en) * | 2022-04-08 | 2022-06-10 | 南昌大学共青城光氢储技术研究院 | Silicon carbide oxide negative electrode material for lithium ion battery and preparation method thereof |
| CN114713256A (en) * | 2022-03-08 | 2022-07-08 | 华南理工大学 | Nitrogen-oxygen double-doped carbon material and preparation method and application thereof |
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| KR20190057571A (en) * | 2017-11-20 | 2019-05-29 | 한국전기연구원 | Anode Active Materails With Long Life Cycle For Li Secondary Battery And Manufacturing Methods Thereof |
| CN110600720A (en) * | 2019-09-20 | 2019-12-20 | 广东省稀有金属研究所 | Composite silicon-based material, negative electrode material, preparation methods of composite silicon-based material and negative electrode material, and lithium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111747396A (en) * | 2020-07-10 | 2020-10-09 | 厦门大学 | Nitrogen-phosphorus-doped two-dimensional carbon/silicon compound and preparation method and application thereof |
| CN113346050A (en) * | 2021-04-21 | 2021-09-03 | 昆山聚创新能源科技有限公司 | Silicon-carbon negative pole piece and preparation method and application thereof |
| CN114229854A (en) * | 2021-12-17 | 2022-03-25 | 新疆晶硕新材料有限公司 | Preparation method of silicon-oxygen-carbon composite material, negative plate and battery |
| CN114713256A (en) * | 2022-03-08 | 2022-07-08 | 华南理工大学 | Nitrogen-oxygen double-doped carbon material and preparation method and application thereof |
| CN114613972A (en) * | 2022-04-08 | 2022-06-10 | 南昌大学共青城光氢储技术研究院 | Silicon carbide oxide negative electrode material for lithium ion battery and preparation method thereof |
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Application publication date: 20200626 |