CN109244384B - 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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- CN109244384B CN109244384B CN201810930603.XA CN201810930603A CN109244384B CN 109244384 B CN109244384 B CN 109244384B CN 201810930603 A CN201810930603 A CN 201810930603A CN 109244384 B CN109244384 B CN 109244384B
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- H01M4/00—Electrodes
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- 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
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- 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
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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
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Abstract
The invention discloses a silicon-carbon cathode material of a lithium ion battery and a preparation method thereof. The material is a composite material of nano silicon, porous carbon and graphite; the preparation method comprises the following steps: according to weight, 10-30 parts of silicon carbide powder with the average particle size of 10-20 mu m are flatly paved in a furnace core of a graphitization furnace, and then 100 parts of silicon carbide powder with the specific surface area of 50-100m2Paving a porous carbon material with the average particle size of 15-25 mu m on the silicon carbide layer, and finally covering a graphite plate and a heat insulating material on the porous carbon layer in sequence; thermally decomposing the silicon carbide layer at 2200-2400 deg.C for 2-10 hr, and controlling the temperature of the porous carbon layer below 1400 deg.C; cooling the materials to room temperature and discharging; the materials are stirred and mixed evenly, and then the mixture is screened by a 300-mesh screen to obtain the lithium ion battery cathode material. The invention greatly improves the energy density of the cathode material and greatly improves the cycling stability of the silicon-based cathode material; meanwhile, the product has low production cost.
Description
Technical Field
The invention relates to the technical 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
The development of lithium ion batteries with high energy density and long cycle life has great significance for the application of portable electronic products and electric automobiles. For this reason, the electrode material must have a high lithium storage capacity and satisfactory cycle stability. As an alternative material to graphite anodes, silicon has a known highest theoretical specific capacity (4200 mAh/g) and a suitable charge-discharge plateau (0.4-0.5V), considered the most promising anode material. However, silicon forms alloys with Li in the presence of complete lithium intercalation22Si5Volume expansion of up to 300% occurs during the process, resulting in electrode powdering, separation from the current collector and rapid decay of specific capacity, thereby affecting the service life of the battery. In view of this, researchers have prepared various silicon-based nanostructures such as silicon nanowires, silicon nanotubes, silicon thin films, and the like, have relieved the volume change of electrodes in the charging and discharging process, have promoted the cycle service life of batteries, and have greatly promoted the development of silicon-based negative electrode materials. However, the preparation processes of silicon nanowires, silicon nanotubes, silicon thin films and the like are complex and high in cost, and are only limited to synthesis in a small amount in a laboratory, so that the industrial requirements cannot be met.
Disclosure of Invention
The invention aims to provide a silicon-carbon negative electrode material of a lithium ion battery and a preparation method thereof, and aims to solve the technical problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the lithium ion battery silicon-carbon cathode material is a composite material of nano-silicon, porous carbon and graphite, wherein the nano-silicon and the graphite are generated by in-situ thermal decomposition of raw material silicon carbide.
As a further embodiment of the invention, the silicon carbide is green silicon carbide with a purity of > 99.9% and an average particle size of 10-20 μm.
As a further scheme of the invention, the specific surface area of the porous carbon material is 50-100m2(iv)/g, average particle size 15-25 μm.
A preparation method of a silicon-carbon negative electrode material of a lithium ion battery comprises the following steps:
1) weighing 10-30 parts by weight of silicon carbide powder, paving the silicon carbide powder in a furnace core of a graphitization furnace, paving 100 parts by weight of porous carbon material on a silicon carbide layer, and sequentially covering a graphite plate and a heat preservation material on the porous carbon layer;
2) the silicon carbide layer is thermally decomposed for 2 to 10 hours at the temperature of 2200 to 2400 ℃, and the temperature of the porous carbon layer is controlled below 1400 ℃;
3) and cooling the materials, discharging, stirring and mixing uniformly, and screening by using a 300-mesh screen to obtain the lithium ion battery cathode material.
The method of claim 4, wherein: the average particle size of the silicon-carbon negative electrode material of the lithium ion battery is 16-28 mu m, and the specific surface area is 30-80m2The first gram capacity is more than 600mAh/g, and the first efficiency is more than 85.4%.
The invention has the beneficial effects that: according to the invention, cheap silicon carbide is used as a precursor of nano silicon, a simple and easily-controlled heat treatment process is adopted to generate the nano silicon in situ, and the generated silicon vapor is deposited in pores of porous carbon due to temperature gradient, so that space is reserved for the volume expansion of the silicon powder; the negative electrode material prepared by the invention has the first gram capacity of more than 600mAh/g, the first efficiency of more than 85.4 percent and the capacity retention rate of more than 85 percent after 200-week circulation, thereby effectively solving the problem of poor cycle performance of the silicon-based negative electrode material; meanwhile, the preparation method is easy to implement industrially.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The silicon-carbon cathode material of the lithium ion battery is prepared by taking porous carbon and silicon carbide as raw materials, thermally decomposing the silicon carbide to generate silicon vapor and graphite with high crystallinity in situ, and depositing the silicon vapor into pores of the porous carbon to form a composite material of nano silicon, the porous carbon and the graphite. In the negative electrode material, the weight ratio of the nano silicon to the porous carbon is 0.07-0.21: 1.
Example 1
By weight, 10 parts of silicon carbide having an average particle size of 10.5 μm and a purity of 99.92% and 100 parts of silicon carbide having an average particle size of 15.8 μm and a specific surface area of 54.6 m were weighed2Porous carbon per gram; spreading silicon carbide in a furnace core of a graphitization furnace, spreading a porous carbon material on a silicon carbide layer, and sequentially covering a graphite plate and a heat preservation material on a porous carbon layer; thermally decomposing the silicon carbide layer at 2200 deg.C for 2 hr, and controlling the temperature of the porous carbon layer below 1400 deg.C; and cooling the materials, discharging, stirring and mixing uniformly, and screening by using a 300-mesh screen to obtain the lithium ion battery cathode material.
Example 2
15 parts by weight of silicon carbide having an average particle size of 12.8 μm and a purity of 99.93% and 100 parts by weight of silicon carbide having an average particle size of 18.2 μm and a specific surface area of 63.8 m were weighed2Porous carbon per gram; spreading silicon carbide in a furnace core of a graphitization furnace, spreading a porous carbon material on a silicon carbide layer, and sequentially covering a graphite plate and a heat preservation material on a porous carbon layer; thermally decomposing the silicon carbide layer at 2250 deg.C for 4 hr, and controlling the temperature of the porous carbon layer below 1400 deg.C; and cooling the materials, discharging, stirring and mixing uniformly, and screening by using a 300-mesh screen to obtain the lithium ion battery cathode material.
Example 3
By weight, 20 parts of silicon carbide having an average particle size of 15.6 μm and a purity of 99.93% and 100 parts of silicon carbide having an average particle size of 20.4 μm and a specific surface area of 72.3 m were weighed2Porous carbon per gram; spreading silicon carbide on graphiteIn a furnace core of the furnace, a porous carbon material is paved on a silicon carbide layer, and a graphite plate and a heat preservation material are sequentially covered on the porous carbon layer; thermally decomposing the silicon carbide layer at 2300 deg.C for 6 hr, and controlling the temperature of the porous carbon layer below 1400 deg.C; and cooling the materials, discharging, stirring and mixing uniformly, and screening by using a 300-mesh screen to obtain the lithium ion battery cathode material.
Example 4
By weight, 25 parts of silicon carbide having an average particle size of 18.2 μm and a purity of 99.93% and 100 parts of silicon carbide having an average particle size of 23.2 μm and a specific surface area of 81.5 m were weighed2Porous carbon per gram; spreading silicon carbide in a furnace core of a graphitization furnace, spreading a porous carbon material on a silicon carbide layer, and sequentially covering a graphite plate and a heat preservation material on a porous carbon layer; thermally decomposing the silicon carbide layer at 2350 deg.C for 8 hr, and controlling the temperature of the porous carbon layer below 1400 deg.C; and cooling the materials, discharging, stirring and mixing uniformly, and sieving by using a 300-mesh sieve to obtain the lithium ion battery cathode material.
Example 5
30 parts by weight of silicon carbide having an average particle size of 19.8 μm and a purity of 99.93% and 100 parts by weight of silicon carbide having an average particle size of 24.8 μm and a specific surface area of 96.5 m were weighed2Porous carbon per gram; spreading silicon carbide in a furnace core of a graphitization furnace, spreading a porous carbon material on a silicon carbide layer, and sequentially covering a graphite plate and a heat preservation material on a porous carbon layer; thermally decomposing the silicon carbide layer at 2400 deg.C for 10 hr, and controlling the temperature of the porous carbon layer below 1400 deg.C; and cooling the materials, discharging, stirring and mixing uniformly, and screening by using a 300-mesh screen to obtain the lithium ion battery cathode material.
The negative electrode materials obtained in examples 1 to 5 were tested using the test standard for electrochemical capacity of Q/TEZI01-2001.5.7, and the test results are as follows.
| Examples | Average particle size (. mu.m) | Specific surface area (m)2/g) | First capacity (mAh/g) | First efficiency (%) | Capacity retention at 200 weeks (%) |
| 1 | 16.5 | 35.4 | 604.5 | 85.6 | 92.3 |
| 2 | 20.3 | 44.6 | 613.4 | 87.5 | 91.5 |
| 3 | 22.5 | 52.4 | 627.8 | 89.1 | 89.4 |
| 4 | 26.2 | 64.8 | 641.5 | 91.2 | 87.5 |
| 5 | 27.8 | 78.7 | 659.0 | 91.8 | 85.2 |
The negative electrode material prepared by the invention has the first gram capacity of more than 600mAh/g, the first efficiency of more than 85.4 percent and the capacity retention rate of more than 85 percent after 200-week circulation, and effectively solves the problem of poor cycle performance of the silicon-based negative electrode material.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. A preparation method of a silicon-carbon cathode material of a lithium ion battery is characterized by comprising the following steps: the negative electrode material is a composite material of nano-silicon, porous carbon and graphite, wherein the nano-silicon and the graphite are generated by in-situ thermal decomposition of raw material silicon carbide;
the method comprises the following steps:
1) weighing 10-30 parts by weight of silicon carbide powder, paving the silicon carbide powder in a furnace core of a graphitization furnace, paving 100 parts by weight of porous carbon material on a silicon carbide layer, and sequentially covering a graphite plate and a heat preservation material on the porous carbon layer;
2) the silicon carbide layer is thermally decomposed for 2 to 10 hours at the temperature of 2200 to 2400 ℃, and the temperature of the porous carbon layer is controlled below 1400 ℃;
3) and cooling the materials, discharging, stirring and mixing uniformly, and screening by using a 300-mesh screen to obtain the lithium ion battery cathode material.
2. The preparation method of the silicon-carbon anode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the silicon carbide is green silicon carbide, the purity is more than 99.9 percent, and the average particle size is 10-20 mu m.
3. The preparation method of the silicon-carbon anode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the specific surface area of the porous carbon material is 50-100m2(iv)/g, average particle size 15-25 μm.
4. The preparation method of the silicon-carbon anode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the average particle size of the silicon-carbon negative electrode material of the lithium ion battery is 16-28 mu m, and the specific surface area is 30-80m2The first gram capacity is more than 600mAh/g, and the first efficiency is more than 85.4%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104600312A (en) * | 2014-12-30 | 2015-05-06 | 东莞市凯金新能源科技有限公司 | Preparation method of lithium ion battery porous negative electrode material |
| CN107534149A (en) * | 2015-05-11 | 2018-01-02 | 昭和电工株式会社 | The manufacture method of ion secondary battery cathode material lithium graphite powder |
| CN107851796A (en) * | 2015-07-16 | 2018-03-27 | 昭和电工株式会社 | The manufacture method and carbon material for battery electrode of secondary cell graphitiferous carbon dust |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104600312A (en) * | 2014-12-30 | 2015-05-06 | 东莞市凯金新能源科技有限公司 | Preparation method of lithium ion battery porous negative electrode material |
| CN107534149A (en) * | 2015-05-11 | 2018-01-02 | 昭和电工株式会社 | The manufacture method of ion secondary battery cathode material lithium graphite powder |
| CN107851796A (en) * | 2015-07-16 | 2018-03-27 | 昭和电工株式会社 | The manufacture method and carbon material for battery electrode of secondary cell graphitiferous carbon dust |
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