CN109659549B - Preparation method of multi-stage structure silicon-porous carbon composite negative electrode material for lithium battery - Google Patents
Preparation method of multi-stage structure silicon-porous carbon composite negative electrode material for lithium battery Download PDFInfo
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- CN109659549B CN109659549B CN201910032944.XA CN201910032944A CN109659549B CN 109659549 B CN109659549 B CN 109659549B CN 201910032944 A CN201910032944 A CN 201910032944A CN 109659549 B CN109659549 B CN 109659549B
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- 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
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- H—ELECTRICITY
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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
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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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- 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
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Abstract
The invention relates to a preparation method of a silicon/porous carbon composite anode material with a multilevel structure, belonging to the field of materials for lithium batteries. And mixing the multilevel structure silicon and porous carbon by adopting a mechanical mixing method to obtain the composite cathode active material, wherein the mass ratio of the multilevel structure silicon to the porous carbon is 0.11-0.43. Compared with graphite, the porous carbon adopted by the invention can effectively improve the liquid absorption amount of the electrolyte on one hand, and further accelerate the transmission of ions; on the other hand, the high conductivity of the porous carbon accelerates the transmission of electrons; thereby obtaining the high-rate lithium battery cathode material.
Description
Technical Field
The invention relates to a preparation method of a multi-stage structure silicon-porous carbon composite anode material for a lithium battery. The multilevel-structure silicon-porous carbon composite negative electrode material obtained by the method can obviously improve the liquid absorption amount and the electronic conductivity of the electrolyte, further obviously improve the transmission speed of lithium ions and electrons, and obtain the high-rate lithium battery negative electrode material.
Background
In recent years, silicon has been known for its high theoretical specific capacity (4200mAh g)-1) Is widely used as a negative electrode material of a lithium ion battery. However, due to its low electronic conductivity and structural instability caused by large volume change during charge and discharge, silicon and graphite are generally mechanically mixed in a certain proportion to serve as a composite negative active material, and better cycle stability is obtained at the expense of a part of capacity.
The graphite and the silicon are mixed, so that the structural instability of the silicon can be relieved, but the electronic conductivity of the graphite is not high; meanwhile, the specific surface area of the graphite is small, so that the electrolyte cannot be effectively adsorbed, and the ionic conductivity is not high. Therefore, in order to obtain a stable high-rate silicon-based negative electrode material, a carbon material with high conductivity and high specific surface area is urgently needed to replace graphite and be mixed with silicon to be used as a negative electrode material of a lithium ion battery.
Disclosure of Invention
The invention aims to disclose a preparation method of a multi-level structure silicon-porous carbon composite negative electrode material for a lithium battery, which is a research for compounding porous carbon and multi-level structure silicon as a negative electrode material of the lithium battery for the first time.
In order to achieve the aim, the method adopts a mechanical mixing method to mix the multilevel structure silicon and the porous carbon according to a certain proportion.
The specific process comprises the following steps:
(1) and preparing the multilevel structure silicon material (Si @ C @ CNT) by adopting spray drying equipment. Firstly, a certain proportion of silicon nano-particles, carbon nano-tubes, sucrose and P123 (EO)20PO70EO20Dispersing in a mixed solvent of ethanol and water to form a mixed solution, wherein EO and PO are ethylene oxide and propylene oxide, respectively; then, converting the mixed solution into fog drops through ultrasonic atomization, and feeding the fog drops into a heated tube furnace by nitrogen to be condensed into solid particles; and finally, calcining the solid particles collected by using filter paper at high temperature in an argon atmosphere to form the Si @ C @ CNT composite particles.
(2) And mechanically grinding the multilevel-structure silicon material Si @ C @ CNT and porous carbon to obtain the Si @ C @ CNT-porous carbon composite negative electrode material.
Preferably, the mass ratio of the silicon nanoparticles, the carbon nanotubes, the sucrose and the P123 in the step (1) is in a range of 1: (0.05-0.1): (0.5-1): (0.5-1).
Preferably, the volume ratio of ethanol to water in the step (1) is in the range of (2-5): 1.
preferably, the flow rate of nitrogen in step (1) is 0.3-0.6L min-1The heating temperature of the tube furnace is 300-500 ℃.
Preferably, the high-temperature calcination temperature in the step (1) is 800-; the flow rate of argon is 0.2-1L min-1。
Preferably, the porous carbon material described in step (2) has a substantially two-dimensional lamellar structure.
Preferably, the porous carbon material in the step (2) has a significant mesoporous structure of 2-10 nm.
Preferably, the mass ratio of Si @ C @ CNT to porous carbon in step (2) is 0.11 to 0.43.
The application field of the multilevel structure silicon-porous carbon composite material includes, but is not limited to, lithium ion batteries.
The invention has the advantages that:
the invention provides a preparation method of a silicon-porous carbon composite material with a multilevel structure. The invention adopts porous carbon and multilevel structure silicon to compound as the lithium ion battery cathode material for the first time. Compared with the prior graphite, on one hand, the large specific surface area of the porous carbon can effectively improve the liquid absorption amount of the electrolyte, thereby accelerating the transmission of ions; on the other hand, the high conductivity of the porous carbon accelerates the transmission of electrons; thereby obtaining the high-rate lithium battery cathode material.
Drawings
FIG. 1 is a graph of rate performance of Si @ C @ CNT-porous carbon electrode obtained in example 1 of the present invention;
FIG. 2 is a graph of Si @ C @ CNT-porous carbon electrode obtained in example 2 of the present invention and Si @ C @ CNT-graphite electrode obtained in comparative example 2 at 160mA g-1Comparing the lower cycle performance curve;
FIG. 3 is a graph of Si @ C @ CNT-porous carbon electrode obtained in example 3 of the invention versus the Si @ C @ CNT-graphite electrode obtained in comparative example 3 at 800mA g-1Comparing the lower cycle performance curve;
Detailed Description
The invention will be described in more detail with reference to the following figures and examples, but the scope of the invention is not limited thereto.
Example 1: a preparation method of a multi-level structure silicon-porous carbon composite material comprises the following specific steps:
(1) and preparing the multilevel structure silicon material (Si @ C @ CNT) by adopting spray drying equipment. First, 1.5g of silicon nanoparticles, 100mg of carbon nanotubes, 1g of sucrose and 1.5g P123 (EO)20PO70EO20Where EO and PO are ethylene oxide and propylene oxide, respectively) was dispersed in 200mL of a mixed solvent of ethanol and water (ethanol: water 3:1, volume ratio) to form a mixed solution; then, the mixed solution was converted into mist droplets by ultrasonic atomization and was purged with nitrogen (0.5L min)-1) Feeding into a heated tube furnace (400 ℃) to be condensed into solid particles; finally, the solid particles collected with filter paper were placed under argon atmosphere (0.4L min)-1) The Si @ C @ CNT composite particles are formed after calcining for 1h at high temperature (900 ℃).
(2) Mechanically grinding the multilevel-structure silicon material Si @ C @ CNT and porous carbon in a mass ratio of 1:9 to obtain the Si @ C @ CNT-porous carbon composite negative electrode material.
And (3) electrochemical performance testing: adding 92mg of Si @ C @ CNT-porous carbon composite negative electrode material, 3mg of carbon black and 5mg of sodium carboxymethylcellulose (CMC) into 2ml of deionized water, uniformly mixing to obtain slurry, coating the slurry on a copper foil, carrying out vacuum drying at 100 ℃ for 12h, and cutting into a wafer with the diameter of 10mm as a working electrode; the lithium sheet is used as a reference electrode and a counter electrode; 1mol L-1LiPF6A solution dissolved in ethylene carbonate/diethyl carbonate (EC/DEC, 1:1, volume ratio) and added with 5 vol% fluoroethylene carbonate additive as an electrolyte; celgard 2400 was used as the separator. And assembling the electrode, the electrolyte and the diaphragm into a No. 2032 button cell for electrochemical performance test.
The rate capability of the Si @ C @ CNT-porous carbon composite anode material prepared in the embodiment is shown in FIG. 1, and as can be seen from FIG. 1, the material has very high rate capability at 4A g-1Can still maintain 570mAh g under high current-1The capacity of (c).
Comparative example 1: different from the embodiment 1, the multilevel-structure silicon material Si @ C @ CNT and graphite are mechanically ground at the mass ratio of 1:9 to obtain the Si @ C @ CNT-graphite composite negative electrode material. The other parts are assembled into a battery to be tested for electrochemical performance as in example 1.
Example 2: different from the embodiment 1, the Si @ C @ CNT-porous carbon composite negative electrode material is obtained by mechanically grinding the multilevel-structure silicon material Si @ C @ CNT and the porous carbon at the mass ratio of 2: 8. The other parts are assembled into a battery to be tested for electrochemical performance as in example 1.
Comparative example 2: different from the embodiment 2, the multilevel-structure silicon material Si @ C @ CNT and graphite are mechanically ground according to the mass ratio of 2:8 to obtain the Si @ C @ CNT-graphite composite negative electrode material. The other parts are assembled into a battery to be tested for electrochemical performance as in example 1.
Example 3: different from the embodiment 1, the Si @ C @ CNT-porous carbon composite negative electrode material is obtained by mechanically grinding the multilevel-structure silicon material Si @ C @ CNT and the porous carbon at the mass ratio of 3: 7. The other parts are assembled into a battery to be tested for electrochemical performance as in example 1.
Comparative example 3: different from the embodiment 2, the multilevel-structure silicon material Si @ C @ CNT and graphite are mechanically ground according to the mass ratio of 3:7 to obtain the Si @ C @ CNT-graphite composite negative electrode material. The other parts are assembled into a battery to be tested for electrochemical performance as in example 1.
The Si @ C @ CNT-porous carbon composite negative electrode material prepared in example 2 and the Si @ C @ CNT-graphite composite negative electrode material prepared in comparative example 2 are 160mA g-1The following cycle performance pairs are shown in fig. 2. As can be seen from FIG. 2, the capacity and cycling stability of the Si @ C @ CNT-porous carbon electrode is significantly higher than that of the Si @ C @ CNT-graphite electrode. After 100 cycles, the capacity retention of the Si @ C @ CNT-porous carbon electrode was 84%, while the Si @ C @ CNT-graphite electrode was 71%.
The Si @ C @ CNT-porous carbon composite anode material prepared in example 3 and the Si @ C @ CNT-graphite composite anode material prepared in comparative example 3 are at 800mA g-1The following cycle performance pairs are shown in fig. 3. As can be seen from FIG. 3, the capacity and cycling stability of the Si @ C @ CNT-porous carbon electrode is significantly higher than that of the Si @ C @ CNT-graphite electrode. At 80% capacity retention, the Si @ C @ CNT-porous carbon electrode can cycle 200 weeks, whereas the Si @ C @ CNT-graphite electrode can cycle only 100 weeks.
Claims (3)
1. A preparation method of a multi-level structure silicon-porous carbon composite anode material for a lithium battery is characterized by comprising the following steps of: the method comprises the following steps:
(1) preparing a multi-level structure silicon material Si @ C @ CNT by adopting spray drying equipment; firstly, a certain proportion of silicon nano-particles, carbon nano-tubes, sucrose and P123 (EO)20PO70EO20) Dispersing in a mixed solvent of ethanol and water to form a mixed solution, wherein EO and PO are ethylene oxide and propylene oxide, respectively; then, converting the mixed solution into fog drops through ultrasonic atomization, and feeding the fog drops into a heated tube furnace by nitrogen to be condensed into solid particles; finally, calcining the solid particles collected by the filter paper at high temperature in an argon atmosphere to form Si @ C @ CNT composite particles;
(2) mechanically grinding a multilevel-structure silicon material Si @ C @ CNT and porous carbon to obtain a Si @ C @ CNT-porous carbon composite negative electrode material;
wherein, the mass ratio range of the silicon nano-particles, the carbon nano-tubes, the sucrose and the P123 in the step (1) is 1: (0.05-0.1): (0.5-1): (0.5-1);
wherein the volume ratio of the ethanol to the water in the step (1) is (2-5): 1;
wherein, the porous carbon material in the step (2) has an obvious mesoporous structure of 2-10 nm;
the flow rate of the nitrogen in the step (1) is 0.3-0.6L min-1The heating temperature of the tube furnace is 300-500 ℃;
the high-temperature calcination temperature in the step (1) is 800-1000 ℃, and the calcination time is 1-3 h; the flow rate of argon is 0.2-1L min-1。
2. The method for preparing the multi-level structure silicon-porous carbon composite anode material for the lithium battery as claimed in claim 1, wherein the method comprises the following steps: the porous carbon material in the step (2) has an obvious two-dimensional lamellar structure.
3. The method for preparing the multi-level structure silicon-porous carbon composite anode material for the lithium battery as claimed in claim 1, wherein the method comprises the following steps: the mass ratio of Si @ C @ CNT to the porous carbon in the step (2) is 0.11-0.43.
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|---|---|---|---|---|
| CN102569759A (en) * | 2012-01-05 | 2012-07-11 | 北京理工大学 | Process for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries |
| CN107492649A (en) * | 2017-08-25 | 2017-12-19 | 南陵县生产力促进中心 | A kind of silicon carbon material for cathode of lithium battery and preparation method thereof |
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| CN104934573A (en) * | 2014-03-19 | 2015-09-23 | 苏州格瑞动力电源科技有限公司 | In-situ solid-phase synthesis method of silicon-graphene spheroidal composite material with multilevel structure and application thereof |
| CN106711415B (en) * | 2016-12-19 | 2019-05-10 | 宁波富理电池材料科技有限公司 | A kind of porous silicon composite cathode material and preparation method thereof |
| CN106957056A (en) * | 2017-03-09 | 2017-07-18 | 武汉工程大学 | A kind of synthetic method of the compound feature onion shape mesoporous material of carbon silicon |
| CN107221654B (en) * | 2017-05-25 | 2020-05-12 | 济南大学 | Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof |
| CN107528063A (en) * | 2017-08-01 | 2017-12-29 | 河南新太行电源股份有限公司 | A kind of preparation method and applications of core shell structure silicon/carbon material of cornstarch porous carbon encapsulation |
| CN108172812A (en) * | 2018-01-30 | 2018-06-15 | 郑州中科新兴产业技术研究院 | A kind of silicon-carbon cathode material available for power battery and preparation method thereof |
| CN108630917A (en) * | 2018-04-04 | 2018-10-09 | 合肥国轩高科动力能源有限公司 | A kind of Si@C@fibrous carbon@C composites and its preparation method and application |
| CN108682785B (en) * | 2018-05-17 | 2021-04-06 | 桑德新能源技术开发有限公司 | Negative electrode for lithium battery, preparation method of negative electrode and lithium battery |
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| CN102569759A (en) * | 2012-01-05 | 2012-07-11 | 北京理工大学 | Process for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries |
| CN107492649A (en) * | 2017-08-25 | 2017-12-19 | 南陵县生产力促进中心 | A kind of silicon carbon material for cathode of lithium battery and preparation method thereof |
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