CN112310382A - SiCO-Si microsphere prepared by coating Si with SiCO and preparation method thereof - Google Patents
SiCO-Si microsphere prepared by coating Si with SiCO and preparation method thereof Download PDFInfo
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Abstract
The invention provides a SiCO-Si microsphere prepared by coating Si with SiCO and a preparation method thereof. According to the method, a SiCO precursor is adopted to coat nano Si powder into balls by an emulsion thermosetting method, and the SiCO-Si microspheres are finally prepared through the steps of curing and ceramization. The SiCO-Si microspheres prepared by the method can be applied to silicon cathode materials to improve the conductivity of the materials, reduce the volume effect and improve the cycle performance. The prepared SiCO-Si microspheres have the advantages of good sphericity, easily-adjusted components and high uniformity, and the balling process has the advantages of simple and convenient process, strong operability, short production period and the like, and has the potential of large-scale production and commercial application.
Description
Technical Field
The invention belongs to the field of silicon-carbon cathode materials, further belongs to the field of Si powder coating, and relates to a SiCO-Si microsphere prepared by coating Si with SiCO and a preparation method thereof.
Background
The silicon material belongs to alloy cathode material, and when the silicon cathode material is completely lithiated into Li22Si5The theoretical specific capacity is 4200 m Ah/g, which is more than 10 times of the theoretical specific capacity of the graphite cathode material. Meanwhile, the lithiation potential of the silicon anode material is lower (<0.5V), the voltage platform is slightly higher than graphite, lithium precipitates are difficult to form on the surface of the material, and the safety performance is better. The silicon negative electrode material becomes a relay carbon-based negative electrode material and a lithium titanate negative electrodeAfter the material is prepared, the cathode material has commercial application potential. But its commercial application also faces some challenges. First, the silicon negative electrode material is a typical semiconductor material and has a slightly lower electrical conductivity. The silicon negative electrode material is easy to expand or contract in volume (about 300%) in the charging and discharging process, so that the pulverization and the structural collapse of the material are caused, and further, the capacity attenuation and the cycle performance reduction are caused. In addition, a Solid Electrolyte Interface (SEI) film on the surface of the silicon negative electrode material is not easily stabilized due to the volume effect, which causes problems of electrolyte consumption and material corrosion. In order to solve the problems of the silicon material size effect, the binder, the silicon/carbon compounding and the like, researchers do a lot of work to improve the performance of the silicon cathode material to a certain extent.
The carbon material has excellent conductivity and mechanical properties, so the conductivity of the silicon negative electrode material is generally improved by adding the carbon material, the volume effect is reduced, and the structural stability is improved. At present, carbon materials such as carbon nanotubes and the like are mainly added in a ball milling and blending mode to form a three-dimensional network structure so as to improve the conductivity and stability of a system. However, the network structure has a large volume and a large stress, and the volume effect of Si is relieved to some extent but the whole structure is gradually destroyed in multiple charging and discharging, so that the network structure has certain limitations. Therefore, the Si powder is coated with carbon and then prepared into a microstructure, so that the mechanical and electrical properties of the silicon-carbon negative electrode material can be further improved.
Disclosure of Invention
The invention aims to solve the problems that the electronic conductivity and the ionic conductivity of a silicon-carbon cathode material are improved, the volume effect of the material in the charge-discharge cycle process is buffered, and the SiCO-Si microsphere prepared by coating Si with SiCO and the preparation method thereof are provided. The method adopts SiCO precursor to coat nano Si powder into balls by an emulsion thermosetting method, and finally prepares the SiCO-Si microspheres through the steps of curing and ceramization. The method has the advantages of simple process, strong operability, short production period and potential for large-scale production and commercial application. The preparation method provides the SiCO-Si microsphere, and the prepared SiCO-Si microsphere has the advantages of good sphericity, easily-adjusted components and high uniformity.
On one hand, the invention provides a preparation method of SiCO-Si microspheres by using SiCO to coat Si, which comprises the following steps:
1) mixing and stirring nano silicon powder and a SiCO precursor to prepare slurry, wherein the volume fraction of the nano silicon powder is 10-50%, adding 1-5% of a dispersing agent, and stirring for 12-24 hours;
2) the resulting slurry was added to the emulsion and stirred. Stirring for 2-6 hours, and then curing for 1-4 hours;
3) washing and centrifuging the emulsion after the solidification is finished, and repeating the ball washing process for 2-5 times to finally obtain the resin-coated nano Si microspheres;
4) and cracking the resin microspheres in a protective atmosphere at the temperature of 800-1200 ℃, keeping the temperature for 1-2 hours, and cooling to obtain the SiCO-Si microspheres.
In the step 1), the particle size of the nano Si powder is 50-300 nm.
In the step 1), the silicon carbide precursor is poly-silicon acetylene, the poly-silicon acetylene is high polymer resin with a main chain of Si and alkynyl which are alternately linked, and the poly-silicon acetylene is liquid brownish red resin at normal temperature and has good fluidity.
In the step 1), the number average molecular weight of the silicon carbide precursor is 1000-2000.
In the step 1), the dispersing agent is selected from cis-9-octadecenoic acid, KOS110, hydroquinone and the like.
In the step 1), the stirring mode is magnetic stirring, and the stirring speed is 300-1000 r/min.
In the step 1), the slurry is prepared by mixing 10-50% of nano silicon powder by volume, adding 1-5% of dispersing agent and SiCO precursor for stirring for 12-24 hours.
In the step 2), the emulsion is selected from glycerol, castor oil, dimethyl silicone oil and the like.
In the step 2), the stirring mode is magnetic stirring, the stirring speed is 300-1000 r/min, and the stirring time is 2-6 hours.
In the step 2), the curing temperature is 160-300 ℃, and the curing time is 1-4 hours.
In the step 3), the detergent is selected from n-hexane, tetrahydrofuran, acetone and the like.
In the step 3), the centrifugation speed is 6000-9000 r/min, and the centrifugation time is 8-12 minutes.
In the step 3), the ball washing process is repeated for 2-5 times so as to fully wash the emulsion on the surface of the microsphere.
In the step 4), the temperature rise system is to heat up to 200-300 ℃ at the temperature rise rate of 2-6 ℃/min and preserve heat for 1-2 hours, and then to heat up to 800-1200 ℃ at the temperature rise rate of 5-10 ℃/min and preserve heat for 1-2 hours.
In step 4), the protective atmosphere is preferably N2The cooling mode is furnace cooling, and SiCO-Si microspheres can be obtained after cooling.
On the other hand, the invention also provides the SiCO-Si microsphere prepared by the preparation method.
In conclusion, the invention provides a SiCO-Si microsphere prepared by coating Si with SiCO and a preparation method thereof. The scheme of the invention has the following advantages:
1. the preparation method provided by the invention is simple to operate and simple and convenient in process, and the SiCO-Si microspheres are prepared by an emulsion thermosetting method in a simple blending and stirring mode, so that the method has low requirement on equipment, has strong operability, is short in process period, small in difficulty in enlarging production scale and has wide commercial potential;
2. the SiCO-Si microsphere provided by the invention has better sphericity, better uniformity and better isotropy. When applied to a negative electrode material, the influence of the size effect can be greatly reduced during charge and discharge cycles. Due to good isotropy, the internal stress of the material can be reduced when the volume of Si in the material is changed, and the structural stability and integrity of the material are maintained, so that the charge and discharge performance of the battery is improved;
3. the SiCO-Si microsphere provided by the invention can adjust the content of Si powder according to specific requirements, the proportion of each element in SiCO can be adjusted by adjusting the molecular structure of a precursor, the particle size of the prepared SiCO-Si microsphere can be adjusted by adjusting the stirring speed and the system viscosity, and the operability is high;
4. the SiCO ceramic in the SiCO-Si microsphere provided by the invention is amorphous, amorphous SiCO can well wrap Si powder particles, amorphous C distributed in the SiCO can be uniformly dispersed in the whole system, a uniform conductive network is provided for the system, and the wrapped Si particles are communicated. Compared with the traditional carbon coating, the SiCO ceramic has higher hardness and strength, is more difficult to collapse due to the volume effect of Si, and has a more stable structure.
Drawings
Fig. 1 is a flowchart illustrating a method for preparing SiCO-Si microspheres by coating Si with SiCO according to an embodiment of the present invention.
FIG. 2 is an SEM photograph of SiCO-Si microspheres prepared by coating Si with SiCO as exemplified in the examples of the present invention.
Detailed Description
The following examples are provided to illustrate the practice and advantages of the present invention, but are not intended to limit the scope of the invention.
Example 1
The particle size of nano silicon powder is 50nm, the SiCO precursor is polysilacetylene with the number average molecular weight of 1200, the nano silicon powder with the volume fraction of 10 percent is mixed and stirred to prepare slurry, cis-9-octadecenoic acid is used as a dispersing agent, the adding amount is 1 percent, and the slurry is stirred for 16 hours. The emulsion was selected to be dimethicone with a viscosity of 350mpa · s, and the resulting slurry was added to dimethicone and stirred. Stirring for 2 hours, and then curing at 180 ℃ for 4 hours. And (3) after the solidification is finished, washing off the dimethyl silicone oil and centrifuging, and repeating the ball washing process for 3 times to finally obtain the resin-coated nano Si microspheres. Adding resin microspheres in N2Cracking under the atmosphere, wherein the cracking temperature is 800 ℃, the heat preservation time is 1 hour, and cooling to obtain the SiCO-Si microspheres. The particle size of the obtained SiCO-Si microspheres is 40-60 mu m, the variation coefficient is 36%, the sphericity is better, and the bonding phenomenon is less.
Example 2
Selecting nanoThe particle size of the silicon powder is 50nm, the SiCO precursor is formed by mixing and stirring polysilacetylene with the number average molecular weight of 1200 to prepare slurry, wherein the volume fraction of the nano silicon powder is 30%, Tween 80 is selected as a dispersing agent, the adding amount is 3%, and the slurry is stirred for 16 hours. The emulsion was selected as dimethicone with a viscosity of 800mpa · s, and the resulting slurry was added to dimethicone and stirred. Stirring for 2 hours, and then curing at 200 ℃ for 4 hours. And (4) after the solidification is finished, washing off the dimethyl silicone oil and centrifuging, and repeating the ball washing process for 5 times to finally obtain the resin-coated nano Si microspheres. Adding resin microspheres in N2Cracking under the atmosphere, wherein the cracking temperature is 1000 ℃, the heat preservation time is 1 hour, and cooling to obtain the SiCO-Si microspheres. The particle size of the obtained SiCO-Si microspheres is 80-120 mu m, the variation coefficient is 48%, the sphericity is better, and a certain bonding phenomenon is realized.
Example 3
The particle size of nano silicon powder is 50nm, the SiCO precursor is polysilacetylene with the number average molecular weight of 1200, the nano silicon powder with the volume fraction of 40 percent and Tween 80 as a dispersing agent are mixed and stirred to prepare slurry, the adding amount is 3 percent, and the slurry is stirred for 16 hours. The emulsion was selected to be dimethicone with a viscosity of 1000mpa · s, and the resulting slurry was added to dimethicone and stirred. Stirring for 2 hours, and then curing at 180 ℃ for 4 hours. And (4) after the solidification is finished, washing off the dimethyl silicone oil and centrifuging, and repeating the ball washing process for 5 times to finally obtain the resin-coated nano Si microspheres. Adding resin microspheres in N2Cracking under the atmosphere, wherein the cracking temperature is 1000 ℃, the heat preservation time is 1 hour, and cooling to obtain the SiCO-Si microspheres. The particle size of the obtained SiCO-Si microspheres is 70-100 mu m, the variation coefficient is 40%, the sphericity is poor, and a certain bonding phenomenon is realized.
Example 4
The particle size of nano silicon powder is 100nm, the SiCO precursor is polysilacetylene with the number average molecular weight of 1200, the nano silicon powder with the volume fraction of 10 percent is mixed and stirred to prepare slurry, KOS110 is used as a dispersing agent, the adding amount is 1 percent, and the slurry is stirred for 16 hours. The emulsion is selected to be dimethyl silicone oil with the viscosity of 600 mpa-s, and the obtained slurry isAdding into dimethyl silicone oil, and stirring. Stirring for 2 hours, and then curing at 180 ℃ for 4 hours. And (4) after the solidification is finished, washing off the dimethyl silicone oil and centrifuging, and repeating the ball washing process for 4 times to finally obtain the resin-coated nano Si microspheres. Adding resin microspheres in N2Cracking under the atmosphere, wherein the cracking temperature is 1200 ℃, the heat preservation time is 1 hour, and cooling to obtain the SiCO-Si microspheres. The particle size of the obtained SiCO-Si microspheres is 90-110 mu m, the variation coefficient is 34%, the sphericity is better, and the bonding phenomenon is less.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as devised in the present application is not limited to the specific combination of features described above, but also covers other embodiments having any combination of features described above or of features together without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (9)
1. A SiCO-Si microsphere prepared by coating Si with SiCO and a preparation method thereof are characterized by comprising the following steps:
mixing and stirring nano silicon powder and a SiCO precursor to prepare slurry, wherein the volume fraction of the nano silicon powder is 10-50%, adding 1-5% of a dispersing agent, and stirring for 12-24 hours; adding the obtained slurry into the emulsion, and stirring; stirring for 2-6 hours, and then curing for 1-4 hours; washing and centrifuging the emulsion after the solidification is finished, and repeating the ball washing process for 2-5 times to finally obtain the resin-coated nano Si microspheres; and cracking the resin microspheres in a protective atmosphere at the temperature of 800-1200 ℃, keeping the temperature for 1-2 hours, and cooling to obtain the SiCO-Si microspheres.
2. The method according to claim 1, wherein the nano Si powder has a particle size of 50 to 300 nm.
3. The method according to claim 1, wherein the silicon carbide precursor is a polysilyne which is a liquid reddish brown resin at normal temperature and has good fluidity.
4. The method according to claim 1, wherein the dispersant of step 1 is selected from cis-9-octadecenoic acid, KOS110, hydroquinone, etc.
5. The method of claim 1, wherein the emulsion in step 2 is selected from the group consisting of glycerin, castor oil, dimethicone, and the like.
6. The method according to claim 1, wherein the stirring rate in the step 2 is 300 to 1000 r/min.
7. The method according to claim 1, wherein the detergent in step 3 is selected from n-hexane, tetrahydrofuran, acetone, etc.
8. The method according to claim 1, wherein the temperature rise rate in step 4 is 2-5 ℃/min, and the protective atmosphere is preferably N2The cooling mode is furnace cooling.
9. A SiCO-Si microsphere produced by the production method according to any one of claims 1 to 8.
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Citations (6)
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| CN101047244A (en) * | 2006-03-27 | 2007-10-03 | 信越化学工业株式会社 | SiCO-Li composite, making method, and non-aqueous electrolyte secondary cell negative electrode material |
| CN102303978A (en) * | 2011-06-03 | 2012-01-04 | 清华大学 | Method for preparing porous silicon carbide ceramic with high strength |
| CN103137968A (en) * | 2011-11-30 | 2013-06-05 | 北京有色金属研究总院 | Positive electrode composite material for lithium ion batteries and preparation method thereof |
| CN104311143A (en) * | 2014-10-14 | 2015-01-28 | 中国人民解放军国防科学技术大学 | Method for improving oxidization resistance of carbon aerogel composite material |
| CN104362311A (en) * | 2014-09-23 | 2015-02-18 | 清华大学深圳研究生院 | Silicon-carbon composite microsphere anode material and preparation method thereof |
| CN104659341A (en) * | 2013-11-25 | 2015-05-27 | 北京有色金属研究总院 | Composite negative material for lithium ion battery and manufacture method of composite negative material |
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2020
- 2020-11-23 CN CN202011325581.8A patent/CN112310382A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101047244A (en) * | 2006-03-27 | 2007-10-03 | 信越化学工业株式会社 | SiCO-Li composite, making method, and non-aqueous electrolyte secondary cell negative electrode material |
| CN102303978A (en) * | 2011-06-03 | 2012-01-04 | 清华大学 | Method for preparing porous silicon carbide ceramic with high strength |
| CN103137968A (en) * | 2011-11-30 | 2013-06-05 | 北京有色金属研究总院 | Positive electrode composite material for lithium ion batteries and preparation method thereof |
| CN104659341A (en) * | 2013-11-25 | 2015-05-27 | 北京有色金属研究总院 | Composite negative material for lithium ion battery and manufacture method of composite negative material |
| CN104362311A (en) * | 2014-09-23 | 2015-02-18 | 清华大学深圳研究生院 | Silicon-carbon composite microsphere anode material and preparation method thereof |
| CN104311143A (en) * | 2014-10-14 | 2015-01-28 | 中国人民解放军国防科学技术大学 | Method for improving oxidization resistance of carbon aerogel composite material |
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