CN111807376A - Graphene modified silicon monoxide/carbon composite material and preparation method thereof - Google Patents
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Abstract
The invention provides a graphene modified silicon monoxide/carbon composite material and a preparation method thereof, wherein the preparation method comprises the following steps: fully mixing graphene, silicon monoxide and a first carbon source to obtain a first mixture; heating the first mixture in an inert atmosphere to perform first carbonization treatment; fully mixing the material subjected to the first carbonization treatment, graphite and a second carbon source to obtain a second mixture; and heating the second mixture in an inert atmosphere, and performing second carbonization treatment to obtain the graphene modified silicon monoxide/carbon composite material. The method has simple process and low cost, and the obtained composite material can show the characteristics of high capacity, high first coulombic efficiency and good cycle performance when being used as the lithium ion battery cathode material, thereby having good application prospect.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a graphene modified silicon monoxide/carbon composite material and a preparation method thereof.
Background
With the rapid development of new energy electric vehicles, the requirements of lithium ion batteries on energy density are higher and higher. The improvement of the energy density is mainly benefited by the capacity improvement of the anode material and the cathode material. Compared with the anode material, the anode material has larger lifting space. At present, the commercial negative electrode materials are mainly graphite materials, but the development of high-energy density lithium ion batteries is restricted due to the low capacity of the graphite materials. Therefore, it is increasingly important to develop new anode materials having higher capacity, low cost, long life, and safety and reliability.
The silicon material has high capacity and moderate voltage platform, can effectively improve the energy density of the battery, and has good application prospect. However, elemental silicon has a large volume change during charge and discharge, thereby causing rapid deterioration of electrochemical cycle performance. Although the capacity of silicon monoxide is slightly lower than that of simple substance silicon, the capacity of silicon monoxide is still far higher than that of graphite-based negative electrode materials, and the volume expansion of silicon monoxide is relatively small, so that the silicon monoxide is expected to become a next-generation high-energy-density lithium ion battery negative electrode material.
However, the silicon monoxide (SiO) alone as the negative electrode material of the lithium ion battery still cannot avoid the rapid capacity attenuation caused by the volume expansion, so a new preparation method of the negative electrode material of the battery is needed to modify the silicon monoxide, so that the negative electrode material of the lithium ion battery with higher capacity and better cycle performance is obtained.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The present invention is directed to overcome at least one of the above-mentioned drawbacks of the prior art, and provides a graphene-modified silicon monoxide/carbon (SiO/C) composite material and a preparation method thereof, so as to solve the problem that the conventional lithium ion battery negative electrode material is difficult to achieve both high capacity and low volume expansion.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a graphene modified silicon monoxide/carbon composite material, which comprises the following steps: fully mixing graphene, silicon monoxide and a first carbon source to obtain a first mixture; heating the first mixture in an inert atmosphere to perform first carbonization treatment; fully mixing the material subjected to the first carbonization treatment, graphite and a second carbon source to obtain a second mixture; and heating the second mixture in an inert atmosphere, and performing second carbonization treatment to obtain the graphene modified silicon monoxide/carbon composite material.
According to one embodiment of the invention, the first carbon source and the second carbon source are each independently selected from one or more of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polyvinylidene fluoride, polyethylene oxide, polyvinyl chloride, polyethylene, chlorinated polyethylene, glucose and pitch.
According to one embodiment of the invention, obtaining the first mixture comprises the steps of: dispersing graphene, silicon monoxide and a first carbon source into water to obtain a first dispersion liquid; stirring the first dispersion liquid for 1-24 h, and then carrying out ball milling treatment for 1-24 h to obtain a first mixed liquid; and drying the first mixed solution to obtain a first mixture.
According to one embodiment of the invention, the mass ratio of the graphene to the silicon monoxide is 1 (10-100), and the mass ratio of the silicon monoxide to the first carbon source is 1: 10-100: 1.
According to one embodiment of the invention, obtaining the second mixture comprises the steps of: dispersing the material subjected to the first carbonization treatment, graphite and a second carbon source into a solvent to obtain a second dispersion liquid; and drying the second dispersion to obtain a second mixture.
According to one embodiment of the invention, the solvent is selected from one or more of ethanol, acetone and water.
According to one embodiment of the invention, the mass ratio of the material after the first carbonization treatment to the graphite is 1:1 to 1:100, and the mass ratio of the graphite to the second carbon source is 1:10 to 100: 1.
According to one embodiment of the invention, the temperature of the first carbonization treatment is 300-1000 ℃ and the time is 1-10 h; the temperature of the second carbonization treatment is 300-1000 ℃, and the time is 1-10 h.
The invention also provides a graphene modified silicon monoxide/carbon composite material prepared by the method.
According to the technical scheme, the invention has the beneficial effects that:
according to the invention, a specific process is adopted, the silicon monoxide/carbon composite material is modified by using the graphene, and the obtained composite material can show the characteristics of high capacity, high first coulombic efficiency and good cycle performance when being used as a lithium ion battery cathode material. The preparation process of the composite material has low cost, high production efficiency, rich raw material resources, easy large-scale production and good industrial application prospect.
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The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope image of the graphene-modified SiO/C composite material of example 1.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a graphene modified silicon monoxide/carbon composite material, which comprises the following steps: fully mixing graphene, silicon monoxide and a first carbon source to obtain a first mixture; heating the first mixture in an inert atmosphere to perform first carbonization treatment; fully mixing the material subjected to the first carbonization treatment, graphite and a second carbon source to obtain a second mixture; and heating the second mixture in an inert atmosphere, and performing second carbonization treatment to obtain the graphene modified silicon monoxide/carbon composite material.
According to the invention, the silicon material has high capacity and moderate voltage platform, can effectively improve the energy density of the battery, but is easy to expand in volume during the use process, thereby causing the rapid attenuation of the battery capacity. The inventor of the invention finds that the graphene is adopted to modify the silicon monoxide/carbon composite material, so that the graphene serving as a negative electrode material has high capacity, high first coulombic efficiency and good cycle performance. The reason is that the excellent conductivity of the graphene can improve the conductivity of the whole composite material, and the good flexibility can effectively relieve the volume expansion of the silicon monoxide.
The following specifically describes a process flow for preparing the graphene-modified silicon monoxide/carbon composite material of the present invention.
First, graphene, silicon monoxide and a first carbon source are fully mixed to obtain a first mixture. Wherein the first carbon source includes, but is not limited to, one or more of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polyvinylidene fluoride, polyethylene oxide, polyvinyl chloride, polyethylene, chlorinated polyethylene, glucose, and asphalt.
In some embodiments, the step of obtaining the first mixture comprises: dispersing graphene, silicon monoxide and a first carbon source into water to obtain a first dispersion liquid; stirring the first dispersion liquid and then performing ball milling treatment to obtain a first mixed liquid; and drying the first mixed solution, such as freeze-drying or drying, to obtain a first mixture.
The mass ratio of the graphene to the silicon monoxide is 1 (10-100), for example, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:90, etc., preferably 1 (10-20). The mass ratio of the SiO to the first carbon source is 1:10 to 100:1, for example, 1:10, 1:5, 5:1, 9:1, 10:1, 20:1, 50:1, and preferably 5:1 to 20: 1.
The stirring time of the first dispersion liquid is 1-24 h, preferably 5-10 h, and the ball milling treatment time is 1-24 h, preferably 5-10 h. The graphene, the silicon monoxide and the first carbon source are fully mixed and dispersed in a mode of combining stirring and ball milling treatment. It is noted that when the first carbon source is polyvinyl alcohol and/or polyvinylpyrrolidone, the first carbon source may also function as a dispersant, so that the graphene can be dispersed in the solution more uniformly.
Next, the first mixture is heated in an inert atmosphere to perform a first carbonization treatment. Wherein the inert atmosphere may be nitrogen, argon, etc., and the present invention is not limited thereto. The first carbonization treatment has the function of uniformly coating a layer of carbon material on the surface of the silicon monoxide to relieve the volume expansion of the silicon monoxide.
In some embodiments, the temperature of the first carbonization treatment is 300 ℃ to 1000 ℃, such as 400 ℃, 500 ℃, 600 ℃, 700 ℃, 1000 ℃, and the like, preferably 500 ℃ to 1000 ℃; the time is 1 to 10 hours, for example, 1 to 5, 7, 8, 10, and preferably 2 to 8 hours.
Further, after the first carbonization treatment, the material after the first carbonization treatment, graphite and a second carbon source are fully mixed to obtain a second mixture. Wherein the second carbon source includes, but is not limited to, one or more of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polyvinylidene fluoride, polyethylene oxide, polyvinyl chloride, polyethylene, chlorinated polyethylene, glucose, and asphalt.
In some embodiments, the step of obtaining the second mixture comprises: dispersing the material subjected to the first carbonization treatment, graphite and a second carbon source into a solvent to obtain a second dispersion liquid; the second dispersion is dried, e.g., lyophilized or oven dried, to provide a second mixture. The solvent may be ethanol, acetone, water, etc., wherein the water is preferably deionized water.
In some embodiments, the mass ratio of the material after the first carbonization treatment to the graphite is 1:1 to 1:100, for example, 1:2, 1:5, 1:8, 1:10, 1:20, 1:40, 1:50, etc., preferably 1:5 to 1: 10; the mass ratio of the graphite to the second carbon source is 1:10 to 100:1, for example, 1:1, 1:5, 1:6, 2:1, 5:1, 10:1, 20:1, and preferably 1:1 to 10: 1.
Next, the obtained second mixture is heated in an inert atmosphere to perform a second carbonization treatment. Wherein the inert atmosphere may be nitrogen, argon, etc., and the present invention is not limited thereto. The second carbonization treatment has the function of enabling the silicon monoxide coated with a layer of carbon material to be uniformly mixed with graphite and then coated with a layer of carbon material, so that the volume expansion of the silicon monoxide is further relieved.
In some embodiments, the temperature of the second carbonization treatment is 300 ℃ to 1000 ℃, such as 400 ℃, 500 ℃, 600 ℃, 700 ℃, 1000 ℃, and the like, preferably 500 ℃ to 1000 ℃; the time is 1 to 10 hours, for example, 1 to 5, 7, 8, 10, and preferably 2 to 8 hours. And after the second carbonization treatment, obtaining the graphene modified silicon monoxide/carbon composite material.
In conclusion, the silicon monoxide/carbon composite material is modified by the graphene through a specific process, and when the obtained composite material is used as a lithium ion battery cathode material, the characteristics of high capacity, high first coulombic efficiency and good cycle performance can be presented. The preparation process of the composite material has low cost, high production efficiency, rich raw material resources, easy large-scale production and good industrial application prospect.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available.
Example 1
1) Dispersing SiO (100g), graphene (5g) and asphalt (20g) into deionized water to obtain mixed solution a1(ii) a Mixing the mixed solution a1Stirring for 5h, then placing the mixture into a ball mill for ball milling for 5h to obtain mixed liquid b1Mixing the obtained mixture b1After freeze-drying, obtaining a mixture c of SiO, graphene and asphalt1；
2) Mixing the mixture c1Placing in argon atmosphere, carbonizing at 900 deg.C for 3h to obtain carbonized sample d1；
3) Sample d after carbonization1Dispersing the graphite (900g) and the asphalt (200g) in deionized water to obtain a mixed solution e1(ii) a Mixed liquor e1Removing the solvent and drying to obtain a mixture f1；
4) Mixing the mixture f1And (3) placing the material in an argon atmosphere, and carrying out carbonization treatment at 800 ℃ for 4h to obtain the graphene modified SiO/C composite material.
Fig. 1 is a scanning electron microscope image of the graphene-modified SiO/C composite material of example 1, as shown in fig. 1, the silicon monoxide is uniformly distributed on the surfaces of the graphite and the graphene. When the lithium ion battery cathode material is used as a lithium ion battery cathode material, the first reversible capacity is 454mAh/g under the current density of 0.5C, the coulombic efficiency is 85.2%, and the capacity retention rate is 83.2% after 500 cycles.
Example 2
1) Dispersing SiO (100g), graphene (6g) and polyvinylpyrrolidone (10g) in ethanol to obtain a mixed solution a2(ii) a Mixing the mixed solution a2Stirring for 6h, then placing the mixture in a ball mill for ball milling treatment for 8h to obtain mixed solution b2Mixing the obtained mixture b2Drying to obtain a mixture c of SiO, graphene and asphalt2；
2) Mixing the mixture c2Placing in nitrogen atmosphere, carbonizing at 800 deg.C for 4h to obtain carbonized sample d2；
3) Sample d after carbonization2Graphite (800g) and polyvinylpyrrolidone (100g) were dispersed in ethanol to obtain a mixed solution e2(ii) a Mixed liquor e2Removing the solvent and drying to obtain a mixture f2；
4) Mixing the mixture f2And (3) placing the material in a nitrogen atmosphere, and carrying out carbonization treatment at 1000 ℃ for 3h to obtain the graphene modified SiO/C composite material. When the lithium ion battery cathode material is used as a lithium ion battery cathode material, under the current density of 0.5C, the first reversible capacity is 464mAh/g, the coulombic efficiency is 84.1%, and the capacity retention rate is 80.5% after 500 cycles.
Example 3
1) Dispersing SiO (100g), graphene (7g) and polyvinyl alcohol (15g) into deionized water to obtain mixed solution a3(ii) a Mixing the mixed solution a3Stirring for 5h, then placing the mixture into a ball mill for ball milling for 5h to obtain mixed liquid b3Mixing the obtained mixture b3After freeze-drying, obtaining a mixture c of SiO, graphene and asphalt3；
2) Mixing the mixture c3Placing in argon atmosphere, and carbonizing at 1000 deg.C for 2 hr to obtain carbonized sample d3；
3) Sample d after carbonization3Dispersing the graphite (850g) and the asphalt (200g) into deionized water to obtain a mixed solution e3(ii) a Mixed liquor e3Removing the solvent and drying to obtain a mixture f3；
4) Mixing the mixture f3And (3) placing the material in an argon atmosphere, and carrying out carbonization treatment at 800 ℃ for 4h to obtain the graphene modified SiO/C composite material. When the lithium ion battery cathode material is used as a lithium ion battery cathode material, the first reversible capacity is 459mAh/g under the current density of 0.5C, the coulombic efficiency is 84.6%, and the capacity retention rate is 82.1% after 500 cycles.
Example 4
1) Dispersing SiO (100g), graphene (6g) and glucose (18g) into deionized water to obtain mixed solution a4(ii) a Mixing the mixed solution a4Stirring for 5h, then placing the mixture into a ball mill for ball milling for 5h to obtain mixed liquid b4Mixing the obtained mixture b4Drying to obtain a mixture c of SiO, graphene and asphalt4；
2) Will be mixed withCompound c4Placing in nitrogen atmosphere, carbonizing at 800 deg.C for 3h to obtain carbonized sample d4；
3) Sample d after carbonization4Dispersing the graphite (900g) and polyvinylpyrrolidone (120g) in deionized water to obtain a mixed solution e4(ii) a Mixed liquor e4Removing the solvent and drying to obtain a mixture f4；
4) Mixing the mixture f4And (3) placing the obtained product in a nitrogen atmosphere, and carrying out carbonization treatment at 900 ℃ for 4h to obtain the graphene modified SiO/C composite material. When the lithium ion battery cathode material is used as a lithium ion battery cathode material, the first reversible capacity is 452mAh/g under the current density of 0.5C, the coulombic efficiency is 83.7 percent, and the capacity retention rate is 81.6 percent after 500 cycles.
Example 5
1) Dispersing SiO (100g), graphene (8g) and asphalt (10g) into deionized water to obtain mixed solution a5(ii) a Mixing the mixed solution a5Stirring for 5h, then placing the mixture into a ball mill for ball milling for 5h to obtain mixed liquid b5Mixing the obtained mixture b5After freeze-drying, obtaining a mixture c of SiO, graphene and asphalt5；
2) Mixing the mixture c5Placing in argon atmosphere, and carbonizing at 1000 deg.C for 2 hr to obtain carbonized sample d5；
3) Sample d after carbonization5Dispersing the graphite (800g) and polyvinyl alcohol (100g) in deionized water to obtain a mixed solution e5(ii) a Mixed liquor e5Removing the solvent and drying to obtain a mixture f5；
4) Mixing the mixture f5And (3) placing the material in an argon atmosphere, and carrying out carbonization treatment at 800 ℃ for 3h to obtain the graphene modified SiO/C composite material. When the lithium ion battery cathode material is used as a lithium ion battery cathode material, the first reversible capacity is 463mAh/g under the current density of 0.5C, the coulombic efficiency is 84.5%, and the capacity retention rate is 82.3% after 500 cycles.
Example 6
1) Dispersing SiO (100g), graphene (5g) and polyvinyl alcohol (20g) into deionized waterObtaining a mixed solution a6(ii) a Mixing the mixed solution a6Stirring for 5h, then placing the mixture into a ball mill for ball milling for 5h to obtain mixed liquid b6Mixing the obtained mixture b6Drying to obtain a mixture c of SiO, graphene and asphalt;
2) mixing the mixture c6Placing in nitrogen atmosphere, carbonizing at 800 deg.C for 3h to obtain carbonized sample d6；
3) Sample d after carbonization6Dispersing the graphite (900g) and glucose (130g) into deionized water to obtain a mixed solution e6(ii) a Mixed liquor e6Removing the solvent and drying to obtain a mixture f6；
4) Mixing the mixture f6And (3) placing the obtained product in a nitrogen atmosphere, and carrying out carbonization treatment at 900 ℃ for 4h to obtain the graphene modified SiO/C composite material. When the lithium ion battery cathode material is used as a lithium ion battery cathode material, the first reversible capacity is 450mAh/g under the current density of 0.5C, the coulombic efficiency is 84.0%, and the capacity retention rate is 80.8% after 500 cycles.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (9)
1. A preparation method of a graphene modified silicon monoxide/carbon composite material is characterized by comprising the following steps:
fully mixing graphene, silicon monoxide and a first carbon source to obtain a first mixture;
heating the first mixture in an inert atmosphere to perform first carbonization treatment;
fully mixing the material subjected to the first carbonization treatment, graphite and a second carbon source to obtain a second mixture; and
and heating the second mixture in an inert atmosphere, and performing second carbonization treatment to obtain the graphene modified silicon monoxide/carbon composite material.
2. The method according to claim 1, wherein the first carbon source and the second carbon source are each independently selected from one or more of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polyvinylidene fluoride, polyethylene oxide, polyvinyl chloride, polyethylene, chlorinated polyethylene, glucose, and asphalt.
3. The method of claim 1, wherein said obtaining a first mixture comprises the steps of:
dispersing graphene, silicon monoxide and a first carbon source into water to obtain a first dispersion liquid;
stirring the first dispersion liquid for 1-24 h, and then carrying out ball milling treatment for 1-24 h to obtain a first mixed liquid; and
and drying the first mixed solution to obtain the first mixture.
4. The preparation method according to claim 1, wherein the mass ratio of the graphene to the silicon monoxide is 1 (10-100), and the mass ratio of the silicon monoxide to the first carbon source is 1: 10-100: 1.
5. The method of claim 1, wherein said obtaining a second mixture comprises the steps of:
dispersing the material subjected to the first carbonization treatment, graphite and a second carbon source into a solvent to obtain a second dispersion liquid; and
and drying the second dispersion liquid to obtain the second mixture.
6. The method according to claim 5, wherein the solvent is one or more selected from the group consisting of ethanol, acetone, and water.
7. The preparation method according to claim 1, wherein the mass ratio of the material subjected to the first carbonization treatment to graphite is 1: 1-1: 100, and the mass ratio of the graphite to the second carbon source is 1: 10-100: 1.
8. The preparation method according to claim 1, wherein the temperature of the first carbonization treatment is 300-1000 ℃ and the time is 1-10 h; the temperature of the second carbonization treatment is 300-1000 ℃, and the time is 1-10 h.
9. A graphene-modified silicon monoxide/carbon composite material prepared by the method of any one of claims 1 to 8.
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| CN106410158A (en) * | 2016-11-07 | 2017-02-15 | 中国科学院化学研究所 | Graphene modified silicon monoxide and carbon composite microsphere, and preparation method and application thereof |
| CN109037636A (en) * | 2018-08-03 | 2018-12-18 | 深圳市斯诺实业发展有限公司 | A kind of preparation method of SiO/ carbon graphite composite negative pole material |
| CN110970611A (en) * | 2019-12-23 | 2020-04-07 | 北京理工大学重庆创新中心 | Hierarchical silicon-carbon composite material and preparation method and application thereof |
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