CN111403723A - Silicon-carbon negative electrode composite material, preparation method thereof and lithium ion battery - Google Patents
Silicon-carbon negative electrode composite material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN111403723A CN111403723A CN202010311216.5A CN202010311216A CN111403723A CN 111403723 A CN111403723 A CN 111403723A CN 202010311216 A CN202010311216 A CN 202010311216A CN 111403723 A CN111403723 A CN 111403723A
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Abstract
The invention provides a preparation method of a silicon-carbon negative electrode composite material, which comprises the following steps: preparing a graphene oxide suspension with the mass content of 0.1-1%; adding silicon powder into the turbid liquid for homogenization to obtain graphene oxide-silicon powder mixed liquid; drying the graphene oxide-silicon powder mixed solution to obtain a graphene oxide-silicon powder composite material; and roasting the graphene oxide-silicon powder composite material for 1-5 hours at 600-1200 ℃ in an inert atmosphere. Also provides the silicon-carbon cathode composite material prepared by the method and a lithium ion battery containing the silicon-carbon cathode composite material. In the preparation method, the graphene oxide-silicon composite material keeps few graphene sheets after reduction, has controllable sheet diameter and has better conductivity than the graphene-silicon composite negative electrode material prepared by a mechanical stripping method. The preparation method provided by the invention can adopt industrial equipment, and the used solvent is non-toxic and pollution-free, is suitable for commercial and large-scale production, and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a silicon-carbon cathode composite material, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries, as a new generation of secondary batteries, have been widely used in many fields such as energy storage devices and consumer electronics products due to their advantages of high energy density, high open-circuit voltage, high output power, low self-discharge, wide operating temperature range, fast charge and discharge speed, no memory effect, etc. With the rapid development of the electric automobile industry, the demand for the lithium ion battery with long cycle life, high specific capacity and high rate performance is more and more strong.
One material that restricts further improvement of the energy density of the lithium ion battery is a lithium ion battery cathode material, and most of the currently commercialized cathode materials are various graphite materials such as hard carbon, soft carbon, natural graphite, artificial graphite, mesophase micro carbon spheres and the like. The specific capacity of the graphite carbon negative electrode material is generally not more than 360mAh/g (the theoretical capacity of graphite is 372mAh/g, and the actual exertion capacity is 310-360 mAh/g), although the actual lithium removal capacity of the existing graphite negative electrode material in a half-cell can be up to 365mAh/g, the actual lithium removal capacity is difficult to further improve, and the actual lithium removal capacity is far away from the specific capacity required by the negative electrode material at present, so that the market demand is more and more difficult to meet. Therefore, a new high energy density negative electrode material must be developed to replace the graphite-based material.
The research finds that the specific mass capacity of the silicon-based material is about 10 times of that of the graphite material, and the silicon-based material has a very low lithium removal voltage platform, so that the silicon is used as a negative electrode material of a lithium ion battery to be studied more deeply. However, when the silicon-carbon negative electrode is subjected to alloying reaction, along with the occurrence of phase change, huge volume expansion (300%) is generated, and such drastic volume change brings a series of problems to the silicon-based material in the circulating process, so that the silicon material is crushed and pulverized on an electrode sheet, an electrode coating falls off and the like, and finally, the capacity is rapidly attenuated, and the practical application of the silicon-carbon negative electrode in a lithium ion battery is seriously hindered. Meanwhile, the silicon material is a semiconductor material and has poorer conductivity compared with a graphite material, which also seriously hinders the commercial application of the silicon-based negative electrode.
In patent CN105762360A, graphene oxide and silicon powder are ultrasonically dispersed and freeze-dried to obtain a graphene-coated silicon negative electrode composite material, although the capacity is high, the freeze-dried material is light, secondary crushing is difficult, and the particle size of the finally obtained silicon carbon negative electrode material is not uniformly controlled.
In patent CN104993109A, the silicon-carbon cathode material is prepared by performing suction filtration centrifugation on ultrasonic graphene dispersion liquid and nano silicon powder dispersion liquid and calcining. Although the process is simple, the ultrasound, the suction filtration and the centrifugation are difficult to realize industrialization and only can stay in a laboratory stage.
Disclosure of Invention
In order to overcome the defects, the invention provides a silicon-carbon negative electrode composite material, a preparation method thereof and a lithium ion battery comprising the silicon-carbon negative electrode composite material.
The invention provides a preparation method of a silicon-carbon negative electrode composite material, which comprises the following steps: emulsifying graphene oxide with the mass content of 0.1-1% to form a suspension with the graphene oxide uniformly dispersed; adding silicon powder into the turbid liquid for homogenization to obtain graphene oxide-silicon powder mixed liquid; drying the graphene oxide-silicon powder mixed solution to obtain a graphene oxide-silicon powder composite material; and roasting the graphene oxide-silicon powder composite material for 1-5 hours at 600-1200 ℃ in an inert atmosphere or a reducing atmosphere.
According to an embodiment of the present invention, the number of graphene oxide layers in the graphene oxide-silicon powder mixture is less than 10, and D is a sheet diameter50Less than 500 nm.
According to another embodiment of the present invention, the solvent of the suspension and the mixed solution is one or both of absolute ethyl alcohol and ultrapure water.
According to another embodiment of the invention, the silicon powder is one or two of micron silicon powder and nanometer silicon powder.
According to another embodiment of the invention, the mass ratio of the graphene oxide to the silicon powder is 1 (0.1-0.3).
According to another embodiment of the present invention, the inert atmosphere is selected from one or more of nitrogen, argon, helium; the reducing atmosphere comprises one or more of hydrogen, methane, carbon monoxide, hydrogen sulfide.
The invention also provides a silicon-carbon negative electrode composite material prepared by the method.
According to an embodiment of the present invention, the number of graphene layers in the composite material is less than 10, and the sheet diameter D is smaller than50Less than 5 μm.
The invention also provides a lithium ion battery comprising the silicon-carbon negative electrode composite material.
According to the preparation method, the graphene oxide and the silicon powder are used as raw materials, and the graphene oxide is reduced into the graphene, so that few sheets and controllable sheet diameter of the graphene can be realized, the ultrahigh conductivity of the graphene is maintained, and the electronic polarization phenomenon caused by poor conductivity of a silicon cathode can be reduced. Meanwhile, the preparation method provided by the invention can adopt industrial equipment, and the used solvent is non-toxic and pollution-free, is suitable for commercial and large-scale production, and is environment-friendly.
Drawings
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
Fig. 1 is an SEM electron micrograph of the silicon carbon anode composite prepared in example 1.
Fig. 2 is a particle size distribution diagram of graphene oxide before emulsification of graphene oxide in example 1.
Fig. 3 is a particle size distribution diagram of graphene oxide after emulsification of graphene oxide in example 1.
Fig. 4 is a particle size distribution diagram of the graphene oxide-silicon powder homogenized in example 1.
Fig. 5 is an atomic force imaging diagram of the silicon carbon anode composite material prepared in example 1.
Fig. 6 is a resistance chart of the silicon carbon anode material prepared in example 2 and a commercially available silicon carbon anode material.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The preparation method of the silicon-carbon negative electrode composite material comprises the following steps: emulsifying graphene oxide with the mass content of 0.1-1% to form a suspension with the graphene oxide uniformly dispersed; adding silicon powder into the turbid liquid for homogenization to obtain graphene oxide-silicon powder mixed liquid; drying the graphene oxide-silicon powder mixed solution to obtain a graphene oxide-silicon powder composite material; and roasting the graphene oxide-silicon powder composite material for 1-5 hours at 600-1200 ℃ in an inert atmosphere.
Through emulsification, the particle size of the graphene oxide can be homogenized, so that the size of the graphene in the prepared silicon-carbon cathode composite material can be controlled. And through emulsification, the graphene oxide can be uniformly dispersed in the turbid liquid, so that the uniformly dispersed mixed liquid can be formed with the silicon powder in a follow-up manner. Emulsification may be by any suitable means, such as an emulsifier or the like. Since graphene oxide includes hydrophilic groups, the use of ethanol and pure water as solvents is advantageous for forming a uniformly dispersed suspension or mixed solution. More preferably, the introduction of impurities can be avoided by using one or both of absolute ethyl alcohol and ultrapure water. The mass content of the graphene oxide in the turbid liquid is 0.1% -1%, and when the mass content is lower than 0.1%, the prepared turbid liquid is easy to separate layers and isolate due to the fact that the content of the graphene oxide is small; when the mass content is more than 1%, a uniform graphene oxide dispersion cannot be obtained due to the large content and the large viscosity. Of course, the mass content of graphene oxide in the suspension may be any value between 0.1% and 1%, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, and the like.
And after forming the turbid liquid, adding silicon powder into the turbid liquid for homogenization to form uniformly dispersed graphene oxide-silicon powder mixed liquid. The homogenization process may be repeated several times until a uniformly dispersed mixed solution is formed. The number of graphene oxide layers in the mixed solution is preferably less than 10, and the sheet diameter D50Less than 500nm is advantageous for forming a more suitable material for use as a battery negative electrode. The silicon powder can be micron-sized silicon powder, nano-sized silicon powder or a mixture of the micron-sized silicon powder and the nano-sized silicon powder, and the proper silicon powder can be selected according to the shape of the silicon powder in the formed product. The mass ratio of the graphene oxide to the silicon powder is preferably 1 (0.1-0.3). When the mass ratio of the graphene oxide to the silicon powder is less than 1: when the time is 0.1, the similarly prepared graphene oxide-silicon powder turbid liquid is easy to separate and settle, and the industrialization efficiency is low; greater than 1: at 0.3, the graphene oxide-silicon powder suspension cannot achieve the effect of uniform dispersion.
And then, drying the mixed solution to form the graphene oxide-silicon powder composite material. The mixture may be dried by any suitable means, such as spray drying.
And finally, roasting in an inert atmosphere or a reducing atmosphere to reduce the graphene oxide into the graphene. Roasting for 1-5 h at 600-1200 ℃. The roasting temperature is lower than 600 ℃ and higher than 1200 ℃, which is not beneficial to the reduction of the graphene oxide. The roasting time is less than 1h, the reduction of the graphene oxide is incomplete, and graphite is possibly formed in more than 5h, so that the roasting time can be selected to be any appropriate time within 1-5 h according to factors such as roasting temperature, the quantity of roasted substances and the like. The inert atmosphere is selected from one or more of nitrogen, argon and helium. The reducing atmosphere may comprise hydrogen, methane, carbon monoxide, hydrogen sulfide, and may also comprise one or more of an inert gas such as nitrogen, argon, helium.
The preparation method aims at the problems of low conductivity and difficult industrialization of the silicon-based cathode, and through the compounding of the silicon powder and the graphene oxide, equipment used in the whole preparation process can be industrialized equipment, so that the industrialization is easy to realize; and secondly, graphene oxide is used as a precursor material to be compounded with silicon powder, so that the graphene oxide-silicon composite material can keep few graphene sheets after reduction, the sheet diameter is controllable, and the graphene oxide-silicon composite material has better conductivity than the graphene-silicon composite negative electrode material prepared by a mechanical stripping method.
According to the silicon-carbon cathode composite material prepared by the method, graphene oxide is agglomerated in the drying and reducing processes, so that the sheet diameter of graphene in the product is larger than that of graphene in the raw material. The number of layers of graphene in the product is preferably controlled to be less than 10, and the sheet diameter D is50Less than 5 μm to obtain better electrochemical performance.
The lithium ion battery taking the silicon-carbon cathode composite material as the cathode can reduce the electron polarization due to better conductivity of the cathode composite material, thereby improving the cycle performance of the lithium ion battery.
The present invention will be further described with reference to the following examples, which are intended to illustrate the present invention and not to limit the contents thereof.
Example 1
1) And emulsifying the graphene oxide solution with the mass content of 0.5% for 30min to homogenize and fully disperse the particle size of the graphene oxide to obtain the suspension of the graphene oxide. Wherein the solvent is water, and the diameter of graphite oxide flake before emulsification is D502.68 μm (see FIG. 2), and the diameter D of the graphite oxide flakes after emulsification50At 140nm (see FIG. 3).
2) Slowly adding silicon powder with the particle size of 50nm into the graphene oxide suspension obtained in the step 1) to homogenize for 5 times. Wherein the ratio of the graphene oxide to the silicon powder is 1:0.1, and a graphene oxide-silicon powder uniformly mixed solution is obtained. After homogenization, the sheet diameter D of the graphene oxide-silicon powder50120nm (see FIG. 4).
3) And (3) carrying out spray drying on the mixed solution obtained in the step 2) to obtain the graphene oxide-silicon composite material.
4) Roasting and carbonizing the graphene oxide-silicon composite material obtained in the step 3) at the high temperature of 600 ℃ in a tubular furnace for 3 hours in the atmosphere of argon gas to finally obtain the silicon-carbon negative electrode material, wherein the number of layers of the silicon-carbon negative electrode material is 9 (see figure 5).
As shown in fig. 1, an SEM electron micrograph of the silicon-carbon negative electrode composite material obtained in this embodiment shows that graphene and nano Si particles are uniformly mixed and the graphene and the nano Si particles are in close contact with each other, so that the conductivity of the silicon-based negative electrode is improved.
Example 2
1) And (3) emulsifying the graphene oxide solution with the mass content of 0.8% for 50min to homogenize and fully disperse the particle size of the graphene oxide to obtain a suspension of the graphene oxide.
2) Slowly adding silicon powder with the particle size of 50nm into the graphene oxide suspension obtained in the step 1) to homogenize for 5 times. Wherein the ratio of the graphene oxide to the silicon powder is 1:0.2, and a graphene oxide-silicon powder uniformly mixed solution is obtained.
3) And (3) carrying out spray drying on the uniform mixed solution obtained in the step 2) to obtain the graphene oxide-silicon composite material.
4) Roasting and carbonizing the graphene oxide-silicon composite material obtained in the step 3) at the high temperature of 1000 ℃ in a tubular furnace for 5 hours in the atmosphere of argon gas to finally obtain the silicon-carbon negative electrode material.
The silicon-carbon negative electrode material prepared in the example 2 and the commercially available existing silicon-carbon negative electrode material are subjected to alternating current impedance detection under the condition that the test frequency is 0.01Hz-100000 Hz. From the detection results (see fig. 6), it can be seen that the composite material of the present invention has relatively small resistance compared to the existing silicon carbon negative electrode material. The silicon-carbon cathode material has good conductivity and can reduce the problem of electron polarization.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. The preparation method of the silicon-carbon negative electrode composite material is characterized by comprising the following steps:
emulsifying graphene oxide with the mass content of 0.1-1% to form a suspension with the graphene oxide uniformly dispersed;
adding silicon powder into the turbid liquid for homogenization to obtain graphene oxide-silicon powder mixed liquid;
drying the graphene oxide-silicon powder mixed solution to obtain a graphene oxide-silicon powder composite material; and roasting the graphene oxide-silicon powder composite material for 1-5 hours at 600-1200 ℃ in an inert atmosphere or a reducing atmosphere.
2. The method for preparing the silicon-carbon negative electrode composite material as claimed in claim 1, wherein the number of graphene oxide layers in the graphene oxide-silicon powder mixed solution is less than 10, and the sheet diameter D is smaller than 1050Less than 500 nm.
3. The method for preparing the silicon-carbon negative electrode composite material according to claim 1, wherein a solvent of the suspension and the mixed solution is one or two of absolute ethyl alcohol and ultrapure water.
4. The method for preparing the silicon-carbon negative electrode composite material according to claim 1, wherein the silicon powder is one or two of micron silicon powder and nanometer silicon powder.
5. The preparation method of the silicon-carbon negative electrode composite material as claimed in claim 1, wherein the mass ratio of the graphene oxide to the silicon powder is 1 (0.1-0.3).
6. The method for preparing the silicon-carbon anode composite material according to claim 1, wherein the inert atmosphere is selected from one or more of nitrogen, argon and helium; the reducing atmosphere comprises one or more of hydrogen, methane, carbon monoxide, hydrogen sulfide.
7. A silicon carbon anode composite material, characterized by being prepared by the method of any one of claims 1 to 6.
8. The silicon-carbon anode composite material according to claim 7, wherein the number of graphene layers in the composite material is less than 10, and the sheet diameter D is50Less than 5 μm.
9. A lithium ion battery comprising the silicon-carbon negative electrode composite material according to claim 7 or 8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916705A (en) * | 2020-08-05 | 2020-11-10 | 西北师范大学 | Preparation and application of high-performance silicon oxide-based composite material |
| CN114497551A (en) * | 2020-10-27 | 2022-05-13 | 山东海科创新研究院有限公司 | Silicon-carbon composite material, preparation method thereof and lithium ion battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916705A (en) * | 2020-08-05 | 2020-11-10 | 西北师范大学 | Preparation and application of high-performance silicon oxide-based composite material |
| CN111916705B (en) * | 2020-08-05 | 2023-01-31 | 西北师范大学 | Preparation and application of high-performance silicon oxide-based composite material |
| CN114497551A (en) * | 2020-10-27 | 2022-05-13 | 山东海科创新研究院有限公司 | Silicon-carbon composite material, preparation method thereof and lithium ion battery |
| CN114497551B (en) * | 2020-10-27 | 2024-04-09 | 山东海科创新研究院有限公司 | Silicon-carbon composite material, preparation method thereof and lithium ion battery |
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