CN111211306A - MXene @ carbon @ porous silicon material and preparation method and application thereof - Google Patents
MXene @ carbon @ porous silicon material and preparation method and application thereof Download PDFInfo
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- CN111211306A CN111211306A CN202010038733.XA CN202010038733A CN111211306A CN 111211306 A CN111211306 A CN 111211306A CN 202010038733 A CN202010038733 A CN 202010038733A CN 111211306 A CN111211306 A CN 111211306A
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- H—ELECTRICITY
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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
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to an MXene @ carbon @ porous silicon material and a preparation method and application thereof. The raw materials comprise silicon-magnesium alloy Mg2The structure of the Si, carbon dioxide, MXene @ carbon @ porous silicon material is that carbon is coated on the outer surface of the porous silicon, and a composite body of the carbon and the porous silicon is embedded in the interlayer space of Mxene. Mixing silicon-magnesium alloy Mg2And reacting Si serving as a precursor with carbon dioxide gas to obtain a product, and carrying out acid washing on the product to obtain the carbon @ porous silicon material. Compounding with MXene to obtain MXene @ carbon @ porous silicon material. The product has good electrical property, uniform carbon coating and controllable thickness.
Description
Technical Field
The invention belongs to the technical field of carbon-carbon composite materials, and particularly relates to an MXene @ carbon @ porous silicon material and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The silicon-carbon composite material has the advantages of good conductivity, good ductility, small density, adaptability to volume change and the like, and is considered as the best material for compounding with the silicon-based material.
The common preparation method of the silicon-carbon composite material comprises the following steps: preparing a compound of nano silicon and graphene by adopting a mechanical mixing and in-situ reduction method; compounding nano silicon and graphene by adopting a spray drying technology; coating silicon using vapor deposition, and the like. In patent CN 108493412 a, silicon dioxide is used as a precursor raw material, porous silicon is prepared by magnesiothermic reduction, and then an intermediate product is pickled and carbon is coated by combining solution evaporation and carbonization methods, so as to finally obtain the porous silicon-carbon composite negative electrode material. The carbon coating obtained by the method is not uniform, and the thickness of the coating is not controllable. In addition, the method requires two times of heating to high temperature, so that silicon in the obtained composite material is partially oxidized, and the purity of the product is reduced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an MXene @ carbon @ porous silicon material, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
in a first aspect, the MXene @ carbon @ porous silicon material comprises silicon-magnesium alloy Mg2The structure of the Si, carbon dioxide, MXene @ carbon @ porous silicon material is that carbon is coated on the outer surface of the porous silicon, and a composite body of the carbon and the porous silicon is embedded in the interlayer space of Mxene.
The carbon dioxide reacts with the silicon-magnesium alloy to obtain carbon-coated porous silicon, the coated product is compounded with MXene, the coated product is embedded into the interlayer spacing of the MXene to form a chimeric structure, the obtained composite material has good conductivity and high specific surface, and the thickness of the carbon coating layer is proper.
In some embodiments, Mxene is Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3、Ti3One or a mixture of more than two of CN.
In a second aspect, a method for preparing a carbon @ porous silicon material in the MXene @ carbon @ porous silicon material comprises the following steps: mixing silicon-magnesium alloy Mg2And reacting Si serving as a precursor with carbon dioxide gas to obtain a product, and carrying out acid washing on the product to obtain the carbon @ porous silicon material.
The reaction of the invention is a preparation process through one-time high-temperature treatment, the silicon-magnesium alloy and carbon dioxide react at one time at high temperature to obtain an intermediate of magnesium oxide and carbon, the by-product magnesium oxide is washed away after acid washing, and the surface of the porous silicon is coated with the carbon. Compared with the prior art, the method has the advantages that the technical scheme is different, the high-temperature times are only once, meanwhile, the prior art is different, the carbon cannot be directly coated by the magnesium thermal reduction method, so the thickness of the carbon coating cannot be controlled.
The preparation method of the MXene @ carbon @ porous silicon material comprises the following steps: and stirring and compounding the carbon-coated porous silicon and MXene at normal temperature to obtain the MXene @ carbon @ porous silicon material.
In some embodiments, the precursor is reacted with carbon dioxide at a temperature of 400 ℃ to 1500 ℃ for a time of 0.1h to 24 h; preferably, the temperature for the reaction of the precursor and the carbon dioxide is 600 ℃ to 1500 ℃. The temperature affects the thickness of the carbon coating formed, the principle being that temperature affects the extent of the reaction of magnesium and carbon dioxide, the higher the temperature, the thicker the carbon coating formed. When the reaction temperature is higher than the above range, by-products are generated, and the purity of the product is lowered.
In some embodiments, the acid cleaning agent used for acid cleaning is one or a mixture of two or more of hydrochloric acid, sulfuric acid, hydrofluoric acid, nitric acid, acetic acid, oxalic acid, and citric acid. And in the acid washing process, acid reacts with the intermediate product to obtain the carbon-coated porous silicon substrate MXene material with high specific surface area.
In some embodiments, the molar ratio of silicon magnesium alloy to carbon dioxide is greater than 1:1.1, and the molar ratio of carbon-coated porous silicon to MXene is from 0.5:1 to 10: 1.
In some embodiments, Mxene is Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3、Ti3One or a mixture of more than two of CN. The carbon-coated porous silicon is compounded with Mxene to further improve the conductivity of the composite material, and the MXene can buffer the volume expansion between layers. Therefore, such a multifunctional structural model is useful for improving the performance of the battery.
In a third aspect, the carbon @ porous silicon material obtained by the preparation method is used as a lithium ion battery negative electrode material in application of a lithium ion battery
The MXene @ carbon @ porous silicon material is applied to a lithium metal battery as a current collector of the lithium metal battery.
The invention has the beneficial effects that:
(1) according to the invention, carbon dioxide is introduced at high temperature to prepare the carbon @ porous silicon material, the thickness of the carbon coating layer can be regulated and controlled through temperature and time, and the obtained carbon coating layer is uniformly coated on the surface of the porous silicon.
(2) The invention obtains the carbon coating layer in the reaction process, so the binding force between the coating layer and the porous silicon is strong.
(3) The invention is coated firstly and then pickled, so the product is not oxidized and the purity is higher.
(4) The carbon coating layer can improve the conductivity of the material, buffer the volume expansion generated in the circulating process, MXene has high conductivity, the conductivity of the material can be further improved, and the volume expansion can be buffered between layers of the MXene. Therefore, such a multifunctional structural model is useful for improving the performance of the battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, 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 invention and not to limit the invention.
FIG. 1 is an XRD pattern of a Si-Mg alloy precursor in example 1;
FIG. 2 is an XRD pattern of the intermediate product of example 1;
FIG. 3 is the XRD of carbon @ porous silicon in example 1;
FIG. 4 is an XRD of MXene @ carbon @ porous silicon of example 1;
FIG. 5 is an SEM of a Si-Mg alloy precursor in example 1;
FIG. 6 is an SEM of an intermediate product of example 1;
FIG. 7 is an SEM of carbon @ porous silicon of example 1, the product structure being porous and having a uniform pore size distribution and a relatively high porosity;
FIG. 8 is an SEM of MXene @ carbon @ porous silicon of example 1 showing roughness and uniform distribution of carbon @ porous silicon;
FIG. 9 is a graph illustrating the electrical properties of carbon @ porous silicon as a negative electrode material of a lithium ion battery in example 1;
FIG. 10 is a graph of the cycle performance test of MXene @ carbon @ porous silicon as a current collector for a lithium metal battery in example 1;
fig. 11 is an XRD of the intermediate product in comparative example 1.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. The invention will be further illustrated by the following examples
Example 1:
taking 5g of silicon-magnesium alloy as a raw material, and introducing titanium dioxide gasHeating at 700 deg.C for 12 hr, stirring the resultant in hydrochloric acid solution for 10 hr, and adding Ti3C2The material is finally centrifugally dried to obtain Ti3C2@ carbon @ porous silicon material (MXene @ carbon @ porous silicon).
From fig. 1, a pure-phase silicon-magnesium alloy can be obtained as a precursor of the silicon-magnesium alloy. Fig. 2 illustrates that the magnesium oxide and silicon composite in the intermediate product, i.e., titanium dioxide reacts with magnesium in the silicon-magnesium alloy precursor to form magnesium oxide and carbon, and the formed carbon coats the surface of silicon. It can be illustrated in fig. 3 that carbon-coated silicon is synthesized and the product purity is high. Figure 4 illustrates that MXene @ carbon @ porous silicon is successfully prepared. The surface of the precursor obtained in fig. 5 is relatively smooth and free of impurities. The intermediate product in fig. 6 has a rough surface, illustrating the apparent reaction of carbon dioxide with the precursor. The structure of carbon @ porous silicon of fig. 7 is porous and has a uniform pore size distribution and a large porosity. FIG. 8 shows that the MXene @ carbon @ porous silicon product is rough and the carbon @ porous silicon is uniformly distributed. Fig. 9 shows the cycle performance and rate performance of carbon @ porous silicon as a negative electrode material of a lithium ion battery, and the carbon @ porous silicon shows good electrochemical performance as the negative electrode material. Fig. 10 illustrates that MXene @ carbon @ porous silicon has good cycling performance as a current collector for a lithium metal battery.
Example 2:
taking 5g of silicon-magnesium alloy as a raw material, introducing titanium dioxide gas, heating at 1500 ℃ for 0.1h, stirring the product in sulfuric acid solution, and then adding Ti2C material, and finally centrifugally drying to obtain Ti2C @ carbon @ porous silicon material.
Example 3:
taking 5g of silicon-magnesium alloy as a raw material, introducing titanium dioxide gas, heating at 600 ℃ for 24h, stirring the product in a nitric acid solution, and then adding Ta4C3The material is finally centrifugally dried to obtain Ta4C3@ carbon @ porous silicon material.
Example 4:
taking 5g of silicon-magnesium alloy as a raw material, introducing titanium dioxide gas, heating for 10h at 1000 ℃, stirring the product in a hydrochloric acid solution, adding a TiNbC material, and finally performing centrifugal drying to obtain the TiNbC @ carbon @ porous silicon material.
Example 5:
taking 5g of silicon-magnesium alloy as a raw material, introducing titanium dioxide gas, heating at 1200 ℃ for 8h, stirring the product in a hydrochloric acid solution, and then adding Nb4C3The material is finally centrifugally dried to obtain Nb4C3@ carbon @ porous silicon material.
Example 6:
taking 5g of silicon-magnesium alloy as a raw material, introducing titanium dioxide gas, heating at 900 ℃ for 20h, stirring the product in a hydrochloric acid solution, and then adding V2Material C, and finally centrifugally drying to obtain V2C @ carbon @ porous silicon material.
Comparative example 1
Compared with the temperature of 1800 ℃ of the reaction of the silicon-magnesium alloy and carbon dioxide gas in the embodiment 1, the obtained product is impure. FIG. 11 is an XRD of the intermediate product of comparative example 1, with Mg in the product2SiO4Is present.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An MXene @ carbon @ porous silicon material is characterized in that: the raw materials comprise silicon-magnesium alloy Mg2The structure of the Si, carbon dioxide, MXene @ carbon @ porous silicon material is that carbon is coated on the outer surface of the porous silicon, and a composite body of the carbon and the porous silicon is embedded in the interlayer space of Mxene.
2. The MXene @ carbon @ porous silica material of claim 1, wherein: mxene is Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3、Ti3One or a mixture of more than two of CN.
3. The method of making the carbon @ porous silica material of the MXene @ carbon @ porous silica material of any one of claims 1-2, wherein: the method comprises the following steps: mixing silicon-magnesium alloy Mg2And reacting Si serving as a precursor with carbon dioxide gas to obtain a product, and carrying out acid washing on the product to obtain the carbon @ porous silicon material.
4. The method of claim 3 wherein said carbon @ porous silica material is selected from the group consisting of MXene @ carbon @ porous silica materials consisting of: compounding the carbon-coated porous silicon with MXene to obtain the MXene @ carbon @ porous silicon material.
5. The method of claim 3 wherein said carbon @ porous silica material is selected from the group consisting of MXene @ carbon @ porous silica materials consisting of: the reaction temperature of the precursor and the carbon dioxide is 400-1500 ℃, and the reaction time is 0.1-24 h.
6. The method of making MXene @ carbon @ porous silica material of claim 5, wherein: the reaction temperature of the precursor and the carbon dioxide is 600-1500 ℃.
7. The method of claim 3 wherein said carbon @ porous silica material is selected from the group consisting of MXene @ carbon @ porous silica materials consisting of: the pickling reagent used for pickling is one or a mixture of more than two of hydrochloric acid, sulfuric acid, hydrofluoric acid, nitric acid, acetic acid, oxalic acid and citric acid.
8. The method of claim 4 wherein said carbon @ porous silica material is selected from the group consisting of MXene @ carbon @ porous silica materials consisting of: the molar ratio of the silicon-magnesium alloy to the carbon dioxide is higher than 1:1.1, and the molar ratio of the product silicon to MXene is 0.5:1-10: 1.
9. The carbon @ porous silicon material obtained by the preparation method of claim 3 is applied to a lithium ion battery as a lithium ion battery negative electrode material.
10. Use of the MXene @ carbon @ porous silicon material of any one of claims 1-2 as a current collector for a lithium metal battery in a lithium metal battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112038641A (en) * | 2020-09-09 | 2020-12-04 | 宁波富理电池材料科技有限公司 | MXene silicon-carbon composite material, preparation method thereof, negative electrode and lithium ion battery |
| CN114335527A (en) * | 2020-09-29 | 2022-04-12 | 山东海科创新研究院有限公司 | High-performance silicon-carbon composite material, preparation method thereof and lithium ion battery |
| CN114430034A (en) * | 2020-10-29 | 2022-05-03 | 北京小米移动软件有限公司 | Composite material, manufacturing method thereof, electrode, battery and electronic equipment |
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Cited By (4)
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| CN112038641A (en) * | 2020-09-09 | 2020-12-04 | 宁波富理电池材料科技有限公司 | MXene silicon-carbon composite material, preparation method thereof, negative electrode and lithium ion battery |
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| CN114335527B (en) * | 2020-09-29 | 2024-04-09 | 山东海科创新研究院有限公司 | High-performance silicon-carbon composite material, preparation method thereof and lithium ion battery |
| CN114430034A (en) * | 2020-10-29 | 2022-05-03 | 北京小米移动软件有限公司 | Composite material, manufacturing method thereof, electrode, battery and electronic equipment |
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