CN116995219A - Porous silicon-carbon composite anode material and preparation method and application thereof - Google Patents
Porous silicon-carbon composite anode material and preparation method and application thereof Download PDFInfo
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- 239000011870 silicon-carbon composite anode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 46
- 239000010703 silicon Substances 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000002114 nanocomposite Substances 0.000 claims abstract description 10
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 27
- 239000003575 carbonaceous material Substances 0.000 claims description 24
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 6
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 229910021426 porous silicon Inorganic materials 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 10
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000000758 substrate Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000002153 silicon-carbon composite material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PNUGDRJNKILROY-UHFFFAOYSA-N [C].[Si].[Li] Chemical compound [C].[Si].[Li] PNUGDRJNKILROY-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- H01M4/362—Composites
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0428—Chemical vapour deposition
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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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The application discloses a porous silicon-carbon composite anode material, a preparation method and application thereof, and belongs to the technical field of energy storage. The porous carbon deposited silicon nanocomposite is compounded by porous carbon and silicon tetrachloride in a plasma chemical vapor deposition method. The application does not need complex preparation conditions and materials, only needs to provide a plasma chemical vapor deposition device so that porous carbon and a silicon source can be vapor deposited and compounded, the preparation process does not involve high-temperature high-pressure reaction, and meets the safety standard, and the prepared porous carbon deposited silicon nanocomposite can effectively buffer the volume change of silicon by depositing silicon in porous carbon in the charging and discharging process, has the advantages of improving the first circle coulomb efficiency, the electrochemical performance, the safety and the like, can be industrially applied, and has good application prospect.
Description
Technical Field
The application relates to the technical field of energy storage, in particular to a porous silicon-carbon composite anode material, a preparation method and application thereof.
Background
At present, the commercialized lithium ion battery mainly uses graphite as a negative electrode material, but in recent years, the requirement of various fields on the energy density of the battery is rapidly increased, and the development of the lithium ion battery with higher energy density is urgently needed. Silicon has the highest theoretical specific capacity (theoretical 4200 mAh. G) -1 ) Is considered as one of the most promising commercial anode materials of the next generation. The working voltage of silicon is slightly higher than that of graphite, so that the generation of lithium dendrite can be effectively avoided, and the higher energy density of the whole battery can be ensured. Although silicon has a plurality of advantages, the silicon cathode has the defects of volume expansion, pulverization and falling off and low conductivity in the charge and discharge process, so that the problems of poor cycle performance, low coulombic efficiency, insufficient rate performance and the like occur in the material use process. The silicon-carbon lithium ion battery anode material can effectively solve the problems, so that the silicon-carbon anode material is an important development point of future anode materials.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a porous silicon-carbon composite anode material, and a preparation method and application thereof. The porous carbon and a silicon source are prepared into a composite material by a plasma chemical vapor deposition method, and the composite material is applied to a lithium ion battery cathode, so that the porous structure can effectively relieve the volume expansion of silicon and the carbon material has high conductivity in the charge and discharge process, and the first-circle coulomb efficiency, the electrochemical performance and the safety can be improved.
In order to achieve the above purpose, the present application provides the following technical solutions:
one of the technical schemes of the application is as follows: a porous silicon-carbon composite anode material is obtained by compositing a porous carbon material and a silicon source.
The porous carbon material is used as a substrate material, the porous structure can effectively buffer the volume change of the silicon negative electrode, and the carbon material has higher conductivity, so that the conductivity of the silicon-carbon composite material is improved, and the first-circle coulomb efficiency, the cycle performance and the service life of the electrode are greatly improved.
Preferably, the pore diameter of the porous carbon material is 20-60nm, and the specific surface area is 100-300m 2 /g。
Preferably, the silicon source comprises silane (SiH 4 ) Silicon tetrachloride (SiCl) 4 ) Silicon tetrafluoride (SiF) 4 ) Etc.
Preferably, the silicon source has a purity of greater than 99.9%.
The second technical scheme of the application is as follows: a porous silicon-carbon composite anode material and a preparation method thereof comprise the following steps: and preparing the porous carbon-silicon nanocomposite by using the porous carbon and a silicon source through a plasma chemical vapor deposition method.
Preferably, the parameters of the plasma chemical vapor deposition are: the Ar/Si source flow ratio is 10/40-80sccm, the reaction temperature is 600-800 ℃, the heating rate is 2-5 ℃/min, the reaction time is 30-90min, the radio frequency power is 300-500W, and the reflection power is 100-200W.
The third technical scheme of the application: an application of a porous silicon-carbon composite anode material in a lithium ion battery.
Compared with the prior art, the application has the following advantages and technical effects:
(1) According to the application, porous carbon is used as a substrate material, and nano silicon is uniformly distributed on the surface of the porous carbon and inside the pore canal, so that the silicon-carbon composite material is formed. The porous structure of carbon can effectively relieve the volume expansion of silicon in the charge and discharge process, and meanwhile, the carbon material has high conductivity, so that the composite material effectively utilizes the advantages of silicon and carbon, and the combination of the silicon and the carbon can improve the first-circle coulomb efficiency, the electrochemical performance and the safety of the anode material.
(2) The preparation method is simple and easy to implement, and the preparation method does not need complex preparation conditions and materials, and only needs to provide one plasma chemical vapor deposition device so as to compound the porous carbon and the silicon source.
(3) The application is green and environment-friendly, does not generate pollution and toxic gas, and meets the environment-friendly standard.
(4) The application is safe and controllable, does not involve high-temperature high-pressure reaction, and accords with the safety standard.
(5) The porous carbon-silicon nanocomposite is prepared by using the porous carbon and the silicon source through the plasma chemical vapor deposition method, the porous structure of the carbon material can buffer the volume change of silicon in the charge-discharge process, the advantages of improving the first-circle coulomb efficiency, the electrochemical performance, the safety and the like are achieved, the industrial application is realized, and the application prospect is good.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a graph showing cycle performance and coulombic efficiency of a lithium ion battery prepared in example 1 of the present application;
fig. 2 is a graph showing cycle performance and coulombic efficiency of the lithium ion battery prepared in comparative example 1 of the present application.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the following examples of the present application are all commercially available.
The nano composite material of porous carbon deposited silicon is formed by compounding porous carbon and silicon tetrachloride in a plasma chemical vapor deposition method. The application does not need complex preparation conditions and materials, only needs to provide a plasma chemical vapor deposition device so that porous carbon and a silicon source can be vapor deposited and compounded, the preparation process does not involve high-temperature high-pressure reaction, and meets the safety standard, and the prepared porous carbon deposited silicon nanocomposite can effectively buffer the volume change of silicon by depositing silicon in porous carbon in the charging and discharging process, has the advantages of improving the first circle coulomb efficiency, the electrochemical performance, the safety and the like, can be industrially applied, and has good application prospect.
The application provides a porous silicon-carbon composite anode material, which is obtained by compounding porous carbon serving as a base material with a silicon source through plasma chemical vapor deposition. The porous structure in the porous carbon can effectively buffer the volume change of the silicon negative electrode, and the carbon material has higher conductivity, so that the conductivity of the silicon-carbon composite material is improved, and the composite material can greatly improve the first-circle coulomb efficiency, the cycle performance and the service life of the electrode.
In the following preferred embodiments of the present application, the porous carbon has a pore diameter of 20 to 60nm and a specific surface area of 100 to 300m 2 And/g. The silicon source comprises Silane (SiH) 4 ) Silicon tetrachloride (SiCl) 4 ) And silicon tetrafluoride (SiF) 4 ) One of them. The purity of the silicon source is greater than 99.9%.
The application also provides a preparation method of the porous silicon-carbon composite anode material, which comprises the following steps: the porous carbon is used as a substrate material and is compounded with a silicon source through plasma chemical vapor deposition.
In the following preferred embodiments of the present application, the parameters of the plasma chemical vapor deposition are: the Ar/Si source flow ratio is 10/40-80sccm, the reaction temperature is 600-800 ℃, the heating rate is 2-5 ℃/min, the reaction time is 30-90min, the radio frequency power is 300-500W, and the reflection power is 100-200W. In the present application "/" means "ratio".
The application also provides application of the porous silicon-carbon composite anode material in a lithium ion battery.
The following examples serve as further illustrations of the technical solutions of the application.
Example 1
Preparing a porous silicon-carbon composite anode material:
firstly, 10g of the material with the aperture of 40nm and the specific surface area of 150m are weighed 2 Placing/g porous carbon material on a substrate table of a plasma chemical vapor deposition device; drawing the apparatus outGas to vacuum degree of 1.0X10 -3 Pa; heating the substrate table at a heating rate of 5 ℃/min to enable the deposition temperature to be 700 ℃; argon and silane gas are introduced into the plasma chemical vapor deposition equipment, and the flow ratio of the argon to the silane gas is 10/60sccm; and (3) starting a radio frequency power supply with 400W and a reflection power of 150W, depositing silicon on the porous carbon material, and reacting for 60min to obtain the porous silicon-carbon composite anode material.
Energy storage performance study:
mixing the porous silicon-carbon composite anode material prepared in the embodiment with conductive carbon black (SP) and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 for 0.5h, then adding 1g of N-methylpyrrolidone (NMP) solvent into each 2g of the mixed material, manually grinding for 5min to form black slurry, coating the slurry on a copper foil current collector according to the thickness of 100 mu m, vacuum drying at 110 ℃ for 12h, taking the obtained silicon-carbon electrode pole piece as an electric anode of a lithium ion battery, and assembling the battery in a glove box filled with argon, wherein the assembling process is as follows: cutting the dried pole piece into a round pole piece with the diameter of 13mm by a punching machine, and 1.0M LiPF 6 in ec:dmc:dec=1:1:1 vol% as electrolyte, celgard 2400 as separator, lithium sheet with diameter of 15mm as reference electrode and counter electrode, CR2016 type stainless steel as battery case were assembled into button type lithium ion battery.
The electrochemical performance of the prepared button lithium ion battery is tested, after the button lithium ion battery is stood for 8 hours at 25 ℃, when the button lithium ion battery is subjected to charge-discharge circulation between 0.01V and 1.5V at the rate of 0.1C, the specific capacity of the button lithium ion battery can reach 751.2mAh/g at the first discharge, the initial coulomb efficiency is as high as 93.8%, the specific capacity is kept at 93.3% after 100 circles of circulation, the coulomb efficiency is kept at 100%, and the button lithium ion battery exceeds the existing commercial silicon carbon material (535 mAh/g), so that the level of the commercial silicon carbon material is reached. The graph of cycle performance and coulombic efficiency is shown in fig. 1, and the result shows that the porous silicon-carbon composite anode material prepared in the embodiment has higher specific discharge capacity and first-circle coulombic efficiency when being applied to a lithium ion battery as an anode material, and the excellent electrochemical performance of the porous silicon-carbon composite anode material is better than that of the anode material in the lithium ion battery compared with the prior commercialized silicon-carbon material (comparative example 1).
Example 2
Firstly, 10g of the materials with the aperture of 20nm and the specific surface area of 100m are weighed 2 Placing/g porous carbon material on a substrate table of a plasma chemical vapor deposition device; the apparatus was evacuated to a vacuum of 1.0X10 -3 Pa; heating the substrate table at a heating rate of 2 ℃/min to enable the deposition temperature to be 600 ℃; argon and silane gas are introduced into the plasma chemical vapor deposition equipment, and the flow ratio of the argon to the silane gas is 10/40sccm; and (3) starting a radio frequency power supply with the power of 300W and the reflected power of 100W, depositing silicon on the porous carbon material, and reacting for 30min to obtain the porous silicon-carbon composite anode material.
Characterization was performed as in example 1 and assembled into lithium ion batteries, and battery performance was investigated. The specific capacity of the lithium ion battery can reach 592.4mAh/g after the first discharge, the coulomb efficiency of the first circle reaches 90.2%, and the specific capacity is kept at 89.8% after 100 circles of circulation.
Example 3
Firstly, 10g of the material with the aperture of 60nm and the specific surface area of 300m are weighed 2 Placing/g porous carbon material on a substrate table of a plasma chemical vapor deposition device; the apparatus was evacuated to a vacuum of 1.0X10 -3 Pa; heating the substrate table at a heating rate of 4 ℃/min to enable the deposition temperature to be 800 ℃; argon and silane gas are introduced into the plasma chemical vapor deposition equipment, and the flow ratio of the argon to the silane gas is 10/80sccm; and (3) starting a radio frequency power supply with power of 500W and reflected power of 200W, depositing silicon on the porous carbon material, and reacting for 90min to obtain the porous silicon-carbon composite anode material.
Characterization was performed as in example 1 and assembled into lithium ion batteries, and battery performance was investigated. The specific capacity of the lithium ion battery can reach 634.7mAh/g after the first discharge, the first-circle coulomb efficiency reaches 91.6%, and the specific capacity is kept at 91.9% after 100 circles of circulation.
Example 4
Firstly, 10g of the material with the aperture of 50nm and the specific surface area of 200m are weighed 2 Placing/g porous carbon material on a substrate table of a plasma chemical vapor deposition device; the apparatus was evacuated to a vacuum of 1.0X10 -3 Pa; heating the substrate table at a heating rate of 5 ℃/minThe deposition temperature is 600 ℃; argon and silane gas are introduced into the plasma chemical vapor deposition equipment, and the flow ratio of the argon to the silane gas is 10/70sccm; and (3) starting a radio frequency power supply with the power of 500W and the reflected power of 200W, depositing silicon on the porous carbon material, and reacting for 60min to obtain the porous silicon-carbon composite anode material.
Characterization was performed as in example 1 and assembled into lithium ion batteries, and battery performance was investigated. The specific capacity of the lithium ion battery can reach 734.7mAh/g after the first discharge, the coulomb efficiency of the first circle reaches 92.4%, and the specific capacity of the lithium ion battery is kept at 92.4% after 100 circles of circulation.
Referring to the method of example 4, composite materials were prepared according to different parameters in table 1, and lithium ion batteries were assembled, and battery performance was studied, specific capacity after 100 cycles at a rate of 0.1C, and the results are shown in the following table.
TABLE 1
Comparative example 1
Electrochemical performance of commercial silicon-carbon composites:
and weighing silicon and graphite according to the mass ratio of silicon to carbon of 7:93, and preparing the silicon-carbon material which is uniformly mixed by a ball milling method.
Characterization was performed as in example 1 and assembled into lithium ion batteries, and battery performance was investigated. The initial discharge specific capacity is only 535mAh/g, the initial coulombic efficiency is 89.9%, the specific capacity is kept at 80% after 100 circles of circulation, and the graph of the circulation performance and the coulombic efficiency is shown in fig. 2. The comparison of electrochemical performance diagrams shows that the specific capacity and the capacity retention rate of the commercial silicon-carbon material are not high, and the specific capacity and the capacity retention rate are required to be improved in the application of the lithium ion battery cathode.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (7)
1. The porous silicon-carbon composite anode material is characterized by being obtained by compositing a porous carbon material and a silicon source.
2. The porous carbon deposited silicon nanocomposite material according to claim 1, wherein the porous carbon material has a pore size of 20 to 60nm and a specific surface area of 100 to 300m 2 /g。
3. The porous silicon carbon deposited silicon nanocomposite of claim 1, wherein the silicon source comprises silane, silicon tetrachloride, or silicon tetrafluoride.
4. The porous carbon deposited silicon nanocomposite of claim 3, wherein the purity of the silicon source is greater than 99.9%.
5. A method for preparing the porous silicon-carbon composite anode material according to any one of claims 1 to 4, comprising the steps of: and preparing the porous carbon material and a silicon source into the porous carbon composite nano silicon material by using a plasma chemical vapor deposition method.
6. The method for preparing a porous carbon deposited silicon nanocomposite according to claim 5, wherein the parameters of the plasma chemical vapor deposition are: the Ar/Si source flow ratio is 10/40-80sccm, the reaction temperature is 600-800 ℃, the heating rate is 2-5 ℃/min, the reaction time is 30-90min, the radio frequency power is 300-500W, and the reflection power is 100-200W.
7. Use of the porous silicon-carbon composite anode material according to any one of claims 1-4 in a lithium ion battery.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311197774.3A CN116995219A (en) | 2023-09-18 | 2023-09-18 | Porous silicon-carbon composite anode material and preparation method and application thereof |
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| CN117995974A (en) * | 2024-01-15 | 2024-05-07 | 浙江大学 | Preparation method of micron-sized silicon-carbon microsphere material, and product and application thereof |
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| CN112768668A (en) * | 2021-02-01 | 2021-05-07 | 株洲弗拉德科技有限公司 | Lithium ion battery silicon-carbon negative electrode material and preparation process and equipment thereof |
| CN114122352A (en) * | 2021-10-29 | 2022-03-01 | 西安交通大学 | Silicon-carbon negative electrode material for inducing silicon deposition by doping porous carbon and preparation method thereof |
| CN115132997A (en) * | 2022-07-13 | 2022-09-30 | Oppo广东移动通信有限公司 | Cathode material, preparation method thereof, battery and electronic equipment |
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| CN112768668A (en) * | 2021-02-01 | 2021-05-07 | 株洲弗拉德科技有限公司 | Lithium ion battery silicon-carbon negative electrode material and preparation process and equipment thereof |
| CN114122352A (en) * | 2021-10-29 | 2022-03-01 | 西安交通大学 | Silicon-carbon negative electrode material for inducing silicon deposition by doping porous carbon and preparation method thereof |
| CN115132997A (en) * | 2022-07-13 | 2022-09-30 | Oppo广东移动通信有限公司 | Cathode material, preparation method thereof, battery and electronic equipment |
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| CN117995974A (en) * | 2024-01-15 | 2024-05-07 | 浙江大学 | Preparation method of micron-sized silicon-carbon microsphere material, and product and application thereof |
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