CN114784253A - Silicon-carbon oxide composite negative electrode material for secondary battery and preparation and application thereof - Google Patents
Silicon-carbon oxide composite negative electrode material for secondary battery and preparation and application thereof Download PDFInfo
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- CN114784253A CN114784253A CN202210549658.2A CN202210549658A CN114784253A CN 114784253 A CN114784253 A CN 114784253A CN 202210549658 A CN202210549658 A CN 202210549658A CN 114784253 A CN114784253 A CN 114784253A
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- AUEPDNOBDJYBBK-UHFFFAOYSA-N [Si].[C-]#[O+] Chemical compound [Si].[C-]#[O+] AUEPDNOBDJYBBK-UHFFFAOYSA-N 0.000 title description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000002135 nanosheet Substances 0.000 claims abstract description 33
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 31
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 239000012298 atmosphere Substances 0.000 claims abstract description 15
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- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 10
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- 230000008569 process Effects 0.000 claims abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 26
- 229910052573 porcelain Inorganic materials 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
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- 239000007789 gas Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- 238000009616 inductively coupled plasma Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
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- NCZAACDHEJVCBX-UHFFFAOYSA-N [Si]=O.[C] Chemical compound [Si]=O.[C] NCZAACDHEJVCBX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 10
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- 238000009826 distribution Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 abstract description 22
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002090 carbon oxide Inorganic materials 0.000 abstract description 2
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- 238000012983 electrochemical energy storage Methods 0.000 abstract 1
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- 239000010406 cathode material Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 235000010413 sodium alginate Nutrition 0.000 description 4
- 239000000661 sodium alginate Substances 0.000 description 4
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 238000009831 deintercalation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
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- 239000003273 ketjen black Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 230000037427 ion transport Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a sub-silicon carbon oxide composite negative electrode material for a secondary battery, and a preparation method and application thereof, and belongs to the technical field of electrochemical energy storage material preparation. Firstly, carrying out disproportionation treatment on a silica powder material at a high temperature, and growing a silicon nanocrystal in an amorphous silica matrix; then ball milling is carried out under inert atmosphere to reduce the particle size of the silicon monoxide; and finally, growing the carbon nanosheets with the vertical structures in situ on the surface of the ball-milled sub-silicon oxide powder by adopting a plasma enhanced chemical vapor deposition method, wherein the carbon nanosheets with the vertical structures effectively improve the conductivity of the composite material and provide a rich approach for the transportation of lithium ions. The method disclosed by the invention is simple in process, efficient and high in controllability, and the first coulombic efficiency, the circulation stability and the reversible capacity of the silicon oxide/carbon composite material are effectively improved.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery cathode materials, in particular to a silicon monoxide carbon composite cathode material for a secondary battery, and preparation and application thereof.
Background
With the rapid development of new energy vehicles, power grid energy storage, consumer electronics and other fields, the demand for high-energy density lithium ion batteries in the market is more and more urgent. Graphite is used as the most widely commercialized negative electrode material of the lithium ion battery, and the theoretical specific capacity (372mAh/g) of the graphite is low, so that the demand of the high-energy density lithium ion battery is difficult to meet. Therefore, it is of great significance to develop a new lithium ion battery anode material with higher energy density and longer cycle life. Among a plurality of negative electrode materials, the silicon material has the advantages of high theoretical specific capacity (3579 mAh/g at normal temperature), low lithium intercalation potential, abundant natural resources, good environmental affinity and the like, and is widely concerned by people. However, silicon as an electrode material can generate severe volume expansion in the lithium intercalation/deintercalation process, which leads to pulverization and exfoliation of active substances, and further leads the active material and a current collector to lose electric contact, which leads to rapid capacity decay, thus seriously hindering the commercial application of silicon materials in lithium ion batteries.
As a derivative of silicon, nonstoichiometric Silica (SiO)x) Materials are highly appreciated by researchers because of their high specific capacity and relatively improved cycling performance. However, SiOxAn unstable Solid Electrolyte Interface (SEI) film is formed during the first charge and discharge process, and active lithium ions are excessively consumed, and simultaneously, the lithium ions and SiOxReaction of O element in the structure to produce Li2O and lithium silicate, resulting in SiOxThe first coulombic efficiency of the material is low, the exertion of the capacity of the anode material is influenced, and the energy density of the lithium ion battery is difficult to improve. In addition, SiOxThe material also has the problem of low conductivity, resulting in poor rate capability. In order to solve the above problems, the present invention providesA carbon nanosheet with a vertical structure grows on the disproportionated silicon oxide surface in situ by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method so as to improve the electrochemical performance of the silicon oxide negative electrode material. The carbon nanosheets with the vertical structure not only increase the contact area between particles on a microscale and remarkably improve the conductivity of the silicon monoxide negative electrode material, but also improve the interface contact area on an electrode level, provide rich transmission channels for the diffusion of lithium ions and greatly improve the dynamics of the electrode process.
Disclosure of Invention
The present invention is directed to SiO in the background artxThe defects of the material provide a preparation method of the silicon oxide carbon composite negative electrode material which has high specific capacity and good cycling stability and is applied to the lithium ion battery.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a silicon carbide oxide composite negative electrode material for a secondary battery specifically comprises the following steps:
step 1: disproportionating the silicon monoxide powder in an inert atmosphere at the temperature of below 1000 ℃, and naturally cooling to room temperature after the disproportionating treatment is finished to prepare disproportionated silicon monoxide;
and 2, step: ball milling the silicon monoxide material obtained after disproportionation in the step 1 in an inert atmosphere to reduce the particle size distribution of the silicon monoxide material;
and step 3: growing carbon nanosheets with vertical structures on the surface of the ball-milled sub-silicon oxide powder in the step 2 by adopting a plasma enhanced chemical vapor deposition method to form the sub-silicon oxide carbon composite material packaged by the carbon nanosheets with the vertical structures, wherein the specific process comprises the following steps: putting the disproportionated silicon monoxide in the step 1 into a porcelain boat, putting the porcelain boat into a tube furnace, heating the porcelain boat to 800 ℃ under the argon atmosphere, keeping the temperature at 800 ℃ for 20min after the temperature is raised to 800 ℃, and introducing carrier gas and carbon source gas to keep the air pressure in the tube furnace between 10 and 20 Pa; and then turning on an inductively coupled plasma radio frequency power supply, wherein the power supply output power is 250W, the carbon growth time is 10-20min, turning off the inductively coupled plasma radio frequency power supply after the reaction is finished, stopping introducing the carbon source gas, and cooling to room temperature under the argon atmosphere to obtain the carbon nano sheet packaged silicon oxide composite negative electrode material with the three-dimensional structure.
Preferably, the step 1 adopts a silica material with the grain diameter of 1-10 μm.
Preferably, the inert atmosphere in step 1 is any one of argon, helium and neon, and the flow rate is 100 sccm.
Preferably, in the step 1, the disproportionation temperature of the silicon monoxide is 1000 ℃, the disproportionation temperature rise rate is 5 ℃/min, and the heat preservation time at the disproportionation temperature is 3 hours; and after the disproportionation treatment is finished, naturally cooling to room temperature.
Preferably, the inert atmosphere in the step 2 is argon atmosphere, the ball milling rotation speed is 600r/min, and the ball milling time is 6 h.
Preferably, the carbon source gas in the step 3 is one or more mixed gases of methane, ethane and acetylene, the flow rate of the mixed gas is 16sccm, the carrier gases are hydrogen and argon, and the flow rates of the carrier gases are 20sccm and 12sccm respectively.
Preferably, the heating rate of heating to 800 ℃ in the step 3 is 32 ℃/min, the temperature is kept at 800 ℃ for 20min, and then hydrogen and methane are introduced for growth of the vertical-structure carbon nanosheets.
The invention also provides a silicon oxide carbon composite negative electrode material for a secondary battery, which is obtained by the preparation method.
The invention also provides application of the silicon oxide carbon composite negative electrode material for the secondary battery in a lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of a silicon carbide oxide composite negative electrode material for a secondary battery, which adopts disproportionation treatment to increase SiOxThe distribution of nano-silicon crystal domains in the material matrix not only effectively improves SiOxThe reversible capacity of the material is improved, and the cycle stability of the material is effectively improved.
2. SiO disproportionated by PECVD methodxMaterial tableThe carbon nano-sheets with the vertical structure grow in situ, and on one hand, the carbon nano-sheets with the vertical structure have better flexibility and grow on SiOxThe integrity of the material structure can be kept in the volume expansion/contraction process caused by lithium intercalation/deintercalation, and the rich pore structures among the carbon nano sheets can effectively release the internal stress generated by volume deformation; on the other hand, the electric contact between particles and the interface contact between an electrode and electrolyte are improved, and the SiO is effectively improvedxThe electronic conductivity and ionic conductivity of the cathode material obviously improve the reversible capacity, rate capability and cycling stability of the electrode.
Drawings
FIG. 1 is an SEM image of a silica negative electrode material of comparative example 1 of the present invention;
FIG. 2 is an SEM image of a disproportionated and ball-milled negative silica electrode material obtained in step 2 of example 3 of the present invention;
fig. 3 is an SEM image of the surface-grown vertical-structure carbon nanosheet-coated silica composite anode material in step 3 of embodiment 3 of the present invention;
FIG. 4 is a Raman spectrum of a silica anode material coated with comparative example 1 silica and example 3 step 3 carbon nanosheets according to the present invention;
FIG. 5 is a graph showing the comparison of the cycle performance of the inventive comparative example 1 silica and the example 3 step 3 carbon nanosheet coated silica anode material at a current density of 0.4A/g;
fig. 6 is a rate performance graph of the carbon nanosheet-coated silica negative electrode material prepared in embodiment 3 of the present invention at different current densities.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The embodiment of the invention provides a preparation method of a sub-silicon carbon oxide composite negative electrode material for a secondary battery, which comprises the following steps:
step 1: disproportionating the silicon monoxide powder at the temperature of below 1000 ℃ in an inert atmosphere, and naturally cooling to room temperature after the disproportionating treatment is finished to prepare disproportionated silicon monoxide;
step 2: ball milling the silicon monoxide material obtained after disproportionation in the step 1 in an inert atmosphere to reduce the particle size distribution of the silicon monoxide material;
and 3, step 3: growing carbon nanosheets with vertical structures on the surface of the ball-milled sub-silicon oxide powder in the step 2 by adopting a plasma enhanced chemical vapor deposition method to form the sub-silicon oxide carbon composite material packaged by the carbon nanosheets with the vertical structures, wherein the specific process comprises the following steps: putting the disproportionated silicon monoxide in the step 1 into a porcelain boat, putting the porcelain boat into a tube furnace, heating the porcelain boat to 800 ℃ under the argon atmosphere, keeping the temperature at 800 ℃ for 20min after the temperature is raised to 800 ℃, and introducing carrier gas and carbon source gas to keep the air pressure in the tube furnace between 10 and 20 Pa; and then turning on an inductively coupled plasma radio frequency power supply, wherein the power supply output power is 250W, the carbon growth time is 10-20min, turning off the inductively coupled plasma radio frequency power supply after the reaction is finished, stopping introducing the carbon source gas, and cooling to room temperature under the argon atmosphere to obtain the three-dimensional carbon nanosheet packaged silicon monoxide composite negative electrode material.
In some embodiments, step 1 employs a silica material having a particle size of 1-10 μm.
In some embodiments, the inert atmosphere in step 1 is any one of argon, helium and neon, and the flow rate is 100 sccm.
In some embodiments, the disproportionation temperature of the silicon monoxide in the step 1 is 1000 ℃, the disproportionation temperature rise rate is 5 ℃/min, and the holding time at the disproportionation temperature is 3 hours; after the disproportionation treatment is finished, naturally cooling to room temperature.
In some embodiments, the inert atmosphere in step 2 is argon atmosphere, the ball milling rotation speed is 600r/min, and the ball milling time is 6 h.
In some embodiments, the carbon source gas in step 3 is one or more of methane, ethane and acetylene, and the carrier gas is hydrogen and argon at a flow rate of 16sccm and 20sccm and 12sccm, respectively.
In some embodiments, the heating rate of the heating to 800 ℃ in the step 3 is 32 ℃/min, the temperature is kept at 800 ℃ for 20min, and then hydrogen and methane are introduced to perform the growth of the vertical-structure carbon nanosheet.
The preparation method is used for obtaining the silicon monoxide carbon composite negative electrode material for the secondary battery.
The silicon monoxide carbon composite negative electrode material for the secondary battery can be applied to a lithium ion battery.
Comparative example 1
An SEM image of the silica negative electrode material without any treatment as shown in fig. 1; as can be seen from FIG. 1, the silica is irregular and has a smooth surface and a particle size of 1-10 μm.
And preparing the silicon monoxide material which is not subjected to any treatment into electrode plates, assembling the prepared electrode plates into a battery in a glove box, and testing the electrochemical performance of the battery. The steps for preparing the electrode slice are as follows: mixing the silicon monoxide material, the conductive agent and the binder according to the mass ratio of 8: 1 to prepare slurry, then coating the slurry on the rough surface of the copper foil, and baking the copper foil in a vacuum oven at 80 ℃ for 12 hours to prepare the electrode slice. The conductive agent comprises any one or more of conductive carbon black, Ketjen black, carbon nano tubes and conductive graphite, the conductive carbon black is selected in the comparative example, the binder comprises one or more of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR), polyvinylidene fluoride (PVDF), Sodium Alginate (SA) and polyacrylic acid (PAA), and the sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) are selected in the comparative example. Cutting the prepared electrode into small discs with the diameter of 10mm, and putting the small discs into a glove box with the oxygen and water contents lower than 0.1 ppm; celgard-2500 was used as a separator, 1.2MLiPF6And a mixed solution obtained by dissolving the materials in a mixed solution with the volume ratio of EC to DEC to FEC being 3:6:1 and 2% of VC being an additive is used as an electrolyte, a lithium sheet is used as a counter electrode, and the CR2032 type button cell is assembled in a glove box.
Example 1
The embodiment provides a preparation method of a silicon oxide carbon composite anode material for a secondary battery, which comprises the following steps:
step 1: placing a silicon monoxide material silicon monoxide powder with the grain diameter of 1 mu m in a porcelain boat, placing the porcelain boat in a tubular furnace, introducing argon with the flow of 100sccm, heating to 1000 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, preserving heat for 3h, carrying out disproportionation treatment at the temperature of 1000 ℃ in the argon atmosphere, naturally cooling to room temperature after the disproportionation treatment is finished, and preparing the disproportionated silicon monoxide negative electrode material;
and 2, step: ball-milling the silicon monoxide material obtained after disproportionation in the step 1 for 6 hours at the rotating speed of 600r/min in the argon atmosphere, and carrying out ball-milling in the inert atmosphere to reduce the particle size distribution; the silicon oxide material with more uniform particle size distribution is obtained.
And step 3: growing carbon nanosheets with vertical structures on the surface of the ball-milled sub-silicon oxide powder in the step 2 by adopting a plasma enhanced chemical vapor deposition method to form the sub-silicon oxide carbon composite material packaged by the carbon nanosheets with the vertical structures, wherein the specific process comprises the following steps: and (2) placing the disproportionated silicon monoxide in the step (1) into a porcelain boat, placing the porcelain boat into a tubular furnace, heating the porcelain boat to 800 ℃ at a heating rate of 32 ℃/min under an argon atmosphere, keeping the temperature at 800 ℃ for 20min, and introducing carrier gas and carbon source gas to keep the air pressure in the tubular furnace at 10-20 Pa, wherein the carbon source gas is one or more of methane, ethane and acetylene, the flow rate of the carbon source gas is 16sccm, the carrier gas is hydrogen and argon, and the flow rates of the carrier gas are 20sccm and 12sccm respectively. And then turning on an inductively coupled plasma radio frequency power supply, wherein the power supply output power is 250W, the carbon growth time is 10min, turning off the inductively coupled plasma radio frequency power supply after the reaction is finished, stopping introducing the carbon source gas, and cooling to room temperature under the argon atmosphere to obtain the carbon nano sheet packaged silicon oxide composite negative electrode material with the three-dimensional structure.
As shown in fig. 2, is an SEM image of the disproportionated and ball-milled negative silica electrode material; as can be seen from fig. 2, compared with comparative example 1, the morphology of the disproportionated and ball-milled silica material is not significantly changed, and is still an irregular block, and the particle size is reduced to below 2 μm, and the distribution is more uniform. The disproportionation treatment does not damage the appearance and structure of the silicon oxide material, and the ball milling treatment effectively reduces the particle size of the silicon oxide material.
As shown in fig. 3, is an SEM image of the carbon nanosheet coated silicon oxide negative electrode material with an in-situ grown vertical structure; the SEM picture shows that the carbon layers on the surface have a bent and wrinkled morphology and are cross-linked with each other to form a porous structure, not only ensuring sufficient contact of the active material with the electrolyte, but also functioning as a rapid lithium ion transport path during lithiation/delithiation.
Preparing the silicon monoxide composite negative electrode material into electrode slices, assembling the prepared electrode slices into a battery in a glove box, and testing the electrochemical performance of the battery. The steps for preparing the electrode slice are as follows: mixing the silicon monoxide material, the conductive agent and the binder according to the mass ratio of 8: 1 to prepare slurry, then coating the slurry on the rough surface of the copper foil, and baking the copper foil in a vacuum oven at 80 ℃ for 12 hours to prepare the electrode slice. The conductive agent comprises any one or more of conductive carbon black, ketjen black, carbon nanotubes and conductive graphite, in the embodiment, the conductive carbon black is selected, the binder comprises one or more of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR), polyvinylidene fluoride (PVDF), Sodium Alginate (SA) and polyacrylic acid (PAA), and in the embodiment, sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) are selected. Cutting the prepared electrode into small discs with the diameter of 10mm, and putting the small discs into a glove box with the oxygen and water contents lower than 0.1 ppm; celgard-2500 as diaphragm, 1.2MLiPF6And a mixed solution obtained by dissolving the mixture in a mixed solution with EC: DEC: FEC in a volume ratio of 3:6:1 and 2% VC as an additive is used as an electrolyte, a lithium sheet is used as a counter electrode, and the CR2032 type button cell is assembled in a glove box.
Example 2
The embodiment provides a preparation method of a silicon oxide carbon composite anode material for a secondary battery, which comprises the following steps:
And 2, ball-milling the disproportionated silicon monoxide in the step 1 for 6 hours at a rotating speed of 600r/min in an argon atmosphere to obtain a silicon monoxide material with more uniform particle size distribution.
And 3, placing the silicon monoxide material treated in the step 2 in a porcelain boat, placing the porcelain boat in a tubular furnace, pumping the pressure in the tubular furnace to 0.1-1Pa, and then introducing argon gas with the flow of 12 sccm. And then, starting to heat to 800 ℃ at a heating rate of 32 ℃/min, preserving the heat for 20min at 800 ℃, introducing hydrogen and methane after the temperature in the tubular furnace is uniformly distributed, wherein the flow rates are respectively 20sccm and 16sccm, and keeping the air pressure in the tubular furnace between 10 and 20 Pa. And then starting an inductively coupled plasma radio frequency power supply to start the growth of the carbon nanosheets with the vertical structure, wherein the output power of the power supply is 250W, the carbon growth time is 20min, closing the inductively coupled plasma radio frequency power supply after the reaction is finished, stopping introducing methane and hydrogen, and naturally cooling to room temperature under the argon atmosphere to obtain the vertical-structure carbon nanosheet packaged silicon monoxide/carbon composite cathode material.
The preparation process of the electrode plate and the assembly and test flow of the button cell are the same as those in example 1.
Example 3
The embodiment provides a preparation method of a silicon oxide carbon composite anode material for a secondary battery, which comprises the following steps:
And 2, ball-milling the disproportionated silicon monoxide in the step 1 for 6 hours at a rotating speed of 600r/min in an argon atmosphere to obtain a silicon monoxide material with more uniform particle size distribution.
And 3, placing the silicon monoxide material treated in the step 2 in a porcelain boat, placing the porcelain boat in a tubular furnace, pumping the pressure in the tubular furnace to 0.1-1Pa, and then introducing argon gas with the flow of 12 sccm. And then, starting to heat to 800 ℃ at a heating rate of 32 ℃/min, keeping the temperature at 800 ℃ for 20min, and introducing hydrogen and methane with the flow rates of 20sccm and 16sccm respectively after the temperature in the tubular furnace is uniformly distributed, so that the air pressure in the tubular furnace is kept between 10 and 20 Pa. And then starting an inductively coupled plasma radio frequency power supply, starting the growth of the carbon nanosheets with the vertical structure, wherein the power output power is 250W, the carbon growth time is 15min, closing the inductively coupled plasma radio frequency power supply after the reaction is finished, stopping introducing methane and hydrogen, and naturally cooling to room temperature under the argon atmosphere to obtain the vertical-structure carbon nanosheet packaged silicon monoxide/carbon composite cathode material.
The preparation process of the electrode plate and the assembly and test flow of the button cell are the same as those in example 1.
FIG. 4 is a Raman spectrum of the silica prepared in comparative example 1 and example 3, the silica obtained by disproportionation and ball milling, and the silica/carbon negative electrode material with vertical carbon nanosheets grown on the surface after disproportionation and ball milling; as shown in fig. 4, the size of the nano-silicon crystal domain in the matrix of the negative electrode material of the silicon monoxide prepared in step 2 of example 3 is larger than that of comparative example 1. The characteristic signal of carbon (D peak: 1329 cm) is shown in the Raman spectrum of the silicon oxide/carbon cathode material prepared in the example 3-1And G peak: about 1600cm-1) The D peak is associated with disorder and defects, which can be attributed to the numerous edges of the perpendicular carbon nanoplatelets. The G peak is caused by in-plane stretching vibration of carbon atom sp2 hybridization. Peaks at 520 and 950cm-1Derived from being embedded in SiOxSilicon nanocrystals in the matrix.
FIG. 5 is a graph showing long cycle performance of the negative electrode materials prepared in comparative example 1 and example 3 of the present invention at a current density of 0.4A/g after cycling for 1 cycle at a current density of 0.1A/g; it can be seen from the figure that after the cycle of 300 cycles, the reversible capacity of the silica material without any treatment is almost attenuated to zero, the reversible capacity and the cycle stability of the disproportionated and ball-milled silica material are both improved to a certain extent, and after the carbon nano-sheets with the vertical structure are grown on the surface of the silica material in situ by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, the first coulombic efficiency reaches 81%, the reversible specific capacity is higher than 1100mAh/g after the cycle of 300 times, and the capacity retention rate exceeds 100% (relative to the second cycle).
FIG. 6 is a graph of rate performance of the SiOx-carbon composite negative electrode material prepared in example 3 according to the present invention at different current densities; as can be seen from fig. 6, the reversible capacity decreased with an increase in current density, and the capacity recovered to 84% of the initial capacity after the current density returned to 0.1A/g, indicating that the electrode structure had high stability during the rate test.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A preparation method of a silicon carbide oxide composite negative electrode material for a secondary battery is characterized by comprising the following steps:
step 1: disproportionating the silicon monoxide powder in an inert atmosphere at the temperature of below 1000 ℃, and naturally cooling to room temperature after the disproportionating treatment is finished to prepare disproportionated silicon monoxide;
and 2, step: ball milling the silicon monoxide material obtained after disproportionation in the step 1 in an inert atmosphere to reduce the particle size distribution of the silicon monoxide material;
and step 3: growing carbon nanosheets with vertical structures on the surface of the ball-milled sub-silicon oxide powder in the step 2 by adopting a plasma enhanced chemical vapor deposition method to form the sub-silicon oxide carbon composite material packaged by the carbon nanosheets with the vertical structures, wherein the specific process comprises the following steps: putting the disproportionated silicon monoxide in the step 1 into a porcelain boat, putting the porcelain boat into a tube furnace, heating the porcelain boat to 800 ℃ under the argon atmosphere, keeping the temperature at 800 ℃ for 20min after the temperature is raised to 800 ℃, and introducing carrier gas and carbon source gas to keep the air pressure in the tube furnace between 10 and 20 Pa; and then turning on an inductively coupled plasma radio frequency power supply, wherein the power supply output power is 250W, the carbon growth time is 10-20min, turning off the inductively coupled plasma radio frequency power supply after the reaction is finished, stopping introducing the carbon source gas, and cooling to room temperature under the argon atmosphere to obtain the carbon nano sheet packaged silicon oxide composite negative electrode material with the three-dimensional structure.
2. The method of preparing a negative electrode material of a secondary battery according to claim 1, wherein: the step 1 adopts a silicon oxide material with the grain diameter of 1-10 mu m.
3. The method for preparing the negative electrode material of claim 1, wherein the negative electrode material comprises at least one of the following components: the inert atmosphere in the step 1 is any one of argon, helium and neon, and the flow rate is 100 sccm.
4. The method of preparing a negative electrode material of a secondary battery according to claim 1, wherein: in the step 1, the disproportionation temperature of the silicon monoxide is 1000 ℃, the disproportionation temperature rise rate is 5 ℃/min, and the heat preservation time at the disproportionation temperature is 3 hours; after the disproportionation treatment is finished, naturally cooling to room temperature.
5. The method for preparing the negative electrode material of claim 1, wherein the inert atmosphere in the step 2 is argon atmosphere, the ball milling speed is 600r/min, and the ball milling time is 6 h.
6. The method of preparing a negative electrode material of a secondary battery according to claim 1, wherein: the carbon source gas in the step 3 is one or more mixed gas of methane, ethane and acetylene, the flow rate is 16sccm, the carrier gas is hydrogen and argon, and the flow rate is 20sccm and 12sccm respectively.
7. The method for preparing the negative electrode material of claim 1, wherein the negative electrode material comprises at least one of the following components: and 3, heating to 800 ℃ in the step 3 at a heating rate of 32 ℃/min, preserving the heat at 800 ℃ for 20min, and then introducing hydrogen and methane to grow the carbon nanosheets with the vertical structures.
8. The negative electrode material for a secondary battery, which is obtained by the production method according to any one of claims 1 to 7.
9. Use of the negative electrode material for a secondary battery of the silicon oxide-carbon composite according to claim 8 in a lithium ion battery.
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