CN114784253B - Silicon-carbon oxide composite negative electrode material for secondary battery, preparation and application - Google Patents
Silicon-carbon oxide composite negative electrode material for secondary battery, preparation and application Download PDFInfo
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- CN114784253B CN114784253B CN202210549658.2A CN202210549658A CN114784253B CN 114784253 B CN114784253 B CN 114784253B CN 202210549658 A CN202210549658 A CN 202210549658A CN 114784253 B CN114784253 B CN 114784253B
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007773 negative electrode material Substances 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 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 120
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 64
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002135 nanosheet Substances 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 18
- NCZAACDHEJVCBX-UHFFFAOYSA-N [Si]=O.[C] Chemical compound [Si]=O.[C] NCZAACDHEJVCBX-UHFFFAOYSA-N 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 5
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- 238000007323 disproportionation reaction Methods 0.000 claims description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000012300 argon atmosphere Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 229910052573 porcelain Inorganic materials 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 12
- 238000009616 inductively coupled plasma Methods 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 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
- 239000002055 nanoplate Substances 0.000 claims description 3
- 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
- 238000004321 preservation Methods 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- 239000011159 matrix material Substances 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 3
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- 239000010703 silicon Substances 0.000 abstract description 3
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- 238000012983 electrochemical energy storage Methods 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
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- 229910052744 lithium Inorganic materials 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
- 239000002033 PVDF binder Substances 0.000 description 4
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- 239000002064 nanoplatelet Substances 0.000 description 4
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- 239000002002 slurry Substances 0.000 description 4
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- 229940005550 sodium alginate Drugs 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 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
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 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
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
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- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 silicon oxide carbon composite negative electrode material for a secondary battery, a preparation method and application thereof, and belongs to the technical field of preparation of electrochemical energy storage materials. Firstly, disproportionating a silica powder material at high temperature, and growing silicon nanocrystals in an amorphous silica matrix; ball milling is carried out in inert atmosphere to reduce the particle size of the silicon oxide; finally, a plasma enhanced chemical vapor deposition method is adopted to grow the carbon nano-sheets with vertical structures on the surface of the ball-milled silica powder in situ, the conductivity of the composite material is effectively improved by the carbon nano-sheets with vertical structures, and a rich way is provided for the transportation of lithium ions. The method of the invention has simple process, high efficiency and high controllability, and effectively improves the first coulomb efficiency, the cycling stability and the reversible capacity of the silicon oxide/carbon composite material.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery anode materials, in particular to a silicon-carbon oxide composite anode material for a secondary battery, and preparation and application thereof.
Background
With the rapid development of the fields of new energy automobiles, power grid energy storage, consumer electronics and the like, the demand of the lithium ion battery with high energy density in the market is more and more urgent. Graphite is used as the anode material with the most widely commercialized lithium ion battery, and the theoretical specific capacity (372 mAh/g) is low, so that the requirement of the lithium ion battery with high energy density is difficult to meet. Therefore, the development of a novel lithium ion battery anode material with higher energy density and longer cycle life has great significance. Among the numerous negative electrode materials, silicon materials have the advantages of high theoretical specific capacity (3579 mAh/g at normal temperature), low lithium intercalation potential, rich natural resources, good environmental affinity and the like, and are receiving extensive attention. However, silicon can generate serious volume expansion in the process of inserting/extracting lithium as an electrode material, so that active substances are pulverized and fall off, and further the active materials and a current collector lose electrical contact, so that the capacity is rapidly reduced, and the commercialization application of the silicon material in a lithium ion battery is seriously hindered.
As a derivative of silicon, a non-stoichiometric silicon oxide (SiO x) material is favored by researchers due to its high specific capacity and relatively improved cycling performance. However, siO x can form an unstable Solid Electrolyte (SEI) film in the first charge and discharge process, active lithium ions are excessively consumed, meanwhile, the lithium ions react with O elements in the SiO x structure to generate inert substances such as Li 2 O, lithium silicate and the like, so that the first coulomb efficiency of the SiO x material is low, the exertion of the capacity of the positive electrode material is influenced, and the energy density of the lithium ion battery is difficult to improve. In addition, siO x materials also have the problem of low conductivity, which results in poor rate performance. In order to solve the above problems, the present invention proposes a method for in-situ growth of a vertical-structured carbon nano-sheet on the surface of disproportionated silicon oxide by plasma chemical vapor deposition (PECVD) to improve the electrochemical performance of the negative electrode material of silicon oxide. The carbon nano-sheet with the vertical structure not only increases the contact area among particles on a microscopic scale and remarkably improves the conductivity of the silicon oxide anode material, but also improves the interface contact area on an electrode level, provides rich transmission channels for the diffusion of lithium ions and greatly improves the dynamics of an electrode process.
Disclosure of Invention
The invention aims at providing a preparation method of a silicon oxide carbon composite anode material with high specific capacity and good cycle stability for application of a lithium ion battery aiming at the defects of the SiO x material in the background technology.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The preparation method of the silicon-carbon oxide composite anode material for the secondary battery specifically comprises the following steps:
Step 1: disproportionation treatment is carried out on the silica powder under the temperature of 1000 ℃ in an inert atmosphere, and the silica powder is naturally cooled to room temperature after the disproportionation treatment is finished, so that disproportionated silica is prepared;
Step 2: ball milling is carried out on the silicon oxide material obtained after the disproportionation in the step 1 under inert atmosphere so as to reduce the particle size distribution of the silicon oxide material;
Step 3: and (3) growing the carbon nano-sheets with the vertical structures on the surface of the silica powder subjected to ball milling in the step (2) by adopting a plasma enhanced chemical vapor deposition method to form the silica carbon composite material packaged by the carbon nano-sheets with the vertical structures, wherein the specific process is as follows: placing the disproportionated silicon oxide in a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 800 ℃ under argon atmosphere, preserving heat for 20min at 800 ℃ after the temperature is increased to 800 ℃, and then introducing carrier gas and carbon source gas to keep the air pressure in the tubular furnace between 10 Pa and 20 Pa; and then turning on an inductively coupled plasma radio frequency power supply, wherein the output power of the power supply is 250W, the carbon growth time is 10-20min, turning off the inductively coupled plasma radio frequency power supply after the reaction is completed, stopping introducing carbon source gas, and cooling to room temperature under argon atmosphere to obtain the three-dimensional carbon nano-sheet packaged silicon oxide composite anode material.
Preferably, the silicon oxide material with a particle size of 1-10 μm is used in the step 1.
Preferably, the inert atmosphere in the step 1 is any one of argon, helium and neon, and the flow rate is 100sccm.
Preferably, the disproportionation temperature of the silicon oxide in the step 1 is 1000 ℃, the disproportionation heating rate is 5 ℃/min, and the heat preservation time is 3 hours at the disproportionation temperature; 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 rotating speed is 600r/min, and the ball milling time is 6h.
Preferably, the carbon source gas in the step 3 is one or more mixed gases selected from methane, ethane and acetylene, the flow rate is 16sccm, the carrier gas is hydrogen and argon, and the flow rates are 20sccm and 12sccm, respectively.
In the preferred mode, the heating rate of the step 3 to 800 ℃ is 32 ℃/min, the temperature is kept at 800 ℃ for 20min, and then hydrogen and methane are introduced to grow the carbon nano-plate with the vertical structure.
The invention also provides the silicon-carbon oxide composite anode material for the secondary battery, which is obtained by the preparation method.
The invention also provides an application of the silicon oxide carbon composite anode 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 oxide carbon composite anode material for a secondary battery, which adopts disproportionation treatment to increase the distribution of nano silicon crystal domains in a SiO x material matrix, thereby not only effectively improving the reversible capacity of the SiO x material, but also effectively improving the circulation stability of the SiO x material.
2. On one hand, the carbon nano-sheets with the vertical structure have better flexibility, the integrity of the material structure can be kept in the volume expansion/contraction process caused by the insertion/removal of lithium from SiO x, and meanwhile, the abundant pore structures among the carbon nano-sheets can effectively release the internal stress generated by the volume deformation; on the other hand, the electric contact between particles and the interface contact between the electrode and the electrolyte are improved, the electronic conductivity and the ionic conductivity of the SiO x anode material are effectively improved, and the reversible capacity, the multiplying power performance and the cycling stability of the electrode are remarkably improved.
Drawings
FIG. 1 is an SEM image of a comparative example 1 of a silicon oxide negative electrode material of the present invention;
FIG. 2 is an SEM image of a negative electrode material of silica after disproportionation and ball-milling according to example 3 of the present invention;
FIG. 3 is an SEM image of a composite anode material of silicon oxide coated with a carbon nano-sheet with a vertical structure grown on the surface of step 3 of the present invention;
FIG. 4 is a Raman spectrum diagram of the silicon oxide of comparative example 1 and the carbon nano-sheet coated silicon oxide negative electrode material of example 3;
FIG. 5 is a graph showing the cycle performance of the comparative example 1 silica, example 3 step 3 carbon nanoplatelets coated silica negative electrode material of the present invention at a current density of 0.4A/g;
fig. 6 is a graph showing the rate performance of the carbon nano-sheet coated silicon oxide negative electrode material prepared in example 3 according to the present invention under different current densities.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The embodiment of the invention provides a preparation method of a silicon oxide carbon composite anode material for a secondary battery, which specifically comprises the following steps:
Step 1: disproportionation treatment is carried out on the silica powder under the temperature of 1000 ℃ in an inert atmosphere, and the silica powder is naturally cooled to room temperature after the disproportionation treatment is finished, so that disproportionated silica is prepared;
Step 2: ball milling is carried out on the silicon oxide material obtained after the disproportionation in the step 1 under inert atmosphere so as to reduce the particle size distribution of the silicon oxide material;
Step 3: and (3) growing the carbon nano-sheets with the vertical structures on the surface of the silica powder subjected to ball milling in the step (2) by adopting a plasma enhanced chemical vapor deposition method to form the silica carbon composite material packaged by the carbon nano-sheets with the vertical structures, wherein the specific process is as follows: placing the disproportionated silicon oxide in a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 800 ℃ under argon atmosphere, preserving heat for 20min at 800 ℃ after the temperature is increased to 800 ℃, and then introducing carrier gas and carbon source gas to keep the air pressure in the tubular furnace between 10 Pa and 20 Pa; and then turning on an inductively coupled plasma radio frequency power supply, wherein the output power of the power supply is 250W, the carbon growth time is 10-20min, turning off the inductively coupled plasma radio frequency power supply after the reaction is completed, stopping introducing carbon source gas, and cooling to room temperature under argon atmosphere to obtain the three-dimensional carbon nano-sheet packaged silicon oxide composite anode material.
In some embodiments, the step 1 uses a silicon oxide material having a particle size of 1-10 μm.
In some embodiments, the inert atmosphere in the step 1 is any one of argon, helium and neon, and the flow is 100sccm.
In some embodiments, the disproportionation temperature of the silicon oxide in the step 1 is 1000 ℃, the disproportionation heating rate is 5 ℃/min, and the holding time is 3 hours at the disproportionation temperature; and after the disproportionation treatment is finished, naturally cooling to room temperature.
In some embodiments, the inert atmosphere in the step 2 is an argon atmosphere, the ball milling speed is 600r/min, and the ball milling time is 6h.
In some embodiments, the carbon source gas in the step 3 is one or a mixture of several gases selected from methane, ethane and acetylene, the flow rate is 16sccm, the carrier gas is hydrogen and argon, and the flow rates are 20sccm and 12sccm, respectively.
In some embodiments, the heating rate of the step 3 to 800 ℃ is 32 ℃/min, and the temperature is kept at 800 ℃ for 20min, and then hydrogen and methane are introduced to grow the carbon nano-plate with the vertical structure.
The preparation method is used for obtaining the silicon oxide carbon composite anode material for the secondary battery.
The silicon oxide carbon composite anode material for the secondary battery can be applied to a lithium ion battery.
Comparative example 1
An SEM image of the silicon oxide negative electrode material without any treatment is shown in fig. 1; as can be seen from FIG. 1, the silica is a few irregular blocks with smooth surface and particle size between 1-10 μm.
The silicon oxide material without any treatment was prepared into an electrode sheet, and the prepared electrode sheet was assembled into a battery in a glove box, and its electrochemical properties were tested. The preparation method of the electrode slice comprises the following steps: mixing the silicon oxide material with a conductive agent and a binder according to the mass ratio of 8:1:1 to prepare slurry, coating the slurry on the rough surface of the copper foil, and drying 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 tube and conductive graphite, wherein the conductive carbon black is selected in the comparative example, the binder comprises one or more of sodium carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), sodium Alginate (SA) and polyacrylic acid (PAA), and the conductive carbon black is selected in the comparative example. Cutting the prepared electrode into small discs with the diameter of 10mm, and putting the small discs in a glove box with the oxygen and water contents of less than 0.1 ppm; celgard-2500 is used as a diaphragm, 1.2MLiPF 6 is dissolved in a mixed solution of EC: DEC: FEC and 2% VC which are used as additives in a volume ratio of 3:6:1 to obtain a mixed solution, a lithium sheet is used as a counter electrode, and the CR2032 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 oxide powder of a silicon oxide material with the particle size of 1 mu m into a porcelain boat, placing into a tube 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 3 hours, performing disproportionation treatment at the temperature of 1000 ℃ in the argon atmosphere, and naturally cooling to room temperature after the disproportionation treatment is completed to obtain a disproportionated silicon oxide anode material;
Step 2: ball-milling the silica material obtained after the disproportionation in the step 1 for 6 hours at the rotating speed of 600r/min under the argon atmosphere, and ball-milling under the inert atmosphere to reduce the particle size distribution; the silica material with more uniform particle size distribution is obtained.
Step 3: and (3) growing the carbon nano-sheets with the vertical structures on the surface of the silica powder subjected to ball milling in the step (2) by adopting a plasma enhanced chemical vapor deposition method to form the silica carbon composite material packaged by the carbon nano-sheets with the vertical structures, wherein the specific process is as follows: placing the disproportionated silicon oxide in a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 800 ℃ at a heating rate of 32 ℃/min under argon atmosphere, preserving heat for 20min at 800 ℃, 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 mixed gases of methane, ethane and acetylene, the flow is 16sccm, the carrier gas is hydrogen and argon, and the flow is 20sccm and 12sccm respectively. And then turning on an inductively coupled plasma radio frequency power supply, wherein the output power of the power supply is 250W, the carbon growth time is 10min, turning off the inductively coupled plasma radio frequency power supply after the reaction is completed, stopping introducing carbon source gas, and cooling to room temperature in an argon atmosphere to obtain the three-dimensional carbon nano-sheet packaged silicon oxide composite anode material.
An SEM image of the silicon oxide anode material after disproportionation and ball milling treatment is shown in fig. 2; as can be seen from FIG. 2, the microstructure of the silica material subjected to ball milling after disproportionation is not significantly changed, and is still irregular, but the particle size is reduced to below 2 μm, and the distribution is more uniform, as compared with comparative example 1. The disproportionation treatment is not damaging the morphology and structure of the silicon oxide material, and the ball milling treatment effectively reduces the particle size of the silicon oxide material.
FIG. 3 is a SEM image of in-situ grown vertical structure carbon nanoplatelets coated silicon oxide negative electrode material; SEM images show that the surface carbon layers have curved and corrugated morphology and cross-connect with each other to form a porous structure, which not only ensures sufficient contact of the active material with the electrolyte, but also plays a role of a rapid lithium ion transport path during lithiation/delithiation.
Preparing the silicon oxide composite negative electrode material into an electrode plate, assembling the prepared electrode plate into a battery in a glove box, and testing the electrochemical performance of the battery. The preparation method of the electrode slice comprises the following steps: mixing the silicon oxide material with a conductive agent and a binder according to the mass ratio of 8:1:1 to prepare slurry, coating the slurry on the rough surface of the copper foil, and drying in a vacuum oven at 80 ℃ for 12 hours to prepare the electrode slice. The conductive agent includes any one or more of conductive carbon black, ketjen black, carbon nanotubes and conductive graphite, and in this embodiment, the conductive carbon black is selected, and the binder includes one or more of sodium carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), sodium Alginate (SA) and polyacrylic acid (PAA), and in this embodiment, sodium hydroxymethyl cellulose (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 in a glove box with the oxygen and water contents of less than 0.1 ppm; celgard-2500 is used as a diaphragm, 1.2MLiPF 6 is dissolved in a mixed solution of EC: DEC: FEC and 2% VC which are used as additives in a volume ratio of 3:6:1 to obtain a mixed solution, a lithium sheet is used as a counter electrode, and the CR2032 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 1, placing a silicon oxide material with the particle size of 10 mu m in a porcelain boat, placing the porcelain boat in a tube furnace, introducing nitrogen with the flow of 100sccm, heating to 1000 ℃ at the heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 3 hours, and naturally cooling to room temperature after disproportionation treatment is completed to obtain a disproportionated silicon oxide anode material.
And 2, ball milling the disproportionated silicon oxide in the step 1 for 6 hours at the rotating speed of 600r/min under the argon atmosphere to obtain the silicon oxide material with more uniform particle size distribution.
And 3, placing the silicon oxide material treated in the step 2 into a porcelain boat, placing the porcelain boat into a tube furnace, firstly pumping the air pressure in the tube furnace to 0.1-1Pa, and then introducing argon with the flow of 12sccm. Then heating to 800 ℃ at a heating rate of 32 ℃/min, preserving heat at 800 ℃ for 20min, and after the temperature distribution in the tube furnace is uniform, introducing hydrogen and methane, wherein the flow rates are respectively 20sccm and 16sccm, so that the air pressure in the tube furnace is kept between 10 Pa and 20 Pa. And then turning on an inductively coupled plasma radio frequency power supply to start the growth of the carbon nano-sheets with the vertical structure, wherein the output power of the power supply is 250W, the carbon growth time is 20min, turning off the inductively coupled plasma radio frequency power supply after the reaction is completed, stopping introducing methane and hydrogen, and naturally cooling to room temperature in an argon atmosphere to obtain the silicon oxide/carbon composite anode material packaged by the carbon nano-sheets with the vertical structure.
The preparation process of the electrode sheet, the assembly and the test procedure of the button cell were the same as 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:
step 1, placing a silicon oxide material with the grain diameter of 5 mu m into a porcelain boat, placing into a tube furnace, introducing helium with the flow of 100sccm, heating to 1000 ℃ at the heating rate of 5 ℃/min in helium atmosphere, preserving heat for 3 hours, and naturally cooling to room temperature after disproportionation treatment is completed to obtain a disproportionated silicon oxide anode material.
And 2, ball milling the disproportionated silicon oxide in the step 1 for 6 hours at the rotating speed of 600r/min under the argon atmosphere to obtain the silicon oxide material with more uniform particle size distribution.
And 3, placing the silicon oxide material treated in the step 2 into a porcelain boat, placing the porcelain boat into a tube furnace, firstly pumping the air pressure in the tube furnace to 0.1-1Pa, and then introducing argon with the flow of 12sccm. Then heating to 800 ℃ at a heating rate of 32 ℃/min, maintaining at 800 ℃ for 20min, and after the temperature distribution in the tube furnace is uniform, introducing hydrogen and methane, wherein the flow rates are respectively 20sccm and 16sccm, so that the air pressure in the tube furnace is maintained between 10 Pa and 20 Pa. And then turning on an inductively coupled plasma radio frequency power supply to start the growth of the carbon nano-sheets with the vertical structure, wherein the output power of the power supply is 250W, the carbon growth time is 15min, turning off the inductively coupled plasma radio frequency power supply after the reaction is completed, stopping introducing methane and hydrogen, and naturally cooling to room temperature in an argon atmosphere to obtain the silicon oxide/carbon composite anode material packaged by the carbon nano-sheets with the vertical structure.
The preparation process of the electrode sheet, the assembly and the test procedure of the button cell were the same as in example 1.
FIG. 4 is a Raman spectrum of the silica prepared in comparative example 1 and example 3, the silica obtained by ball milling after disproportionation, and the silica/carbon negative electrode material obtained by growing vertical carbon nanoplatelets on the surface after disproportionation and ball milling; as can be seen from fig. 4, the silicon oxide negative electrode material prepared in step 2 of example 3 has an increased nano silicon domain in the matrix compared with comparative example 1. The silica/carbon negative electrode material prepared in example 3 shows characteristic signals of carbon (D peak: -1329 cm -1 and G peak: -1600 cm -1), the D peak being associated with disorder and defects, which can be attributed to numerous edges of the vertical carbon nanoplatelets. The G peak is caused by in-plane stretching vibration of sp2 hybridization of carbon atoms. Peaks at 520 and 950cm -1 originate from silicon nanocrystals embedded in the SiO x matrix.
FIG. 5 is a graph showing the long cycle performance of the negative electrode materials prepared in comparative example 1 and example 3 according to the present invention at a current density of 0.4A/g after 1 cycle at a current density of 0.1A/g; as can be seen from the graph, after 300 circles of circulation, the reversible capacity of the silicon oxide material without any treatment is almost attenuated to zero, the reversible capacity and the circulation stability of the silicon oxide material after disproportionation and ball milling are improved to a certain extent, after the vertical structure carbon nano-sheet is grown on the surface of the silicon oxide material in situ by a plasma chemical vapor deposition (PECVD), the initial coulomb efficiency reaches 81%, the reversible specific capacity after 300 circles is higher than 1100mAh/g, and the capacity retention rate exceeds 100% (relative to the second circle).
FIG. 6 is a graph showing the rate performance of the silica-carbon composite anode material prepared in example 3 of the present invention at different current densities; as can be seen from fig. 6, the reversible capacity decreases with increasing current density, and after the current density returns to 0.1A/g, the capacity returns to 84% of the initial capacity, indicating high stability of the electrode structure during the rate test.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims of this invention, which are within the skill of those skilled in the art, can be made without departing from the spirit and scope of the invention disclosed herein.
Claims (9)
1. The preparation method of the silicon oxide carbon composite anode material for the secondary battery is characterized by comprising the following steps of:
Step 1: disproportionation treatment is carried out on the silica powder under the temperature of 1000 ℃ in an inert atmosphere, and the silica powder is naturally cooled to room temperature after the disproportionation treatment is finished, so that disproportionated silica is prepared;
Step 2: ball milling is carried out on the silicon oxide material obtained after the disproportionation in the step 1 under inert atmosphere so as to reduce the particle size distribution of the silicon oxide material;
Step 3: and (3) growing the carbon nano-sheets with the vertical structures on the surface of the silica powder subjected to ball milling in the step (2) by adopting a plasma enhanced chemical vapor deposition method to form the silica carbon composite material packaged by the carbon nano-sheets with the vertical structures, wherein the specific process is as follows: placing the disproportionated silicon oxide in a porcelain boat, placing the porcelain boat in a tubular furnace, heating to 800 ℃ under argon atmosphere, preserving heat for 20min at 800 ℃ after the temperature is increased to 800 ℃, and then introducing carrier gas and carbon source gas to keep the air pressure in the tubular furnace between 10 Pa and 20 Pa; and then turning on an inductively coupled plasma radio frequency power supply, wherein the output power of the power supply is 250W, the carbon growth time is 10-20min, turning off the inductively coupled plasma radio frequency power supply after the reaction is completed, stopping introducing carbon source gas, and cooling to room temperature under argon atmosphere to obtain the three-dimensional carbon nano-sheet packaged silicon oxide composite anode material, wherein the prepared anode material is the SiO x material surface in-situ grown carbon nano-sheet with a vertical structure.
2. The method for preparing the silicon oxide carbon composite anode material for the secondary battery according to claim 1, wherein the method comprises the following steps: the silicon oxide material with the particle size of 1-10 mu m is adopted in the step 1.
3. The method for preparing the silicon oxide carbon composite anode material for the secondary battery according to claim 1, wherein the method comprises the following steps: the inert atmosphere in the step 1 is any one of argon, helium and neon, and the flow is 100sccm.
4. The method for preparing the silicon oxide carbon composite anode material for the secondary battery according to claim 1, wherein the method comprises the following steps: the disproportionation temperature of the silicon oxide in the step 1 is 1000 ℃, the disproportionation heating rate is 5 ℃/min, and the heat preservation time is 3 hours at the disproportionation temperature; and after the disproportionation treatment is finished, naturally cooling to room temperature.
5. The method for preparing the silicon carbide composite anode material for the secondary battery according to 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 6h.
6. The method for preparing the silicon oxide carbon composite anode material for the secondary battery according to claim 1, wherein the method comprises the following steps: the carbon source gas in the step3 is one or more mixed gases of methane, ethane and acetylene, the flow rate is 16sccm, the carrier gas is hydrogen and argon, and the flow rates are 20sccm and 12sccm respectively.
7. The method for preparing the silicon oxide carbon composite anode material for the secondary battery according to claim 1, wherein the method comprises the following steps: and 3, heating to 800 ℃ in the step, wherein the heating rate is 32 ℃/min, preserving heat for 20min at 800 ℃, and then introducing hydrogen and methane to grow the carbon nano-plate with the vertical structure.
8. A silicon oxide carbon composite anode material for a secondary battery obtained by the production method according to any one of claims 1 to 7.
9. Use of the silicon carbide composite negative electrode material for secondary batteries according to claim 8 in lithium ion batteries.
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