CN116387497B - Method for preparing lithium ion battery anode material by treating silicon waste material through molten salt method - Google Patents
Method for preparing lithium ion battery anode material by treating silicon waste material through molten salt method Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 102
- 239000010703 silicon Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 75
- 239000002699 waste material Substances 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- 239000010405 anode material Substances 0.000 title claims abstract description 28
- 150000003839 salts Chemical class 0.000 title claims abstract description 15
- 239000002210 silicon-based material Substances 0.000 claims abstract description 65
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000005416 organic matter Substances 0.000 claims abstract description 20
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 49
- 239000011259 mixed solution Substances 0.000 claims description 48
- 239000012065 filter cake Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 21
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 20
- 238000005520 cutting process Methods 0.000 claims description 19
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 150000003376 silicon Chemical group 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002341 toxic gas Substances 0.000 abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052573 porcelain Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000011856 silicon-based particle Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000000110 cooling liquid Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002153 silicon-carbon composite material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910021430 silicon nanotube Inorganic materials 0.000 description 1
- 239000002620 silicon nanotube Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003911 water pollution 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
- H01M4/366—Composites as layered products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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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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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a lithium ion battery anode material by treating silicon waste material by a molten salt method, and belongs to the technical field of methods or devices for directly converting chemical energy into electric energy. The method comprises the following steps: s1, removing stains on the surface of silicon waste to obtain a impurity-removed silicon raw material; s2, coating the surface of the impurity-removed silicon raw material to form an organic matter layer, so as to obtain an organic matter coated silicon material; s3, combining the carbonate mixture with the organic matter coated silicon material in a physical mode to obtain a pre-baked silicon material; s4, roasting the pre-roasted silicon material in an oxygen-free environment to obtain a carbon-coated silicon material; s5, washing to remove the water-soluble silicate generated in the carbon-coated silicon material, and obtaining the lithium ion battery anode material. The invention shortens the process flow, improves the production efficiency, generates no toxic gas and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of methods or devices for directly converting chemical energy into electric energy, in particular to a method for preparing a lithium ion battery anode material by treating silicon waste by a molten salt method.
Background
Silicon is a promising material in the next generation of lithium ion battery cathode materials as a battery material with high energy density, the theoretical specific capacity of which exceeds 10 times of that of the graphite electrode material. But greatly limits the development of silicon-based materials due to the poor conductivity of silicon itself and the volume change caused during charge and discharge. Efforts have been made to overcome these problems, such as the use of nanostructures (silicon nanowires, silicon nanotubes, silicon nanospheres, etc.) to mitigate the volume expansion of the silicon negative electrode during lithium intercalation and deintercalation. However, the cost of silicon nanomaterials remains too high to be suitable for large scale production. Therefore, a low-cost, high-performance silicon material is urgently needed to meet the market demand of lithium ion batteries. The carbonaceous negative electrode material has small volume change in the charge and discharge process and good cycle stability, and the carbonaceous negative electrode material is a mixture of ions and electrons; in addition, silicon has similar chemical properties to carbon, and the two can be closely combined, so carbon is often used as a preferred matrix for compositing with silicon.
Based on the principle, chinese patent CN108767220A discloses a silicon-carbon composite material, a preparation method thereof, a battery cathode material and a battery. The silicon-carbon composite material is of a hollow microsphere structure and comprises a shell and a cavity, wherein the shell covers the cavity, the shell is mainly formed by compounding silicon and carbon, and space is provided for volume change of the silicon in the charging and discharging process through the cavity, so that the problems of volume expansion and structural collapse of the silicon in the charging and discharging process are effectively solved, and the cycle stability and the battery capacity of a battery are improved; and the conductivity of the composite material is improved through the synergistic effect of silicon and carbon. However, the preparation process of the invention is complex and SiO needs to be prepared 2 Sol, more raw material limitation and narrower source surface; in addition, indissolvable metal simple substance is needed to be added as a reducing agent in the preparation process, impurities are easy to introduce and difficult to remove, and the production efficiency is low.
The semiconductor material silicon has unique photoelectric effect and is widely applied to the semiconductor and photovoltaic industries. In the preparation process of the crystalline silicon solar cell, a polycrystalline silicon ingot or a monocrystalline silicon rod is firstly formed into a square rod, and then the square rod is sliced into polycrystalline silicon wafers or monocrystalline silicon wafers with the thickness of 0.18-0.19 mm. Because the diameter of the cutting wire is not much different from the thickness of the required crystalline silicon ingot, 40-50% of crystalline silicon with mass fraction is cut in the online cutting process to form cutting scraps, and the quantity is huge; in addition, the particle size of the silicon cutting waste is extremely fine and is 1-10 mu m, if the silicon cutting waste is improperly treated, the silicon cutting waste can cause serious environmental hazard, and powder pollution or water pollution can be formed. Therefore, if the partially cut silicon waste materials can be recycled and utilized in the preparation process of the lithium ion battery anode material, the environmental pollution can be reduced, the secondary utilization of resources can be realized, and great economic benefits can be brought. At present, the recovery method of the cut silicon waste mainly comprises a chemical treatment method, a thermal plasma smelting method and a high-temperature induction smelting method, the previous research mainly focuses on removing impurities in silicon powder, and the research on directly using the cut silicon waste for lithium ion battery materials by carrying out surface treatment on the cut silicon waste is extremely rare. Compared with nano silicon powder, the granularity of the cut silicon waste belongs to the micron level, and the tap density is high, so that the cut silicon waste has the practical application value of a battery, and the production cost is greatly reduced by taking the cut silicon waste as a raw material.
In summary, the invention provides a method for directly converting low-cost and micron-sized silicon waste into a lithium ion battery silicon-based anode material with high added value. Considering that an oxide film is formed on the surface of silicon waste in the cutting process, the existence of a thicker oxide film greatly influences the electrochemical performance of the material, reduces the electronic and ionic conductivity of the material and the specific capacity of the material, so that the removal of the oxide layer on the surface of silicon particles and the design of a reasonable silicon-carbon composite structure are key to improving the lithium storage performance of the cut silicon waste. However, when reducing with a reducing agent such as carbon or hydrogen, which is common, the reduction rate is extremely low due to kinetic limitations. A common method for removing oxide films on the surfaces of silicon particles is etching with hydrofluoric acid: siO (SiO) 2 +4HF=SiF 4 (g)+2H 2 O, but the use of hydrofluoric acid increases equipment corrosion on the one hand and SiF on the other hand 4 Such toxic gases cause secondary pollution, and also cause silicon loss and difficult recovery. Based on the method, the invention provides a method for etching oxide on the surface of the silicon particle by using molten salt and carrying out silicon-carbon recombination, so that cut silicon waste is successfully and directly converted into a battery anode material with high added value, strong acid and strong alkali are not used in the whole process, and no toxic is generatedThe secondary pollutants such as gas, etc., are environment-friendly, the silicon loss is small, the technological process is short, the production cost is low, and the operation is simple.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, in a first aspect of the present invention, there is provided a method for preparing a lithium ion battery anode material by treating silicon waste material by a molten salt method, which is environment-friendly and simple in process, comprising the steps of:
s1, removing stains on the surface of silicon waste to obtain a impurity-removed silicon raw material;
s2, coating the surface of the impurity-removed silicon raw material to form an organic matter layer, so as to obtain an organic matter coated silicon material;
s3, combining the carbonate mixture with the organic matter coated silicon material in a physical mode to obtain a pre-baked silicon material;
s4, roasting the pre-roasted silicon material in an oxygen-free environment to obtain a carbon-coated silicon material;
s5, washing to remove the water-soluble silicate generated in the carbon-coated silicon material, and obtaining the lithium ion battery anode material.
According to the method, silicon waste is used as a silicon source, a carbon-containing organic matter layer is formed on the surface of the silicon waste in a coating mode, and then the surface of silicon particles is subjected to pyrolysis carbonization on the coated organic matter through roasting treatment under an anaerobic condition; at the same time, siO on the surface of the silicon scrap particles 2 Can be used as a sacrificial layer to react with carbonate mixture to generate water-soluble silicate and carbon dioxide. In the roasting process, a carbon layer and a water-soluble silicate layer are synchronously formed, finally, the water-soluble silicate is removed through washing, and a cavity is reserved between the silicon core and the carbon layer, so that the multi-layer core-shell composite structure with the silicon core/the cavity/the carbon layer, namely the lithium ion battery anode material, is obtained. The cavity effectively relieves the volume expansion effect of silicon particles in the charging and discharging processes. While the carbon layer of the outer shell enhances the conductivity of the electrode material on the one hand and also mitigates the volume expansion of silicon on the other hand. The whole process flow is simple, no toxic gas is generated, and the method is safe and harmless.
Preferably, in the step S1, the silicon scrap is a dicing scrap formed during the dicing process of the crystalline silicon.
Preferably, the specific method of step S1 is as follows: washing the silicon waste to primarily remove organic stains on the surface; and (3) placing the primarily-decontaminated silicon waste material in an anaerobic environment for heat treatment, and further removing residual organic matters to obtain the decontaminated silicon raw material.
Preferably, the specific method of step S2 is as follows: dissolving a carbon source and a nitrogen source in water, uniformly mixing to obtain a carbon-nitrogen source mixed solution, adding the impurity-removed silicon raw material into the carbon-nitrogen source mixed solution, and performing hydrothermal reaction in an oxygen-free environment to form an organic matter layer on the surface of the impurity-removed silicon raw material; and after the hydrothermal reaction is finished, filtering a reaction product, collecting a filter cake, and washing and drying the filter cake to obtain the organic matter coated silicon material.
Further preferably, the carbon source is resorcinol and formaldehyde.
Further preferably, the nitrogen source is one of melamine, sodium nitrate, potassium nitrate, and ammonium nitrate.
Further, the preparation method of the carbon-nitrogen source mixed solution comprises the following steps of: adding 2-5 parts of resorcinol and 5-10 parts of 37% formaldehyde aqueous solution into 30 parts of water, and uniformly mixing to obtain a first mixed solution; adding 5 parts of nitrogen source and 9 parts of formaldehyde aqueous solution with the mass percentage concentration of 37% into 30 parts of water, and uniformly mixing to obtain a second mixed solution; and uniformly mixing the first mixed solution and the second mixed solution to obtain the carbon-nitrogen source mixed solution.
Further preferably, the mass ratio of the carbon-nitrogen source mixed solution to the impurity-removed silicon raw material is 40.5-44.5: 1.
further preferably, the temperature of the hydrothermal reaction is 75-85 ℃, and the reaction time is 18-30 hours.
Preferably, the specific method of step S3 is as follows: and mixing the organic matter coated silicon material with a carbonate mixture containing carbonate ions, and then performing ball milling treatment and tabletting treatment to obtain the pre-baked silicon material.
Further preferably, the ball milling treatment time is 2-6 hours.
Further preferably, the pressure of the tabletting treatment is 2-6 MPa.
Preferably, in the step S3, the carbonate mixture is a mixture of sodium carbonate and potassium carbonate, and the molar ratio of sodium carbonate to potassium carbonate is 59:41.
the relevant reactions of sodium carbonate and potassium carbonate for silicon dioxide etching are as follows:
Na 2 CO 3 +SiO 2 =Na 2 SiO 3 +CO 2 (g)；
K 2 CO 3 +SiO 2 =K 2 SiO 3 +CO 2 (g)。
preferably, in the step S3, the molar ratio of the silicon element in the organic coating silicon material to the carbonate ion in the carbonate mixture is 1 to 10:1.
the carbonate ions can react with silicon to generate carbon, and the addition amount of the carbonate mixture can be regulated and controlled to ensure that a small amount of carbon is additionally generated in the reaction process, so that the conductivity of the silicon is enhanced, and the volume change of the silicon in the charge and discharge processes is further relieved to a certain extent.
Preferably, in the step S4, the temperature of the baking treatment is 600-750 ℃ and the treatment time is 4-6 hours.
Preferably, the specific method of step S5 is as follows: and washing the carbon-coated silicon material with water to remove water-soluble silicate generated in the roasting treatment, filtering and collecting a filter cake after washing, and drying the filter cake to obtain the lithium ion battery anode material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a method for preparing a lithium ion battery anode material by treating silicon waste by a molten salt method, which takes the silicon waste as a raw material, reduces the production cost and realizes the recycling of the silicon waste. The method takes oxidation of the surface of the silicon waste as a natural sacrificial template, firstly coats the silicon waste to form an organic layer, and then utilizes a carbonate mixture to etch the oxidation layer in roasting treatment, so that a cavity capable of relieving the volume expansion of silicon is reserved between a silicon core and an outer carbon shell, and the conductivity of the material is enhanced by the outer carbon shell. In the method, the etching process of the mixture of the carbon layer and the carbonate is completed in one step in the roasting process, so that the process flow is shortened, and the production efficiency is improved. The molten salt etching process of the carbonate mixture avoids toxic gas generated in the process of etching by hydrofluoric acid, and is environment-friendly.
Drawings
Fig. 1 is an effect schematic diagram of a part of a process of a method for preparing a lithium ion battery anode material by treating silicon waste material by a molten salt method.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples:
dilute hydrochloric acid: 2mol/L;
aqueous formaldehyde solution: 37wt.%;
carbonate mixture: the molar ratio of sodium carbonate to potassium carbonate is 59:41 are mixed.
Example 1
The method for preparing the lithium ion battery cathode material by treating silicon waste material by a molten salt method comprises the following steps:
s1, firstly, washing cutting waste formed in the cutting process of crystalline silicon with dilute hydrochloric acid and anhydrous acetone in sequence, and primarily removing impurities and organic cooling liquid on the surface of the silicon waste; then placing the primarily decontaminated silicon waste material into a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of argon, performing heat treatment at the temperature for 3 hours, further removing residual organic matters, and naturally cooling the furnace body to room temperature after heat treatment to obtain a decontaminated silicon raw material;
s2, adding 4g of resorcinol and 6g of formaldehyde aqueous solution to 30mL of deionized water, and continuously stirring for 2 hours at 40 ℃ to obtain a first mixed solution; dissolving 5g of melamine and 9g of formaldehyde in 30mL of deionized water, and stirring at 80 ℃ until the solution becomes clear, so as to obtain a second mixed solution; uniformly mixing the first mixed solution and the second mixed solution to obtain a carbon-nitrogen source mixed solution, then adding 2g of the impurity-removed silicon raw material into the carbon-nitrogen source mixed solution, uniformly mixing, transferring into a closed three-neck flask, heating at a constant temperature of 80 ℃ for 24 hours for hydrothermal reaction, and coating the surface of the impurity-removed silicon raw material to form an organic layer; after the hydrothermal reaction is finished, filtering a reaction product, collecting a filter cake, washing the filter cake, and drying the filter cake at 100 ℃ for 4 hours to obtain an organic matter coated silicon material;
s3, mixing the organic coating silicon material with a carbonate mixture containing carbonate ions, wherein the molar ratio of silicon element in the organic coating silicon material to carbonate ions in the carbonate mixture is 2:1, a step of; after ball milling treatment for 4 hours, tabletting is completed under the pressure of 4MPa, and a pre-baked silicon material is prepared;
s4, placing the pre-baked silicon material into an alumina small porcelain boat, placing the alumina small porcelain boat into a tube furnace, roasting at 600 ℃ for 4 hours in an argon atmosphere, naturally cooling to room temperature in the argon atmosphere after roasting is finished, and taking out to obtain a carbon-coated silicon material;
s5, washing to remove water-soluble silicate generated by the carbon-coated silicon material in the roasting treatment, filtering to collect a filter cake after washing, and drying the filter cake to obtain the lithium ion battery anode material.
The structural transition between the impurity-removed silicon waste, the organic coating silicon material and the lithium ion battery anode material is shown in the schematic diagram of fig. 1. The lithium ion battery cathode material is a multi-layer core-shell composite structure of silicon core/cavity/carbon layer. Lithium ion electrochemical storage testing was performed on the lithium ion battery negative electrode material of example 1 by using a blue battery charge-discharge tester at room temperature, and the material was tested in the form of a button cell. The first-cycle discharge specific capacity of the lithium ion battery anode material under the current density of 1A/g is up to 2500mAh/g, and after 300 cycles, the discharge specific capacity is still maintained at 1050mAh/g. The test result shows that the lithium ion battery anode material has excellent circulation stability, and the multi-layer core-shell composite structure of the silicon core/cavity/carbon layer is beneficial to relieving the volume expansion effect of silicon particles in the charge and discharge process while increasing the conductivity of the material.
Example 2
The method for preparing the lithium ion battery cathode material by treating silicon waste material by a molten salt method comprises the following steps:
s1, firstly, washing cutting waste formed in the cutting process of crystalline silicon with dilute hydrochloric acid and anhydrous acetone in sequence, and primarily removing impurities and organic cooling liquid on the surface of the silicon waste; then placing the primarily decontaminated silicon waste material into a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of argon, performing heat treatment at the temperature for 3 hours, further removing residual organic matters, and naturally cooling the furnace body to room temperature after heat treatment to obtain a decontaminated silicon raw material;
s2, adding 2g of resorcinol and 5g of formaldehyde aqueous solution to 30mL of deionized water, and continuously stirring for 2 hours at 40 ℃ to obtain a first mixed solution; dissolving 5g of sodium nitrate and 9g of formaldehyde aqueous solution in 30mL of deionized water, and stirring at 80 ℃ until the solution becomes clear, so as to obtain a second mixed solution; uniformly mixing the first mixed solution and the second mixed solution to obtain a carbon-nitrogen source mixed solution, then adding 2g of the impurity-removed silicon raw material into the carbon-nitrogen source mixed solution, uniformly mixing, transferring into a closed three-neck flask, heating at a constant temperature of 75 ℃ for 30 hours for hydrothermal reaction, and coating the surface of the impurity-removed silicon raw material to form an organic layer; after the hydrothermal reaction is finished, filtering a reaction product, collecting a filter cake, washing the filter cake, and drying the filter cake at 100 ℃ for 4 hours to obtain an organic matter coated silicon material;
s3, mixing the organic coating silicon material with a carbonate mixture containing carbonate ions, wherein the molar ratio of silicon element in the organic coating silicon material to carbonate ions in the carbonate mixture is 1:1, a step of; after ball milling treatment for 6 hours, tabletting is completed under the pressure of 6MPa, and a pre-baked silicon material is prepared;
s4, placing the pre-baked silicon material into an alumina small porcelain boat, placing the alumina small porcelain boat into a tube furnace, roasting at 600 ℃ for 6 hours in an argon atmosphere, naturally cooling to room temperature in the argon atmosphere after roasting, and taking out to obtain a carbon-coated silicon material;
s5, washing to remove water-soluble silicate generated by the carbon-coated silicon material in the roasting treatment, filtering to collect a filter cake after washing, and drying the filter cake to obtain the lithium ion battery anode material.
Example 3
The method for preparing the lithium ion battery cathode material by treating silicon waste material by a molten salt method comprises the following steps:
s1, firstly, washing cutting waste formed in the cutting process of crystalline silicon with dilute hydrochloric acid and anhydrous acetone in sequence, and primarily removing impurities and organic cooling liquid on the surface of the silicon waste; then placing the primarily decontaminated silicon waste material into a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of argon, performing heat treatment at the temperature for 3 hours, further removing residual organic matters, and naturally cooling the furnace body to room temperature after heat treatment to obtain a decontaminated silicon raw material;
s2, adding 5g of resorcinol and 10g of formaldehyde aqueous solution to 30mL of deionized water, and continuously stirring for 2 hours at 40 ℃ to obtain a first mixed solution; dissolving 5g of potassium nitrate and 9g of formaldehyde aqueous solution in 30mL of deionized water, and stirring at 80 ℃ until the solution becomes clear, so as to obtain a second mixed solution; uniformly mixing the first mixed solution and the second mixed solution to obtain a carbon-nitrogen source mixed solution, then adding 2g of the impurity-removed silicon raw material into the carbon-nitrogen source mixed solution, uniformly mixing, transferring into a closed three-neck flask, heating at a constant temperature of 85 ℃ for 18h for hydrothermal reaction, and coating the surface of the impurity-removed silicon raw material to form an organic layer; after the hydrothermal reaction is finished, filtering a reaction product, collecting a filter cake, washing the filter cake, and drying the filter cake at 100 ℃ for 4 hours to obtain an organic matter coated silicon material;
s3, mixing the organic coating silicon material with a carbonate mixture containing carbonate ions, wherein the molar ratio of silicon element in the organic coating silicon material to carbonate ions in the carbonate mixture is 10:1, a step of; after ball milling treatment for 2 hours, tabletting is completed under the pressure of 2MPa, and a pre-baked silicon material is prepared;
s4, placing the pre-baked silicon material into an alumina small porcelain boat, placing the alumina small porcelain boat into a tube furnace, roasting at 750 ℃ for 4 hours in an argon atmosphere, naturally cooling to room temperature in the argon atmosphere after roasting is finished, and taking out to obtain a carbon-coated silicon material;
s5, washing to remove water-soluble silicate generated by the carbon-coated silicon material in the roasting treatment, filtering to collect a filter cake after washing, and drying the filter cake to obtain the lithium ion battery anode material.
Example 4
The method for preparing the lithium ion battery cathode material by treating silicon waste material by a molten salt method comprises the following steps:
s1, firstly, washing cutting waste formed in the cutting process of crystalline silicon with dilute hydrochloric acid and anhydrous acetone in sequence, and primarily removing impurities and organic cooling liquid on the surface of the silicon waste; then placing the primarily decontaminated silicon waste material into a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of argon, performing heat treatment at the temperature for 3 hours, further removing residual organic matters, and naturally cooling the furnace body to room temperature after heat treatment to obtain a decontaminated silicon raw material;
s2, adding 4g of resorcinol and 6g of formaldehyde aqueous solution to 30mL of deionized water, and continuously stirring for 2 hours at 40 ℃ to obtain a first mixed solution; 5g of ammonium nitrate and 9g of formaldehyde aqueous solution are dissolved in 30mL of deionized water, and stirred at 80 ℃ until the solution becomes clear, so as to obtain a second mixed solution; uniformly mixing the first mixed solution and the second mixed solution to obtain a carbon-nitrogen source mixed solution, then adding 2g of the impurity-removed silicon raw material into the carbon-nitrogen source mixed solution, uniformly mixing, transferring into a closed three-neck flask, heating at a constant temperature of 80 ℃ for 24 hours for hydrothermal reaction, and coating the surface of the impurity-removed silicon raw material to form an organic layer; after the hydrothermal reaction is finished, filtering a reaction product, collecting a filter cake, washing the filter cake, and drying the filter cake at 100 ℃ for 4 hours to obtain an organic matter coated silicon material;
s3, mixing the organic coating silicon material with a carbonate mixture containing carbonate ions, wherein the molar ratio of silicon element in the organic coating silicon material to carbonate ions in the carbonate mixture is 2:1, a step of; after ball milling treatment for 4 hours, tabletting is completed under the pressure of 4MPa, and a pre-baked silicon material is prepared;
s4, placing the pre-baked silicon material into an alumina small porcelain boat, placing the alumina small porcelain boat into a tube furnace, roasting at 600 ℃ for 4 hours in an argon atmosphere, naturally cooling to room temperature in the argon atmosphere after roasting is finished, and taking out to obtain a carbon-coated silicon material;
s5, washing to remove water-soluble silicate generated by the carbon-coated silicon material in the roasting treatment, filtering to collect a filter cake after washing, and drying the filter cake to obtain the lithium ion battery anode material.
Example 5
The method for preparing the lithium ion battery cathode material by treating silicon waste material by a molten salt method comprises the following steps:
s1, firstly, washing cutting waste formed in the cutting process of crystalline silicon with dilute hydrochloric acid and anhydrous acetone in sequence, and primarily removing impurities and organic cooling liquid on the surface of the silicon waste; then placing the primarily decontaminated silicon waste material into a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of argon, performing heat treatment at the temperature for 3 hours, further removing residual organic matters, and naturally cooling the furnace body to room temperature after heat treatment to obtain a decontaminated silicon raw material;
s2, adding 4g of resorcinol and 6g of formaldehyde aqueous solution to 30mL of deionized water, and continuously stirring for 2 hours at 40 ℃ to obtain a first mixed solution; dissolving 5g of melamine and 9g of formaldehyde in 30mL of deionized water, and stirring at 80 ℃ until the solution becomes clear, so as to obtain a second mixed solution; uniformly mixing the first mixed solution and the second mixed solution to obtain a carbon-nitrogen source mixed solution, then adding 2g of the impurity-removed silicon raw material into the carbon-nitrogen source mixed solution, uniformly mixing, transferring into a closed three-neck flask, heating at a constant temperature of 80 ℃ for 24 hours for hydrothermal reaction, and coating the surface of the impurity-removed silicon raw material to form an organic layer; after the hydrothermal reaction is finished, filtering a reaction product, collecting a filter cake, washing the filter cake, and drying the filter cake at 100 ℃ for 4 hours to obtain an organic matter coated silicon material;
s3, mixing the organic coating silicon material with a carbonate mixture containing carbonate ions, wherein the molar ratio of silicon element in the organic coating silicon material to carbonate ions in the carbonate mixture is set to be a preset value; after ball milling treatment for 4 hours, tabletting is completed under the pressure of 4MPa, and a pre-baked silicon material is prepared;
s4, placing the pre-baked silicon material into an alumina small porcelain boat and placing the alumina small porcelain boat into a tube furnace, roasting under set conditions in an argon atmosphere, naturally cooling to room temperature in the argon atmosphere after roasting is finished, and taking out to obtain a carbon-coated silicon material;
s5, washing to remove water-soluble silicate generated by the carbon-coated silicon material in the roasting treatment, filtering to collect a filter cake after washing, and drying the filter cake to obtain the lithium ion battery anode material.
In this embodiment, n (Si) in step S3 is controlled: n (CO) 3 2- ) The ratio of (2), the temperature and time of the baking treatment in step S4) are divided into experimental groups in table 1, and the corresponding lithium ion battery anode material is prepared under predetermined process conditions.
Table 1: different parameters of different production processes of experimental group
In the embodiment, experimental groups with different process parameters can be adopted to prepare the lithium ion battery anode material with a multi-layer core-shell composite structure.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (6)
1. The method for preparing the lithium ion battery anode material by treating the silicon waste material by a molten salt method is characterized by comprising the following steps of:
s1, removing stains on the surface of silicon waste to obtain a impurity-removed silicon raw material;
s2, dissolving resorcinol, formaldehyde and a nitrogen source in water, and uniformly mixing to obtain a carbon-nitrogen source mixed solution; adding the impurity-removed silicon raw material into the carbon-nitrogen source mixed solution, and then carrying out hydrothermal reaction in an oxygen-free environment to form an organic layer on the surface of the impurity-removed silicon raw material; after the hydrothermal reaction is finished, filtering a reaction product, collecting a filter cake, and washing and drying the filter cake to obtain an organic matter coated silicon material;
s3, combining the carbonate mixture with the organic matter coated silicon material in a physical mode to obtain a pre-baked silicon material;
s4, roasting the pre-roasted silicon material in an oxygen-free environment to obtain a carbon-coated silicon material;
s5, washing to remove the water-soluble silicate generated in the carbon-coated silicon material to obtain a lithium ion battery anode material;
the surface of the impurity-removed silicon raw material is provided with a silicon dioxide layer;
the nitrogen source is one of melamine, sodium nitrate, potassium nitrate and ammonium nitrate; the mass ratio of the carbon-nitrogen source mixed solution to the impurity-removed silicon raw material is 40.5-44.5: 1, a step of; the temperature of the hydrothermal reaction is 75-85 ℃, and the reaction time is 18-30 h;
the carbonate mixture is sodium carbonate and potassium carbonate with a mole ratio of 59: 41; the molar ratio of silicon element in the organic matter coated silicon material to carbonate ions in the carbonate mixture is 1-10: 1, a step of;
the temperature of the roasting treatment is 600-750 ℃ and the treatment time is 4-6 hours;
the lithium ion battery anode material has a multi-layer core-shell composite structure of a silicon core/a cavity/a carbon layer.
2. The method according to claim 1, wherein the specific method of step S1 is as follows: washing the silicon waste to primarily remove organic stains on the surface; placing the primarily decontaminated silicon waste material in an anaerobic environment for heat treatment, and further removing residual organic matters to obtain a decontaminated silicon raw material; the silicon scraps are cutting scraps formed in the cutting processing process of crystalline silicon.
3. The method according to claim 1, wherein the preparation method of the carbon-nitrogen source mixed solution comprises the following steps of: adding 2-5 parts of resorcinol and 5-10 parts of 37% formaldehyde aqueous solution into 30 parts of water, and uniformly mixing to obtain a first mixed solution; adding 5 parts of nitrogen source and 9 parts of formaldehyde aqueous solution with the mass percentage concentration of 37% into 30 parts of water, and uniformly mixing to obtain a second mixed solution; and uniformly mixing the first mixed solution and the second mixed solution to obtain the carbon-nitrogen source mixed solution.
4. The method according to claim 1, wherein the specific method of step S3 is as follows: and mixing the organic matter coated silicon material with a carbonate mixture containing carbonate ions, and then performing ball milling treatment and tabletting treatment to obtain the pre-baked silicon material.
5. The method according to claim 4, wherein: the ball milling treatment time is 2-6 hours; the pressure of the tabletting treatment is 2-6 MPa.
6. The method according to claim 1, wherein the specific method of step S5 is as follows: and washing the carbon-coated silicon material with water to remove water-soluble silicate generated in the roasting treatment, filtering and collecting a filter cake after washing, and drying the filter cake to obtain the lithium ion battery anode material.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337613A (en) * | 2013-07-04 | 2013-10-02 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| CN107768618A (en) * | 2017-09-25 | 2018-03-06 | 北京博雅合众环保科技有限公司 | The preparation method of Si-C composite material and its application as lithium ion battery negative material |
| CN109755482A (en) * | 2017-11-01 | 2019-05-14 | 同济大学 | Silicon/carbon composite material and preparation method thereof |
| CN110289408A (en) * | 2019-06-26 | 2019-09-27 | 东北大学 | Nano-silicon and silicon/carbon composite materials based on cutting silicon waste and their preparation methods and applications |
| AU2020101077A4 (en) * | 2019-06-20 | 2020-07-23 | Xiamen University | Silicon/carbon composite and preparation method and use thereof |
| CN111816857A (en) * | 2020-07-21 | 2020-10-23 | 黄杰 | Nano-silicon composite material with core-shell structure and preparation method and application thereof |
| CN111807345A (en) * | 2020-06-17 | 2020-10-23 | 银隆新能源股份有限公司 | Silicon carbon composite material, preparation method thereof, negative electrode material for lithium battery and lithium battery |
| CN112652758A (en) * | 2020-12-14 | 2021-04-13 | 云帆(镇江)新能源材料有限公司 | Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof |
| CN113659122A (en) * | 2021-08-16 | 2021-11-16 | 四川金汇能新材料股份有限公司 | A kind of silicon carbon anode material, preparation method and application |
| CN114122336A (en) * | 2020-08-28 | 2022-03-01 | 南京工业大学 | A kind of preparation method of hollow structure silicon carbon composite material decorated with ultrafine metal nanoparticles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3654413A1 (en) * | 2018-11-14 | 2020-05-20 | Université de Liège | Silicon-carbon composite anode material |
-
2023
- 2023-06-05 CN CN202310653960.7A patent/CN116387497B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337613A (en) * | 2013-07-04 | 2013-10-02 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| CN107768618A (en) * | 2017-09-25 | 2018-03-06 | 北京博雅合众环保科技有限公司 | The preparation method of Si-C composite material and its application as lithium ion battery negative material |
| CN109755482A (en) * | 2017-11-01 | 2019-05-14 | 同济大学 | Silicon/carbon composite material and preparation method thereof |
| AU2020101077A4 (en) * | 2019-06-20 | 2020-07-23 | Xiamen University | Silicon/carbon composite and preparation method and use thereof |
| CN110289408A (en) * | 2019-06-26 | 2019-09-27 | 东北大学 | Nano-silicon and silicon/carbon composite materials based on cutting silicon waste and their preparation methods and applications |
| CN111807345A (en) * | 2020-06-17 | 2020-10-23 | 银隆新能源股份有限公司 | Silicon carbon composite material, preparation method thereof, negative electrode material for lithium battery and lithium battery |
| CN111816857A (en) * | 2020-07-21 | 2020-10-23 | 黄杰 | Nano-silicon composite material with core-shell structure and preparation method and application thereof |
| CN114122336A (en) * | 2020-08-28 | 2022-03-01 | 南京工业大学 | A kind of preparation method of hollow structure silicon carbon composite material decorated with ultrafine metal nanoparticles |
| CN112652758A (en) * | 2020-12-14 | 2021-04-13 | 云帆(镇江)新能源材料有限公司 | Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof |
| CN113659122A (en) * | 2021-08-16 | 2021-11-16 | 四川金汇能新材料股份有限公司 | A kind of silicon carbon anode material, preparation method and application |
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