CN113991099A - Method for preparing nano silicon-based negative electrode material from silicon cutting waste - Google Patents
Method for preparing nano silicon-based negative electrode material from silicon cutting waste Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 76
- 239000010703 silicon Substances 0.000 title claims abstract description 76
- 239000002699 waste material Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000005520 cutting process Methods 0.000 title claims abstract description 37
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 24
- 239000007773 negative electrode material Substances 0.000 title claims description 8
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 47
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000002905 metal composite material Substances 0.000 claims abstract description 14
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003570 air Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
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- 238000000151 deposition Methods 0.000 claims description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910021471 metal-silicon alloy Inorganic materials 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 4
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 2
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 2
- 229910020252 KAuCl4 Inorganic materials 0.000 claims description 2
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 description 27
- 229910000990 Ni alloy Inorganic materials 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000002210 silicon-based material Substances 0.000 description 15
- 239000000956 alloy Substances 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000010949 copper Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 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 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
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- 238000006243 chemical reaction Methods 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 235000010413 sodium alginate Nutrition 0.000 description 5
- 239000000661 sodium alginate Substances 0.000 description 5
- 229940005550 sodium alginate Drugs 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
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- 235000012431 wafers Nutrition 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
- RPFLLVICGMTMIE-UHFFFAOYSA-L calcium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[Ca+2] RPFLLVICGMTMIE-UHFFFAOYSA-L 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- WTFCBWXBJBYVOS-UHFFFAOYSA-L lithium;sodium;dichloride Chemical compound [Li+].[Na+].[Cl-].[Cl-] WTFCBWXBJBYVOS-UHFFFAOYSA-L 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 239000011856 silicon-based particle Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a method for preparing a nano silicon-based anode material from silicon cutting waste, belonging to the technical field of silicon waste recycling. The method comprises the steps of carrying out constant-temperature heat treatment on silicon cutting waste in a protective gas or vacuum atmosphere, cooling, crushing and grinding to obtain waste silicon powder; placing waste silicon powder in HF-metal salt-alcohol mixed solution to deposit metal nanoparticles, adding an oxidant to perform metal nanoparticle-assisted etching so as to introduce a porous structure into the silicon powder and embed the metal nanoparticles to obtain a pre-oxidized porous silicon/metal composite material; grinding the pre-oxidized porous silicon/metal composite material into powder or uniformly mixing the powder with an additive, pressing the mixture into a tablet, and roasting the tablet to obtain porous silicon oxide/metal oxide powder or porous silicon oxide/metal composite material; preparing an electrode from the porous silicon oxide/metal oxide powder or the porous silicon oxide/metal composite material as a cathode, and electrolyzing the anode with graphite as an anode at constant voltage in a molten salt electrolyte system to obtain the nano silicon-based anode material.
Description
Technical Field
The invention relates to a method for preparing a nano silicon-based anode material from silicon cutting waste, belonging to the technical field of silicon waste recycling.
Background
According to the requirement of energy storage of high energy density lithium ion batteries, silicon materials are widely considered as lithium ion battery cathode materials with the greatest development prospect. However, silicon-based negative electrode materials still face a great challenge, and during charging and discharging, the silicon materials undergo severe volume expansion (-300%), which leads to the active materials falling off from the current collector, and the volume expansion effect also causes the repeated growth and continuous thickening of the SEI film on the silicon negative electrode. In addition, silicon materials also have a problem of low conductivity. Due to the problems, when the silicon-based material is used as a negative electrode of a lithium battery, the capacity loss is fast, the initial coulombic efficiency is low, and the electrochemical performance is poor. Many strategies have been developed to improve the electrochemical performance of silicon-based anodes. Researches find that the silicon particles with the nanometer scale can overcome the problem of large expansion/contraction, and the reasonable silicon nanostructure design is helpful for further improving the structural integrity and the electrochemical performance of the silicon-based material as the lithium battery cathode; it is also a mainstream method to improve the poor conductivity and electrochemical properties of silicon materials by introducing conductive materials (such as metal nanoparticles, carbonaceous materials) into silicon-based materials or forming silicon-based alloys with the conductive materials. Although the electrochemical performance of the silicon-based cathode is remarkably improved by using the methods, the preparation of related nano silicon-based materials often has the problems of complicated process flow, high cost, high energy consumption and the like, so that the nano silicon-based materials are difficult to be applied in a large scale.
With the increasing emphasis on clean renewable energy, clean energy photovoltaic power generation is rapidly increasing at a rate of over 35% per year; this brings about a steady increase in the consumption of silicon wafers for solar cells. In the solar energy industry, the production process of the silicon chip for the cell is mainly completed by a multi-line cutting mode, and because the ratio of the diameter of a cutting line to the thickness of the silicon chip is about 1:3, the loss of crystalline silicon is about 35 percent in the slicing process of high-purity silicon materials (the purity is more than 6N). Taking 2020 years in China as an example, to realize the cutting of 235GW monocrystalline silicon wafers, up to 25 ten thousand tons of cut silicon waste is generated. The direct discharge of such a large amount of fine and easily-oxidized cutting silicon waste materials causes serious environmental pollution and resource waste, because the preparation of the solar-grade high-purity silicon material is a process with a long flow and high energy consumption.
Therefore, an efficient and feasible technical route or process is sought to realize the comprehensive recycling of the silicon waste, so that the problem of treatment of the silicon waste in the photovoltaic industry can be solved greatly, and huge economic and environmental benefits can be brought.
Disclosure of Invention
Aiming at the technical problems of simultaneous recycling of a silicon-based negative electrode material of a lithium ion battery and a silicon cutting waste, the invention provides a method for preparing a nano silicon-based negative electrode material by using the silicon cutting waste, namely, the introduction of a porous structure on a silicon material, the embedding of metal/metal oxide nano particles and the effective removal of impurities in the cut silicon waste are realized by one step of metal nano particle assisted etching treatment; and then the silicon-based material is oxidized and sintered and then used as an electrode to carry out molten salt electrolysis to prepare Si/metal or Si-metal alloy and other silicon-based materials with a nano porous structure or a nano wire structure, so that the silicon-based negative electrode material of the lithium ion battery with excellent electrochemical performance is obtained.
A method for preparing a nano silicon-based anode material from silicon cutting waste comprises the following specific steps:
(1) carrying out constant-temperature heat treatment on the silicon cutting waste in a protective gas or vacuum atmosphere to volatilize organic substances on the surface of the cutting waste silicon material, cooling, crushing and grinding to obtain waste silicon powder;
(2) placing the waste silicon powder obtained in the step (1) in a HF-metal salt-alcohol mixed solution, depositing metal nanoparticles for 0.5-5 min at the temperature of 20-80 ℃, adding an oxidant to perform metal nanoparticle assisted etching for 1-300 min so as to introduce a porous structure into the silicon powder and embed the metal nanoparticles, performing solid-liquid separation, and drying to obtain a pre-oxidized porous silicon/metal composite material;
(3) grinding the pre-oxidized porous silicon/metal composite material into powder or uniformly mixing the powder with an additive, pressing the mixture into tablets, and roasting the tablets at the temperature of 400-1200 ℃ for 0.5-10 hours to obtain porous silicon oxide/metal oxide powder or porous silicon oxide/metal composite material; wherein the additive is a binder and/or a pore-forming agent;
(4) preparing an electrode from porous silicon oxide/metal oxide powder or a porous silicon oxide/metal composite material as a cathode, taking graphite as an anode, carrying out constant-voltage electrolysis for 0.5-20 h in a molten salt electrolyte system under a protective gas atmosphere to obtain an electrolytic cathode, cooling the electrolytic cathode, cleaning and removing the molten salt electrolyte to obtain a Si/metal cathode material or a Si-metal alloy cathode material with a nano porous structure or a nano wire structure;
the temperature of the constant-temperature heat treatment in the step (1) is 100-300 ℃, and the time is 0.5-48 h;
in the HF-metal salt-alcohol solution system in the step (2), the concentration of HF is 0.1-10 mol/L, the concentration of metal salt is 0.01-20 mol/L, and the concentration of alcohol is 0.1-20 mol/L; the liquid-solid ratio mL of the HF-metal salt-alcohol solution system to the waste silicon powder is (3-50): 1; the metal salt is KAuCl4、HAuCl4、K2PtCl6、H2PtCl6、PdCl2、AgNO3、Fe(NO3)3、NiSO4、Ni(NO3)2、C2H2NiO4、CuSO4、CuCl2Or Cu (NO)3)2The alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol;
further, the oxidant in the step (2) is H2O2、HNO3、Fe(NO3)3、KMnO4、KBrO3、K2Cr2O7Or Na2S2O8The addition amount of the oxidant is 0.01-10 mol/L;
the binder in the step (3) is PMMA, PVP, PEG or PVA, and the pore-forming agent is starch, ammonium bicarbonate and urea;
the addition amount of the additive in the step (3) is 0.5-10 wt.% of the pre-oxidized porous silicon/metal composite material;
further, the tabletting pressure in the step (3) is 1-15 MPa, and the pressure maintaining time is 1-100 min;
the roasting atmosphere in the step (3) is nitrogen, argon, oxygen or air;
the molten salt electrolyte in the step (4) is one or more of aluminum chloride, magnesium chloride, calcium chloride, lithium chloride, sodium chloride, potassium chloride and strontium chloride;
the protective gas in the step (4) is argon or nitrogen, and the constant voltage is 1.0-3.0V.
The invention has the beneficial effects that:
(1) the method has the advantages of simple equipment requirement, easy operation and easy amplification, can effectively solve the problem of difficult recovery of silicon cutting waste in the photovoltaic industry, and can also effectively prepare the high-performance novel nano silicon-based negative electrode material;
(2) according to the invention, the method for assisting the cutting of the silicon waste by metal nano particles is skillfully utilized, so that the effective removal of impurities, the introduction of a porous structure and the embedding of nano metal particles are realized in one step; the nano metal effectively embedded in the porous silicon structure not only increases the conductivity of the silicon-based material, but also can directly guide and promote nucleation and growth of the silicon nanowire in cooperation with the porous structure in the molten salt electrolysis process;
(3) according to the invention, the silicon waste can be cut to prepare the novel silicon-based anode material with a nano porous structure or a nano wire structure, such as Si/metal or Si-metal alloy, by combining a molten salt electrolysis mode under a low temperature condition, so that the problems of volume expansion and poor conductivity of the silicon material in the charging and discharging processes of the lithium ion battery can be effectively solved, and the electrochemical performance of the silicon-based anode material is remarkably improved.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a comparison of the performance test results of the lithium ion battery in example 1 when the nanoporous silicon/Nano-Ag composite material and the cut silicon waste material are used as the negative electrode respectively;
FIG. 3 is a comparison of the performance test results of the lithium ion battery in example 2, in which the nanoporous silicon-Cu alloy material and the cut silicon scrap material are used as the negative electrode respectively;
FIG. 4 is a comparison of the performance test results of the lithium ion battery of example 3 when the nanoporous silicon-Ni alloy material and the cut silicon scrap material are used as the negative electrode, respectively;
FIG. 5 is a comparison of the performance test results of the lithium ion battery of example 4 when the silicon nanowire-Ni alloy material and the cut silicon scrap material are used as the negative electrode, respectively;
FIG. 6 is a comparison of the performance test results of the lithium ion battery of example 5, in which the silicon nanowire-Ni alloy material and the cut silicon scrap material are used as the negative electrode, respectively.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for preparing a nano silicon-based anode material from silicon cutting waste (see figure 1) comprises the following specific steps:
(1) placing the silicon cutting waste in a vacuum condition, carrying out constant-temperature heat treatment for 10 hours at the temperature of 100 ℃, naturally cooling, crushing and grinding to obtain waste silicon powder;
(2) placing the waste silicon powder obtained by the pretreatment in the step (1) in HF-AgNO3Depositing Ag nanoparticles in an ethanol mixture at 20 ℃ for 1min, wherein the HF concentration in the mixture is 4.6mol/L, AgNO3The concentration is 0.01mol/L, the ethanol concentration is 0.1mol/L, the liquid-solid ratio mL of the mixed solution and the waste silicon powder is 10:1, and then an oxidizing agent (commercially available H) is added2O2) Carrying out metal nanoparticle assisted etching for 30min, carrying out solid-liquid separation after the reaction is finished, and drying at the temperature of 80 ℃ in an air atmosphere to obtain a pre-oxidized porous silicon/Nano-Ag composite material; wherein the oxidant (commercially available H)2O2) The addition amount of (A) is 0.1 mol/L;
(3) grinding the porous silicon/Nano-Ag composite material pre-oxidized in the step (2) into powder, and sintering the powder for 1 hour at the temperature of 600 ℃ in a nitrogen atmosphere to prepare porous silicon oxide/Nano-Ag composite material powder;
(4) directly placing the porous silicon oxide/Nano-Ag composite material powder obtained in the step (3) in a self-made graphite porous container connected with a graphite rod lead to form a contact electrode, placing the contact electrode as a cathode in a graphite crucible filled with strontium chloride molten salt electrolyte, directly serving as an anode, carrying out constant-voltage electrolysis for 10 hours under the condition of argon protective gas atmosphere and 150 ℃, cooling, taking out an electrolysis product, washing with a large amount of water to remove molten salt, filtering and separating to obtain the Nano-porous silicon/Nano-Ag composite material; wherein the constant voltage is 3.0V;
(5) assembling the electrode plate prepared from the Nano-porous silicon/Nano-Ag composite material in the step (4), a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70:15:15 into a battery by taking a lithium plate as a counter electrode in a glove box, and performing charge-discharge test at a current density of 0.5A/g;
the performance result of the battery prepared by taking the Nano-porous silicon/Nano-Ag composite material as the lithium battery cathode is shown in fig. 2, the initial discharge capacity is up to 3207mAh/g, the initial coulombic efficiency can reach 86.8%, and the reversible capacity after 50 cycles still maintains 1955 mAh/g; compared with the test result of the silicon waste material electrode battery under the same experimental conditions in the figure 2, the Nano porous silicon/Nano-Ag battery has obviously improved performance.
Example 2: a method for preparing a nano silicon-based anode material from silicon cutting waste comprises the following specific steps:
(1) placing the silicon cutting waste into an argon protective atmosphere, carrying out constant-temperature heat treatment for 10 hours at the temperature of 300 ℃, naturally cooling, crushing and grinding to obtain waste silicon powder;
(2) placing the waste silicon powder obtained by the pretreatment in the step (1) in HF-Cu (NO)3)2Depositing Cu nanoparticles in an ethanol mixed solution at 40 ℃ for 1min, wherein the HF concentration in the mixed solution is 3.5mol/L, Cu (NO)3)2The concentration is 0.5mol/L, the ethanol concentration is 1mol/L, the liquid-solid ratio mL of the mixed solution and the waste silicon powder is 8:1, and then an oxidizing agent (commercially available H) is added2O2) Carrying out metal nanoparticle assisted etching for 120min, carrying out solid-liquid separation after the reaction is finished, and drying at the temperature of 150 ℃ in an air atmosphere to obtain a pre-oxidized porous silicon/Cu composite material; wherein the oxidant (commercially available H)2O2) The addition amount of (A) is 0.5 mol/L;
(3) finely grinding the porous silicon/Cu composite material pre-oxidized in the step (2) into powder, and sintering the powder for 2 hours at the temperature of 400 ℃ in an air atmosphere to prepare porous silicon oxide/copper oxide composite material powder;
(4) directly placing the porous silicon oxide/copper oxide composite material powder obtained in the step (3) in a self-made graphite porous container connected with a graphite rod lead to form a contact electrode, placing the contact electrode as a cathode in a graphite crucible filled with strontium chloride molten salt, directly serving as an anode, carrying out constant-voltage electrolysis for 5 hours under the condition of argon protective gas atmosphere and at the temperature of 650 ℃, cooling, taking out an electrolysis product, washing with a large amount of water to remove the molten salt, filtering and separating to obtain a nano porous silicon-Cu alloy material; wherein the constant voltage is 1.5V;
(5) assembling the electrode plate prepared from the nano-porous silicon-Cu alloy material in the step (4), a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70:15:15 into a battery in a glove box by taking a lithium plate as a counter electrode, and performing charge-discharge test at a current density of 0.5A/g;
the performance result of the battery prepared by taking the nano-porous silicon-Cu alloy as the negative electrode of the lithium battery is shown in fig. 3, the first discharge capacity is up to 2989mAh/g, the first coulombic efficiency can reach 87.4%, and the reversible capacity after 50 cycles is still kept at 1562 mAh/g; compared with the test result of the silicon waste material raw material electrode battery in the same experimental condition shown in fig. 3, the performance of the nano porous silicon-Cu alloy battery is remarkably improved.
Example 3: a method for preparing a nano silicon-based anode material from silicon cutting waste comprises the following specific steps:
(1) placing the silicon cutting waste into a nitrogen protective atmosphere, carrying out constant-temperature heat treatment for 12h at the temperature of 200 ℃, naturally cooling, crushing and grinding to obtain waste silicon powder;
(2) waste silicon powder obtained by pretreatment is placed in HF-Ni (NO)3)2Depositing Ni nanoparticles in a mixed solution of ethylene glycol at 40 ℃ for 2min, wherein the HF concentration in the mixed solution is 2mol/L, Ni (NO)3)2The concentration is 1mol/L, the concentration of glycol is 2mol/L, the liquid-solid ratio mL of the mixed solution to the waste silicon powder is 20:1, and then an oxidant KMnO is added4Carrying out metal nanoparticle assisted etching for 60min, carrying out solid-liquid separation after the reaction is finished, and drying at 100 ℃ in an air atmosphere to obtain a pre-oxidized porous silicon/Ni composite material; it is composed ofMedium oxidant KMnO4The addition amount of (A) is 1 mol/L;
(3) finely grinding the porous silicon/Ni composite material pre-oxidized in the step (2) into powder, and sintering the powder for 4 hours at the temperature of 500 ℃ in an air atmosphere to prepare porous silicon oxide/nickel oxide composite material powder;
(4) directly placing the porous silicon oxide/nickel oxide composite material powder obtained in the step (3) in a self-made graphite porous container connected with a graphite rod lead to form a contact electrode, placing the contact electrode as a cathode in a graphite crucible filled with sodium chloride-lithium chloride composite molten salt, directly using the graphite crucible as an anode, carrying out constant-voltage electrolysis for 8 hours in an argon protective gas atmosphere at the temperature of 850 ℃, cooling, taking out an electrolysis product, washing with a large amount of water to remove the molten salt, filtering and separating to obtain a nano porous silicon-Ni alloy material; wherein the constant voltage is 1.0V;
(5) assembling the electrode plate prepared from the nano porous silicon-Ni alloy material in the step (4), a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70:15:15 into a glove box, and performing charge-discharge test under a current density of 0.5A/g by using a lithium plate as a counter electrode;
the performance result of the battery prepared by taking the nano-porous silicon-Ni alloy as the negative electrode of the lithium battery is shown in fig. 4, the first discharge capacity is up to 3007mAh/g, the first coulombic efficiency can reach 86.5%, and the reversible capacity after 50 cycles can still be kept at 1685 mAh/g; compared with the test result of the silicon waste material raw material electrode battery in the same experimental condition in the figure 4, the performance of the nano porous silicon-Ni alloy battery is obviously improved.
Example 4: a method for preparing a nano silicon-based anode material from silicon cutting waste comprises the following specific steps:
(1) placing the silicon cutting waste into a vacuum atmosphere, carrying out constant-temperature heat treatment for 12h at the temperature of 200 ℃, naturally cooling, crushing and grinding to obtain waste silicon powder;
(2) placing the waste silicon powder obtained by pretreatment in HF-C2H2NiO4Depositing Ni nanoparticles in an ethanol mixed solution at a temperature of 60 ℃ for 5min, wherein the concentration of HF in the mixed solution is 1mol/L, C2H2NiO4The concentration is 3mol/L, the ethanol concentration is 4mol/L, and the mixed solution and the waste silicon powderG is 15:1, then adding oxidant H2O2Carrying out metal nanoparticle assisted etching for 240min, carrying out solid-liquid separation after the reaction is finished, and drying at the temperature of 200 ℃ in an air atmosphere to obtain a pre-oxidized porous silicon/Ni composite material; wherein the oxidant H2O2The addition amount of (A) is 0.1 mol/L;
(3) uniformly grinding the porous silicon/Ni composite material pre-oxidized in the step (2), 0.5% of starch and 1% of PMMA, pressing into tablets, wherein the tablet pressing pressure is 3MPa, the pressure maintaining time is 5min, and sintering at 1200 ℃ in a nitrogen atmosphere for 0.5h to prepare a porous silicon oxide/Ni composite material sheet material;
(4) punching the middle of the porous silicon oxide/Ni composite material sheet material in the step (3), fixing the porous silicon oxide/Ni composite material sheet material on a molybdenum rod wire to form a contact electrode, placing the contact electrode as a cathode in a graphite crucible filled with calcium chloride molten salt electrolyte, directly using the graphite crucible as an anode, carrying out constant-voltage electrolysis for 6h under the condition of argon protective gas atmosphere and at the temperature of 950 ℃, cooling, taking out an electrolysis product, washing with a large amount of water to remove molten salt, filtering and separating to obtain a silicon nanowire-Ni alloy material; wherein the constant voltage is 1.5V;
(5) assembling the electrode plate prepared from the silicon nanowire-Ni alloy material in the step (4), a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70:15:15 into a glove box, assembling a battery by taking a lithium sheet as a counter electrode, and performing charge-discharge test at a current density of 0.5A/g;
the performance result of the battery prepared by taking the silicon nanowire-Ni alloy as the lithium battery cathode is shown in fig. 5, the first discharge capacity is as high as 2310mAh/g, the first coulombic efficiency can reach 84.8%, and the reversible capacity after 50 cycles is still maintained at 735.8 mAh/g; compared with the test result of the silicon waste material raw material electrode battery under the same experimental condition in the figure 5, the performance of the silicon nanowire-Ni alloy battery is obviously improved.
Example 5: a method for preparing a nano silicon-based anode material from silicon cutting waste comprises the following specific steps:
(1) placing the silicon cutting waste into a vacuum atmosphere, carrying out constant-temperature heat treatment for 48 hours at the temperature of 180 ℃, naturally cooling, crushing and grinding to obtain waste silicon powder;
(2) waste silicon powder obtained by pretreatmentIs placed in HF-C2H2NiO4Depositing Ni nanoparticles in an ethanol mixed solution at 80 ℃ for 3min, wherein the HF concentration in the mixed solution is 5mol/L, C2H2NiO4The concentration is 5mol/L, the ethanol concentration is 2mol/L, the liquid-solid ratio mL of the mixed solution and the waste silicon powder is 20:1, and then an oxidant (commercial HNO) is added3) Carrying out metal nanoparticle assisted etching for 300min, carrying out solid-liquid separation after the reaction is finished, and drying at the temperature of 80 ℃ in an air atmosphere to obtain a pre-oxidized porous silicon/Ni composite material; wherein the oxidant (commercially available HNO)3) The addition amount of (A) is 0.01 mol/L;
(3) uniformly grinding the porous silicon/Ni composite material pre-oxidized in the step (2), 1% of PMMA and 1% of ammonium bicarbonate, and preparing the porous silicon/Ni composite material into a sheet material in an air atmosphere by adopting a hot pressing mode, wherein the hot pressing temperature is 1000 ℃, the pressing pressure is 10MPa, and the pressure maintaining time is 100 min;
(4) punching the middle of the porous silicon oxide/nickel oxide composite material sheet material obtained in the step (3), fixing the punched porous silicon oxide/nickel oxide composite material sheet material on a molybdenum rod wire to form a contact electrode, placing the contact electrode as a cathode in a graphite crucible filled with calcium chloride-sodium chloride molten salt electrolyte, directly using the graphite crucible as an anode, electrolyzing for 10 hours at constant voltage under the condition of argon protective gas atmosphere and 100 ℃, cooling, taking out an electrolysis product, washing with a large amount of water to remove molten salt, filtering and separating to obtain a silicon nanowire-Ni alloy material; wherein the constant voltage is 1.8V;
(5) assembling the electrode plate prepared from the silicon nanowire-Ni alloy material in the step (4), a conductive agent carbon black and a sodium alginate binder according to a mass ratio of 70:15:15 into a glove box, assembling a battery by taking a lithium sheet as a counter electrode, and performing charge-discharge test at a current density of 0.5A/g;
the performance result of the battery prepared by taking the silicon nanowire-Ni alloy as the negative electrode of the lithium battery is shown in FIG. 6, the first discharge capacity is up to 1175mAh/g, the first coulombic efficiency can reach 86.9 percent, and the reversible capacity after 50 cycles is still maintained at 865 mAh/g; compared with the test result of the silicon waste electrode battery in the same experimental condition as that in FIG. 6, the performance of the silicon nanowire-Ni alloy battery is remarkably improved.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (9)
1. A method for preparing a nano silicon-based anode material from silicon cutting waste is characterized by comprising the following specific steps:
(1) carrying out constant-temperature heat treatment on the silicon cutting waste in a protective gas or vacuum atmosphere, and crushing and grinding the silicon cutting waste after cooling to obtain waste silicon powder;
(2) placing the waste silicon powder obtained in the step (1) in a HF-metal salt-alcohol mixed solution, depositing metal nanoparticles for 0.5-5 min at the temperature of 20-80 ℃, adding an oxidant to perform metal nanoparticle assisted etching for 1-300 min so as to introduce a porous structure into the silicon powder and embed the metal nanoparticles, performing solid-liquid separation, and drying to obtain a pre-oxidized porous silicon/metal composite material;
(3) grinding the pre-oxidized porous silicon/metal composite material into powder or uniformly mixing the powder with an additive, pressing the mixture into tablets, and roasting the tablets at the temperature of 400-1200 ℃ for 0.5-10 hours to obtain porous silicon oxide/metal oxide powder or porous silicon oxide/metal composite material; wherein the additive is a binder and/or a pore-forming agent;
(4) preparing an electrode from porous silicon oxide/metal oxide powder or a porous silicon oxide/metal composite material as a cathode, taking graphite as an anode, carrying out constant-voltage electrolysis for 0.5-20 h in a molten salt electrolyte system under a protective gas atmosphere to obtain an electrolytic cathode, cooling the electrolytic cathode, cleaning and removing the molten salt electrolyte to obtain the Si/metal anode material or the Si-metal alloy anode material with a nano porous structure or a nano wire structure.
2. The method for preparing the nano silicon-based anode material from the silicon cutting waste material as claimed in claim 1, wherein the method comprises the following steps: the temperature of the constant-temperature heat treatment in the step (1) is 100-300 ℃, and the time is 0.5-48 h.
3. Production of nano silicon from silicon cutting waste material according to claim 1A method of forming a negative electrode material, comprising: in the step (2), the concentration of HF, metal salt and alcohol in an HF-metal salt-alcohol solution system is 0.1-10 mol/L, the concentration of metal salt is 0.01-20 mol/L and the concentration of alcohol is 0.1-20 mol/L; the liquid-solid ratio mL of the HF-metal salt-alcohol solution system to the waste silicon powder is (3-50): 1; the metal salt is KAuCl4、HAuCl4、K2PtCl6、H2PtCl6、PdCl2、AgNO3、Fe(NO3)3、NiSO4、Ni(NO3)2、C2H2NiO4、CuSO4、CuCl2Or Cu (NO)3)2The alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol.
4. The method for preparing the nano silicon-based anode material from the silicon cutting waste material as claimed in claim 3, wherein the method comprises the following steps: step (2) the oxidant is H2O2、HNO3、Fe(NO3)3、KMnO4、KBrO3、K2Cr2O7Or Na2S2O8The addition amount of the oxidant is 0.01-10 mol/L.
5. The method for preparing the nano silicon-based anode material from the silicon cutting waste material as claimed in claim 1, wherein the method comprises the following steps: and (3) the binder is PMMA, PVP, PEG or PVA, and the pore-forming agent is starch, ammonium bicarbonate and urea.
6. The method for preparing the nano silicon-based anode material from the silicon cutting waste material as claimed in claim 1, wherein the method comprises the following steps: and (4) adding the additive in the step (3) in an amount of 0.5-10 wt% of the pre-oxidized porous silicon/metal composite material.
7. The method for preparing the nano silicon-based anode material from the silicon cutting waste material as claimed in claim 1, wherein the method comprises the following steps: and (3) roasting in nitrogen, argon, oxygen or air.
8. The method for preparing the nano silicon-based anode material from the silicon cutting waste material as claimed in claim 1, wherein the method comprises the following steps: the molten salt electrolyte in the step (4) is one or more of aluminum chloride, magnesium chloride, calcium chloride, lithium chloride, sodium chloride, potassium chloride and strontium chloride.
9. The method for preparing the nano silicon-based anode material from the silicon cutting waste material as claimed in claim 1, wherein the method comprises the following steps: and (4) the protective gas in the step (4) is argon or nitrogen, and the constant voltage is 1.0-3.0V.
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