CN112652758B - Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Silicon oxide/carbon microsphere composite negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 66
- 239000004005 microsphere Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005530 etching Methods 0.000 claims abstract description 4
- 229910000077 silane Inorganic materials 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000010405 anode material Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- ADMWVBXCJSMQLF-UHFFFAOYSA-N C(C)O.[Si] Chemical compound C(C)O.[Si] ADMWVBXCJSMQLF-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- JSECNWXDEZOMPD-UHFFFAOYSA-N tetrakis(2-methoxyethyl) silicate Chemical compound COCCO[Si](OCCOC)(OCCOC)OCCOC JSECNWXDEZOMPD-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- NASVITFAUKYCPM-UHFFFAOYSA-N ethanol;tetraethyl silicate Chemical compound CCO.CCO[Si](OCC)(OCC)OCC NASVITFAUKYCPM-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000011856 silicon-based particle Substances 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000003068 static effect Effects 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
-
- 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
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
Abstract
The invention discloses a silicon oxide/carbon microsphere composite negative electrode material for a lithium ion battery and a preparation method thereof. The silicon oxide/carbon microspheres are prepared from silane, resorcinol, formaldehyde, an etching solution, a reducing agent, ethanol, ammonia water and deionized water; the silicon oxide/carbon microsphere composite negative electrode material is of a core-shell structure, the diameter of the core-shell structure is 100-300 nm, a gap with the distance of 15-45 nm is formed between the core silicon oxide and the carbon shell, the diameter of the core silicon oxide is 30-150 nm, the thickness of the carbon shell is 20-30 nm, and according to mass percentage, 15-40% of silicon, 13-21% of oxygen and 45-70% of carbon are contained. The silicon oxide/carbon microsphere composite negative electrode material has the advantages of simple process, good reproducibility and easy implementation, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of nano material preparation, relates to a lithium ion battery preparation technology, and particularly relates to a silicon oxide/carbon microsphere composite anode material based on a lithium ion battery and a preparation method thereof.
Background
With the development and progress of society, the demand for energy is more and more, fossil energy is greatly consumed, environmental pollution is increasingly serious, and the demand for clean energy is more and more intense. Lithium ion batteries play an increasingly important role in the fields of civil use, military, aerospace and the like due to the advantages of high capacity, environmental protection and the like, and have been widely applied in the fields of electronic equipment, power automobiles, static energy storage and the like. Especially, under the encouragement of the policy of the state for vigorously developing new energy electric vehicles, the demand of the lithium ion battery is also rapidly increased. With the rapid development of new energy automobiles with lithium batteries, the energy density and the cycle life of power lithium ion batteries must be greatly improved. The cathode material, as an important component of the lithium ion battery, determines the performance and safety of the lithium ion battery. The capacity of the most widely applied graphite carbon negative electrode material in the current market is close to the theoretical capacity 372mAh/g, the promotion space is very limited, and the low capacity density seriously inhibits the wide application of the lithium ion battery.
The silicon negative electrode material is considered to be a negative electrode material with great application prospect in the next generation of lithium ion batteries due to the advantages of high specific capacity (4200mAh/g), low lithium removal potential and the like. However, the high production cost of silicon negative electrode materials and the large volume change (over 300%) during the lithium extraction process lead to pulverization, shedding and capacity fading of silicon particles; the continuous growth of Solid Electrolyte (SEI) films on the surface of silicon particles limits the wide application of the SEI films as negative electrode materials due to irreversible consumption of electrolyte and lithium source from the positive electrode. On the other hand, silicon oxide (SiO)x,0<x<2) Compared with crystalline silicon nano-particles, the nano-crystalline silicon nano-particles have high theoretical capacity (more than 1500 mAh/g), and also have other advantages, such as small volume change in the charge and discharge process and capability of generating silicon and Li in the charge and discharge process2O and Li4Si4O4. Thus, the in-situ generated silicon is uniformly dispersed in Li2O and Li4Si4O4In the matrix, the volume expansion in the process of lithium intercalation and deintercalation of Si can be buffered to a certain degree, the agglomeration of Si particles can be prevented, the volume change of the silicon-lithium alloy can be buffered, and the like. Currently silicon oxide (SiO)x) The anode material is one of the new generation of high capacity silicon-based anode materials that the industry considers to be most promising for industrialization. Although SiO is presentxThese advantages exist, but SiOxThe low conductivity and the first coulombic efficiency and the non-negligible volume change limit the wide application of the material as a negative electrode material in the field of power lithium batteries.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a silicon oxide/carbon microsphere composite negative electrode material for a lithium ion battery and a preparation method thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a silicon oxide/carbon microsphere composite negative electrode material for a lithium ion battery is characterized in that the silicon oxide/carbon microsphere is prepared from silane, resorcinol, formaldehyde, an etching solution, a reducing agent, ethanol, ammonia water and deionized water; the silicon oxide/carbon microsphere composite negative electrode material is of a core-shell structure, the diameter of the core-shell structure is 100-300 nm, a gap with the distance of 15-45 nm is formed between the core silicon oxide and the carbon shell, the diameter of the core silicon oxide is 30-150 nm, the thickness of the carbon shell is 20-30 nm, and according to mass percentage, 15-40% of silicon, 13-21% of oxygen and 45-70% of carbon are contained.
Further preferably, the silane is one of tetra (2-methoxyethoxy) silane, tetramethoxysilane and tetraethoxysilane or a mixture of a plurality of silanes in any mass ratio.
Further preferably, the etching solution is one or a mixture of potassium hydroxide solution, sodium hydroxide solution and sodium carbonate solution in any mass ratio, or hydrofluoric acid solution.
Further preferably, the reducing agent is one or a mixture of aluminum, magnesium, sodium and potassium metal powder in any mass ratio.
A preparation method of a silicon oxide/carbon microsphere composite negative electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) mixing ammonia water with ammonia content of 25-28%, deionized water and ethanol according to a volume ratio of 0.5-0.8: 1: 1.5-3, and mixing the mixed solution according to a volume ratio of 1:1, adding the mixture into a silane ethanol solution with the concentration of 0.05-0.1 g/L, and stirring for 2-5 hours to obtain a solution A;
(2) adding resorcinol and formaldehyde into the solution A obtained in the step (1), and stirring for 24-36 hours, wherein the concentration of resorcinol in A is 6.25-17.5 g/L, and the mass ratio of resorcinol to formaldehyde is 2-3: 1; then transferring the mixture into a high-pressure reaction kettle, and keeping the temperature at 90-110 ℃ for 20-30 hours; naturally cooling to room temperature, performing centrifugal separation, washing the obtained product with ethanol and deionized water for 2-3 times, and performing vacuum drying at 70-90 ℃ for 20-30 hours to obtain a product B;
(3) placing the product B obtained in the step (2) in a tubular furnace, introducing nitrogen or argon or nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 800-1100 ℃ at the speed of 2-5 ℃/min under the protection of atmosphere, keeping for 3-5 hours, and then naturally cooling to room temperature to obtain a product C;
(4) placing the product C obtained in the step (3) in a sodium hydroxide solution, stirring and reacting for 5-20 hours at room temperature, then washing the precipitate with ethanol and deionized water for 2-3 times in sequence until the filtrate is neutral, and then drying in vacuum at 70-90 ℃ for 24-36 hours to obtain a product D;
(5) uniformly mixing the product D obtained in the step (4) with a reducing agent according to the mass ratio of 3-5: 1, placing the mixture in a tubular furnace, introducing nitrogen or argon or a nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 700-800 ℃ at the speed of 2-5 ℃/min under the protection of atmosphere, keeping the temperature for 3-5 hours, and naturally cooling to room temperature to obtain a product E;
(6) fully mixing and stirring the product E obtained in the step (5) with a dilute hydrochloric acid solution, reacting for 24 hours, then washing with ethanol and deionized water for 2-3 times in sequence until the filtrate is neutral, and then drying in vacuum at 70-90 ℃ for 24-36 hours to obtain the final product, namely the silicon oxide/carbon microsphere composite anode material
An application of a silicon oxide/carbon microsphere composite negative electrode material in a lithium ion battery is provided.
An application method of a silicon oxide/carbon microsphere composite negative electrode material is applied to a CR2032 button type lithium ion battery and comprises the following specific steps: uniformly mixing the silicon-oxygen-carbon composite material, the conductive agent Super P and the adhesive polyvinylidene fluoride according to the mass ratio of 70:20: 10; and then according to the mass ratio of 20: 80 mixing the uniformly mixed solid mixture (the mixture of the silicon oxide/carbon microsphere composite material, Super P and polyvinylidene fluoride) with N-methylpyrrolidone, and uniformly stirring to prepare slurry; and then coating the slurry on a copper foil, and drying and rolling to obtain the lithium ion battery electrode negative plate with the thickness of 13-23 mu m. Then, a lithium plate is taken as an electrode positive plate, a microporous polypropylene film is taken as a diaphragm, and 1mol/L LiPF6And (the solvent is dimethyl carbonate and dipropyl carbonate with the same volume) as the electrolyte, and the electrode negative plate is assembled into the CR2032 button lithium ion battery in a glove box filled with argon.
The invention has the advantages and beneficial effects that:
when the silicon oxide/carbon microsphere composite negative electrode material with the core-shell structure is used as a negative electrode material of a lithium battery, the volume change of a silicon oxide core used as an active material is smaller than that of simple substance silicon in the charge and discharge processes; the carbon shell can relieve the volume change of the silicon oxide material in the charging and discharging process, so that the cycle performance and the coulombic efficiency of the lithium battery can be improved, and the conductivity of the material can be improved, so that the rate performance can be improved. In addition, the method has simple process, good reproducibility and easy implementation, and is suitable for large-scale production.
Drawings
Fig. 1 is an XRD of a silicon oxide/carbon (SiOx/C) microsphere composite prepared in example 1 of the present invention. Two broad peaks between 20-25 ° and around 45 ° correspond to amorphous silicon oxide and amorphous carbon.
Fig. 2 is a transmission electron microscope image of the silicon oxide/carbon microsphere composite anode material prepared in example 1 of the present invention. As can be seen from the transmission electron microscope picture, the silicon oxide/carbon microsphere is of a yolk-eggshell structure, the diameter of the silicon oxide/carbon microsphere is 110nm, a certain gap is formed between the inner core and the shell, the diameter of the silicon oxide of the inner core is 55.5nm, and the thickness of the carbon shell is 9 nm.
Fig. 3 is an EDS spectrum of the silicon oxide/carbon microsphere composite anode material prepared in example 1 of the present invention. It can be seen that the composite material is composed of elements of C, Si, O. The peak of the copper element is the peak of the substrate copper sheet.
Fig. 4 is a transmission electron microscope image of the silicon oxide/carbon microsphere composite anode material prepared in example 1 of the present invention. As can be seen from the transmission electron microscope picture, the silicon oxide/carbon microsphere is of a yolk-eggshell structure, the diameter of the silicon oxide/carbon microsphere is 200nm, a certain gap is formed between the inner core and the shell, the distance between the gaps is 11nm, the diameter of the silicon oxide of the inner core is 149nm, and the thickness of the carbon shell is 14.5 nm.
FIG. 5 shows that the silicon oxide/carbon microsphere composite material prepared in example 1 of the present invention is used as a negative electrode material of a lithium ion battery at 500mA g-1Cycle performance graph below.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A silicon oxide/carbon microsphere composite negative electrode material for a lithium ion battery comprises the following specific steps:
(1) mixing 6ml of ammonia water (the content of ammonia is 25-28%), 10ml of deionized water and 22ml of ethanol, uniformly stirring, adding the mixture into 38ml of tetraethoxysilane ethanol solution (0.07mg/ml), and continuously stirring for 2-5 hours to obtain solution A;
(2) adding 1.31g of resorcinol and 0.44g of formaldehyde into the solution A obtained in the step (1), stirring for 24-36 hours, and then transferring into a high-pressure reaction kettle to keep the temperature at 100 ℃ for 24 hours; then cooling to room temperature, and carrying out centrifugal separation at the rotating speed of 5000 r/min; then washing the obtained precipitate with ethanol and deionized water for 3 times in sequence, and then drying in vacuum at 70 ℃ for 20 hours to obtain a silicon dioxide/phenolic resin composite material B;
(3) and (3) placing the product B obtained in the step (2) in a tubular furnace, introducing nitrogen or argon or nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 1100 ℃ at the speed of 2 ℃/min under the atmosphere protection, keeping for 3 hours, and naturally cooling to room temperature to obtain a product C.
(4) Placing the product C obtained in the step (3) in a sodium hydroxide solution (6%), continuously stirring and reacting for 8 hours at room temperature, then washing the precipitate for 3 times by using ethanol and deionized water successively until the filtrate is neutral, and then drying for 36 hours in vacuum at 90 ℃ to obtain a product D;
(5) and (3) uniformly mixing the product D obtained in the step (4) with a reducing agent according to the mass ratio of 3:1, placing the mixture in a tubular furnace, introducing nitrogen or argon or nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 700 ℃ at the speed of 2 ℃/min under the protection of atmosphere, keeping for 3 hours, and naturally cooling to room temperature to obtain a product E.
(6) And (3) fully mixing and stirring the product E obtained in the step (5) with a dilute hydrochloric acid solution (10%), reacting for more than 24 hours, then washing for 3 times with ethanol and deionized water sequentially until the filtrate is neutral, and then drying in vacuum at 90 ℃ for 24 hours to obtain the final product, namely the silicon oxide/carbon microsphere composite negative electrode material.
Assembling and testing the performance of the lithium ion battery, namely uniformly mixing the silicon-oxygen-carbon composite material, the conductive agent Super P and the adhesive polyvinylidene fluoride according to the mass ratio of 70:20: 10; and then according to the mass ratio of 20: 80 mixing the solid mixture (the mixture of the silicon oxide/carbon microsphere composite material, Super P and polyvinylidene fluoride) and N-methylpyrrolidone, and uniformly stirring to prepare slurry; and then coating the slurry on a copper foil, and drying and rolling to obtain the lithium ion battery electrode negative plate with the thickness of 13-23 mu m. Then, a lithium plate is taken as an electrode positive plate, a microporous polypropylene film is taken as a diaphragm, and 1mol/L LiPF6(the solvent is dimethyl carbonate and dipropyl carbonate with equal volume) as electrolyte, and the electrode negative plate is assembled into a CR2032 button type lithium ion battery in a glove box filled with argon. After the lithium ion battery is kept stand for 24 hours, the first circle is at 100mA g-1Carrying out charge and discharge tests under current, wherein the charge and discharge voltage interval is between 0.01 and 3.0V; starting from the second turn at 500mA g-1Then, a charge-discharge test is carried out, and the charge-discharge interval is between 0.01 and 3.0V. The test results are shown in fig. 1-5. Wherein the content of the first and second substances,
FIG. 1 shows two broad peaks between 20 DEG and 25 DEG and around 45 DEG, corresponding to amorphous silicon oxide and amorphous carbon.
Fig. 2 shows from a transmission electron microscope picture that the silicon oxide/carbon microsphere is a yolk-eggshell structure, the diameter of the silicon oxide/carbon microsphere is 110nm, a certain gap is formed between the inner core and the shell, the diameter of the silicon oxide of the inner core is 55.5nm, and the thickness of the carbon outer shell is 9 nm.
Fig. 3 shows that the composite material is composed of C, Si and O elements. The peak of the copper element is the peak of the substrate copper sheet.
Fig. 4 shows from the transmission electron microscope picture that the silicon oxide/carbon microsphere is a yolk-eggshell structure, the diameter of the silicon oxide/carbon microsphere is 200nm, a certain gap is formed between the core and the shell, the distance of the gap is 11nm, the diameter of the silicon oxide of the core is 149nm, and the thickness of the carbon shell is 14.5 nm.
FIG. 5 shows that the silicon oxide/carbon microsphere composite material prepared in example 1 of the present invention is used as a negative electrode material of a lithium ion battery at 500mA g-1Cycle performance graph below.
Example 2
A silicon oxide/carbon microsphere composite negative electrode material for a lithium ion battery comprises the following specific steps:
(1) mixing 6ml of ammonia water (the content of ammonia is 25-28%), 10ml of deionized water and 22ml of ethanol, uniformly stirring, adding the mixture into 38ml of tetraethoxysilane ethanol solution (0.1mg/ml), and continuously stirring for 2-5 hours to obtain solution A;
(2) adding 1.06g of resorcinol and 0.53g of formaldehyde into the solution A obtained in the step (1), stirring for 24-36 hours, and then transferring into a high-pressure reaction kettle to keep at 100 ℃ for 24 hours; then cooling to room temperature, and carrying out centrifugal separation at the rotating speed of 5000 r/min; then washing the obtained precipitate with ethanol and deionized water for 3 times in sequence, and then drying in vacuum at 70 ℃ for 20 hours to obtain a silicon dioxide/phenolic resin composite material B;
(3) and (3) placing the product B obtained in the step (2) in a tubular furnace, introducing nitrogen or argon or nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 1100 ℃ at the speed of 2 ℃/min under the atmosphere protection, keeping for 3 hours, and naturally cooling to room temperature to obtain a product C.
(4) Putting the product C obtained in the step (3) into a sodium hydroxide solution (6%), continuously stirring and reacting for 20 hours at room temperature, then washing the precipitate for 3 times by using ethanol and deionized water successively until the filtrate is neutral, and then carrying out vacuum drying for 36 hours at the temperature of 90 ℃ to obtain a product D;
(5) and (5) uniformly mixing the product D obtained in the step (4) with a reducing agent according to the mass ratio of 3:1, placing the mixture in a tubular furnace, introducing nitrogen or argon or a nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 700 ℃ at the speed of 2 ℃/min under the protection of atmosphere, keeping for 3 hours, and naturally cooling to room temperature to obtain a product E.
(6) And (3) fully mixing and stirring the product E obtained in the step (5) with a dilute hydrochloric acid solution (10%), reacting for more than 24 hours, then washing for 3 times with ethanol and deionized water sequentially until the filtrate is neutral, and then drying in vacuum at 90 ℃ for 24 hours to obtain the final product, namely the silicon oxide/carbon microsphere composite negative electrode material.
Example 3
A silicon oxide/carbon microsphere composite negative electrode material for a lithium ion battery comprises the following specific steps:
(1) mixing 5ml of ammonia water (the content of ammonia is 25-28%), 10ml of deionized water and 25ml of ethanol, uniformly stirring, adding the mixture into 40ml of tetraethoxysilane ethanol solution (0.05mg/ml), and continuously stirring for 2-5 hours to obtain solution A;
(2) adding 0.83g of resorcinol and 0.42g of formaldehyde into the solution A obtained in the step (1), stirring for 24-36 hours, and then transferring into a high-pressure reaction kettle to keep the temperature at 100 ℃ for 24 hours; then cooling to room temperature, and carrying out centrifugal separation at the rotating speed of 5000 r/min; then washing the obtained precipitate with ethanol and deionized water for 3 times in sequence, and then drying in vacuum at 70 ℃ for 20 hours to obtain a silicon dioxide/phenolic resin composite material B;
(3) and (3) placing the product B obtained in the step (2) in a tubular furnace, introducing nitrogen or argon or nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 1000 ℃ at the speed of 2 ℃/min under the atmosphere protection, keeping for 3 hours, and naturally cooling to room temperature to obtain a product C.
(4) Placing the product C obtained in the step (3) in a sodium hydroxide solution (6%), continuously stirring and reacting for 12 hours at room temperature, then washing the precipitate for 3 times by using ethanol and deionized water successively until the filtrate is neutral, and then drying for 36 hours in vacuum at 90 ℃ to obtain a product D;
(5) and (3) uniformly mixing the product D obtained in the step (4) with a reducing agent according to the mass ratio of 3:1, placing the mixture in a tubular furnace, introducing nitrogen or argon or nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 800 ℃ at the speed of 2 ℃/min under the protection of atmosphere, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain a product E.
(6) And (3) fully mixing and stirring the product E obtained in the step (5) and a dilute hydrochloric acid solution (10%), reacting for more than 24 hours, then washing for 3 times by using ethanol and deionized water sequentially until the filtrate is neutral, and then drying in vacuum at 90 ℃ for 24 hours to obtain the final product, namely the silicon oxide/carbon microsphere composite negative electrode material.
Table 1 shows that the lithium ion batteries of examples 1 to 3 are operated at 500mA g-1And (4) carrying out charge and discharge tests under current to obtain the capacity and the capacity retention rate at the 2 nd circle and the 200 th circle.
Table 1:
as can be seen from Table 1, when the silicon oxide/carbon microspheres provided by the invention are used as an electrode negative electrode material and applied to a lithium ion battery, the charging capacity is 786.8mAh g after 200 cycles of circulation-1Above, the capacity retention rate is above 83.3%, and the graphite anode material has good cycle performance and is still far higher than that of the current commercialized graphite anode material.
Table 2 mass% and atomic% of Si, O, and C in the silicon oxide/carbon microsphere composite anode material in example 1
Table 2:
| kind of element | Wt％ | Atomic％ |
| C | 58.43 | 70.80 |
| O | 19.55 | 17.79 |
| Si | 22.02 | 11.41 |
| Total amount of | 100.00 | 100.00 |
It can be seen that the atomic number ratio of Si, O, C in the silicon oxide/carbon (SiOx/C) microsphere composite was 1:1.56: 6.21.
The foregoing is only a preferred embodiment of the present invention. The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such equivalent changes and modifications as would be obvious to one skilled in the art be included within the scope of the appended claims.
Claims (5)
1. A preparation method of a silicon oxide/carbon microsphere composite negative electrode material for a lithium ion battery is characterized in that the silicon oxide/carbon microsphere composite negative electrode material is of a core-shell structure, the diameter of the silicon oxide/carbon microsphere composite negative electrode material is 100-300 nm, a gap with a distance of 15-45 nm is formed between a core silicon oxide and a carbon shell, the diameter of the core silicon oxide is 30-150 nm, the thickness of the carbon shell is 20-30 nm, and according to mass percent, 15-40% of silicon, 13-21% of oxygen and 45-70% of carbon are contained; the preparation method is characterized by comprising the following steps:
(1) mixing ammonia water with ammonia content of 25-28%, deionized water and ethanol according to a volume ratio of 0.5-0.8: 1: 1.5-3, and mixing the mixed solution according to a volume ratio of 1:1, adding the mixture into a silane ethanol solution with the concentration of 0.05-0.1 g/L, and stirring for 2-5 hours to obtain a solution A;
(2) adding resorcinol and formaldehyde into the solution A obtained in the step (1), and stirring for 24-36 hours, wherein the concentration of resorcinol in A is 6.25-17.5 g/L, and the mass ratio of resorcinol to formaldehyde is 2-3: 1; then transferring the mixture into a high-pressure reaction kettle, and keeping the temperature at 90-110 ℃ for 20-30 hours; naturally cooling to room temperature, performing centrifugal separation, washing the obtained product with ethanol and deionized water for 2-3 times, and performing vacuum drying at 70-90 ℃ for 20-30 hours to obtain a product B;
(3) placing the product B obtained in the step (2) in a tubular furnace, introducing nitrogen or argon or nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 800-1100 ℃ at the speed of 2-5 ℃/min under the protection of atmosphere, keeping for 3-5 hours, and then naturally cooling to room temperature to obtain a product C;
(4) placing the product C obtained in the step (3) in a sodium hydroxide solution, stirring and reacting for 5-20 hours at room temperature, then washing the precipitate with ethanol and deionized water for 2-3 times in sequence until the filtrate is neutral, and then drying in vacuum at 70-90 ℃ for 24-36 hours to obtain a product D;
(5) uniformly mixing the product D obtained in the step (4) with a reducing agent according to the mass ratio of 3-5: 1, placing the mixture in a tubular furnace, introducing nitrogen or argon or a nitrogen-argon mixed gas in any proportion into the tubular furnace, heating to 700-800 ℃ at the speed of 2-5 ℃/min under the protection of atmosphere, keeping the temperature for 3-5 hours, and naturally cooling to room temperature to obtain a product E;
(6) and (3) fully mixing and stirring the product E obtained in the step (5) with a dilute hydrochloric acid solution, reacting for 24 hours, then washing with ethanol and deionized water for 2-3 times in sequence until the filtrate is neutral, and then drying in vacuum at 70-90 ℃ for 24-36 hours to obtain the final product, namely the silicon oxide/carbon microsphere composite negative electrode material.
2. The method for preparing the silicon oxide/carbon microsphere composite anode material for the lithium ion battery as claimed in claim 1, wherein the silane is one or a mixture of tetra (2-methoxyethoxy) silane, tetramethoxysilane and tetraethoxysilane in any mass ratio.
3. The preparation method of the silicon oxide/carbon microsphere composite anode material for the lithium ion battery according to claim 1, wherein the etching solution is one or a mixture of potassium hydroxide solution, sodium hydroxide solution and sodium carbonate solution in any mass ratio, or hydrofluoric acid solution.
4. The preparation method of the silicon oxide/carbon microsphere composite anode material for the lithium ion battery as claimed in claim 1, wherein the reducing agent is one or more of aluminum, magnesium, sodium and potassium metal powder in any mass ratio.
5. The silicon oxide/carbon microsphere composite anode material for the lithium ion battery, which is prepared by the preparation method of the silicon oxide/carbon microsphere composite anode material for the lithium ion battery according to any one of claims 1 to 4.
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