CN114843482B - Core-shell type silicon-carbon composite material and preparation method and application thereof - Google Patents
Core-shell type silicon-carbon composite material and preparation method and application thereof Download PDFInfo
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- CN114843482B CN114843482B CN202210567480.4A CN202210567480A CN114843482B CN 114843482 B CN114843482 B CN 114843482B CN 202210567480 A CN202210567480 A CN 202210567480A CN 114843482 B CN114843482 B CN 114843482B
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 36
- 239000011258 core-shell material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010416 ion conductor Substances 0.000 claims abstract description 26
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 23
- 238000007740 vapor deposition Methods 0.000 claims abstract description 14
- 229920002472 Starch Polymers 0.000 claims abstract description 12
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000008107 starch Substances 0.000 claims abstract description 9
- 235000019698 starch Nutrition 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- -1 3-mercaptopropyl Chemical group 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 229920001592 potato starch Polymers 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920002261 Corn starch Polymers 0.000 claims description 4
- 239000008120 corn starch Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- HRNWETBDIWJQRN-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) hexanethioate Chemical compound CCCCCC(=O)SCCC[Si](OCC)(OCC)OCC HRNWETBDIWJQRN-UHFFFAOYSA-N 0.000 claims description 2
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 29
- 239000002210 silicon-based material Substances 0.000 abstract description 19
- 229910021385 hard carbon Inorganic materials 0.000 abstract description 17
- 239000002131 composite material Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 11
- 238000000498 ball milling Methods 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003610 charcoal Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000005543 nano-size silicon particle Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The embodiment of the invention discloses a core-shell type silicon-carbon composite material, wherein the inner core is a composite material comprising hard carbon, amorphous carbon and silicon-based material components, and the outer shell is a fast ion conductor; wherein the silicon-based material is a mixture of silicon oxide and silicon powder, and the mass ratio of the silicon oxide to the silicon powder is 1:0.02-0.2; the composite material is prepared by mixing and ball milling silicon oxide, silicon powder, a silane coupling agent and starch raw materials, performing a spray drying to obtain an inner core, and depositing a fast ion conductor on the surface of the inner core by an atomic vapor deposition method to obtain the core-shell type silicon-carbon composite material. The silicon-based material in the core-shell silicon-carbon composite material improves the specific capacity, and the expansion in the charge and discharge process can be reduced when the silicon-based material is embedded into hard carbon; the shell is a fast ion conductor, the fast charging performance of the material is improved, and the fast ion conductor is coated on the surface of the inner core by adopting an atomic vapor deposition method, so that the defect of the surface of the inner core is greatly reduced, and the first efficiency of the material is improved.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a core-shell type silicon-carbon composite material, and a preparation method and application thereof.
Background
The hard carbon material has the advantages of good quick charge performance (the interlayer spacing is more than or equal to 0.38 nm), good safety performance (the voltage platform is 0.2V), zero expansion, wide material sources (carbon-containing compounds such as coconut shells, starch, asphalt, resin and the like) and the like, is used as one of the selection of quick charge anode materials, and is applied to quick charge lithium ion batteries and sodium ion batteries, but the hard carbon has the defect of low specific capacity (300 Ah/g), is lower than the specific capacity (355 Ah/g) of the marketized graphite material, and has the first efficiency of only 80 percent and is far lower than the first efficiency of 92-94 percent of the graphite material.
The theoretical specific capacity of the silicon material is 4200Ah/g, but the silicon material has the defect of high full-charge expansion rate (300%), so that the silicon material is easy to collapse in crystal structure in the circulating process, and the conductive network structure of the electrode is damaged, so that the service life of the battery is greatly shortened; meanwhile, silicon is a semiconductor material, and conductivity is extremely poor, so that the rate characteristics of the battery are affected. Therefore, silicon cannot be independently used as a negative electrode material, and the volume expansion is relieved mainly by forming a silicon-carbon composite material from nano silicon and a carbon-based material, so that the cycle and multiplying power characteristics of the material are improved. Although the energy density and the multiplying power performance of the general silicon-carbon composite material are improved to a certain extent, the defects of low primary efficiency and the like still exist, so that the silicon-carbon composite material which has both the energy density and the quick charge performance and can improve the primary efficiency of the material needs to be developed.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a core-shell type silicon-carbon composite material, which is prepared by doping a silicon-based material into porous hard carbon to improve energy density and restrict expansion, and simultaneously coating a fast ion conductor material on an outer layer, wherein on one hand, the rate of intercalation and deintercalation of lithium ions in a charge-discharge process is improved, and on the other hand, the coating on the outer surface reduces side reaction of the composite material to improve first efficiency.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
The technical purpose of the first aspect of the invention is to provide a core-shell type silicon-carbon composite material, wherein the inner core is a composite material comprising hard carbon, amorphous carbon and silicon-based material components, and the outer shell is a fast ion conductor; the mass percentage of the shell is 1% -10% based on the total weight of the core-shell type silicon-carbon composite material being 100%; based on the total weight of the inner core as 100%, the mass percentage of hard carbon is 50% -90%, the mass percentage of silicon-based material is 5% -40%, and the balance is amorphous carbon; wherein the silicon-based material is a mixture of silicon oxide and silicon powder, and the mass ratio of the silicon oxide to the silicon powder is 1:0.02-0.2, preferably 1:0.05-0.1.
Further, in the core-shell type silicon-carbon composite material, the fast ion conductor is LixNyWz, wherein X is more than or equal to 1.5 and more than or equal to 0.5, Y is more than or equal to3 and more than or equal to 0.5, and N is one of Ni, co, mn, al, cr, fe, mg, V, zn and Cu; w is selected from one of SiO 4-、SO4 2-、MoO4 2-、PO4 3-、TiO3 2- and ZrO 4 3-. Preferably, the fast ion conductor is selected from at least one of LiNiSO 4、LiCoMoO4 and liaaltio 3.
Further, the particle size ratio of the silicon-based material silicon oxide to silicon powder is 1-5:1, and the particle size of the silicon oxide is 0.5-2 mu m.
Further, in the core-shell type silicon-carbon composite material, the total weight of the core is 100%, wherein the mass percentages of the components are preferably as follows:
50 to 80 percent of hard carbon
10 To 20 percent of silicon-based material
Amorphous carbon 10% -30%
The technical purpose of the second aspect of the invention is to provide a preparation method of the core-shell type silicon-carbon composite material, which comprises the following steps:
Preparing a core: dispersing silicon oxide, silicon powder and a silane coupling agent in an organic solvent, mixing, spray drying, adding the obtained solid material into a starch aqueous solution, mixing, spray drying, and carbonizing in an inert atmosphere to obtain a core;
and (3) coating a shell: and depositing a fast ion conductor on the surface of the inner core by an atomic vapor deposition method to obtain the core-shell type silicon-carbon composite material.
In the preparation method, when preparing the kernel, the raw materials are added according to the following mass ratio: silicon powder: organic solvent: silane coupling agent: starch=50: (1-10): (100-500): (1-10):800-1200.
In the preparation method, the particle size ratio of the silicon oxide to the silicon powder is 1-5:1, and the particle size of the silicon oxide is 0.5-2 mu m.
In the above preparation method, the silane coupling agent is a sulfur-containing silane coupling agent, more specifically, the silane coupling agent is at least one selected from bis (3-propyltriethoxysilane coupling agent) disulfide, bis (3-propyltriethoxysilane coupling agent) tetrasulfide, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyldimethoxysilane, 3-mercaptopropyl ethyloxy di (tridecylpenta-diethyl ether) silane, 3-mercaptopropyl ethyloxy di (propylhexa-propyl ether) silane, 3-hexanoylthio-1-propyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, and 3-octanoylthio-1-propylethoxy (2-methyl-1, 3-propanediol subunit) silane.
In the above preparation method, the organic solvent is at least one selected from carbon tetrachloride, N-methylpyrrolidone, xylene and cyclohexane.
In the above preparation method, the starch is at least one selected from potato starch, corn starch, wheat starch and sweet potato starch.
In the preparation method, the carbonization is carried out for 1-6 hours at 800-1200 ℃ under inert atmosphere.
In the preparation method, the ball milling mode is adopted for twice mixing when preparing the kernel.
In the above preparation method, the atomic vapor deposition method specifically includes: vacuumizing the reaction chamber to 50-100toor, heating to 100-300 ℃, gasifying the fast ion conductor, carrying the fast ion conductor into the reaction chamber by nitrogen at a flow rate of 10-100sccm, adsorbing the fast ion conductor on the surface of the inner core until the air pressure of the reaction chamber reaches 5-20toor, and keeping for 1-120s to realize coating of the fast ion conductor.
The technical purpose of the third aspect of the invention is to provide the application of the core-shell type silicon-carbon composite material as a battery anode material.
The implementation of the embodiment of the invention has the following beneficial effects:
(1) The silicon-carbon composite material has a core-shell structure, the inner core is a composite material of hard carbon and a silicon-based material, the silicon-based material improves specific capacity, and the expansion in the charge and discharge process can be reduced when the silicon-carbon composite material is embedded into the hard carbon; the shell is a fast ion conductor, so that the fast charging performance of the material is improved, the surface of the inner core is coated, the defects of the surface of the inner core are reduced, and the first efficiency of the material is improved. In addition, the silicon-based material silicon oxide and the nano silicon powder are connected through the coupling agent to form a network structure, and the silicon oxide with relatively large particle size is further adopted, so that the agglomeration of the nano silicon can be reduced, the nano silicon powder has the characteristic of high electronic conductivity, and the rate capability in the charge and discharge process is improved.
(2) According to the core-shell type silicon-carbon composite material, starch is adopted as a hard carbon raw material in the preparation process of a core, porous hard carbon is formed after carbonization, and silicon-based materials are doped in pores of the hard carbon in the carbonization process to obtain a composite material core, so that on one hand, the silicon-based materials can improve the specific capacity of the material, and on the other hand, the silicon-based materials are embedded in the carbon-based materials to reduce expansion in the charge and discharge processes; and a silane coupling agent is also added in the preparation process of the inner core to connect carbon with silicon, so that the expansion of the material in the charge and discharge processes is further reduced. The shell deposits the fast ion conductor on the surface of the hard carbon-silicon of the inner core through an atomic vapor deposition method, on one hand, the fast charge performance of the material is improved by virtue of the characteristic of high conductivity in the charge and discharge process of the fast ion conductor, on the other hand, the fast ion conductor is coated on the surface of the inner core through the atomic vapor deposition method, so that the defect of the surface of the inner core is greatly reduced, and the first efficiency of the material is improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Wherein:
fig. 1 is an SEM image of the core-shell type silicon-carbon composite material prepared in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Core-shell silicon-carbon composites were prepared in examples 1-3:
Example 1
S1, preparing a kernel:
Mixing 50g of silicon oxide, 5g of nano silicon powder and 300g of N-methyl pyrrolidone organic solvent, wherein the average particle size of the silicon oxide is 1000nm, the average particle size of the nano silicon powder is 200nm, adding 5g of bis (3-propyltriethoxysilane coupling agent) disulfide after uniform dispersion, ball milling and spray drying, adding the obtained material into 10000mL of 10wt% potato starch aqueous solution, ball milling and spray drying, and carbonizing at 800 ℃ for 3h under an argon inert atmosphere to obtain the silicon-carbon composite material serving as an inner core.
S2, preparing a shell:
And vacuumizing the reaction chamber to 80toor ℃ by an atomic vapor deposition method, heating to 200 ℃, gasifying LiNiSO 4, pulsing into the reaction chamber at a flow rate of 50sccm under the carrying of nitrogen, and adsorbing LiNiSO 4 on the surface of the inner core until the air pressure of the reaction chamber reaches 10toor, and maintaining for 60 seconds to obtain the core-shell type silicon-carbon composite material.
Example 2
S1, preparing a kernel:
mixing 50g of silicon oxide, 1g of nano silicon powder and 100g of carbon tetrachloride, wherein the average particle size of the silicon oxide is 500nm, the average particle size of the nano silicon powder is 100nm, adding 1g of bis (3-propyltriethoxysilane coupling agent) tetrasulfide after uniform dispersion, ball milling and spray drying, adding the obtained material into 10000mL of 10wt% corn starch aqueous solution, ball milling and spray drying, and carbonizing at 800 ℃ for 6 hours under an argon inert atmosphere to obtain the silicon-carbon composite material serving as an inner core.
S2, preparing a shell:
And vacuumizing the reaction chamber to 50toor ℃ by an atomic vapor deposition method, heating to 100 ℃, gasifying LiCoMoO 4, carrying nitrogen, pulsing into the reaction chamber at a flow rate of 10sccm, and adsorbing LiCoMoO 4 on the surface of the inner core until the air pressure of the reaction chamber reaches 5toor, and keeping for 1s to obtain the core-shell type silicon-carbon composite material.
Example 3
S1, preparing a kernel:
Mixing 50g of silicon oxide, 10g of nano silicon powder and 500g of cyclohexane organic solvent, wherein the average particle size of the silicon oxide is 2000nm, the average particle size of the nano silicon powder is 500nm, adding 10g of 3-mercaptopropyl ethoxy di (tridecyl pentamethylene ether) silane after uniform dispersion, ball milling and spray drying, adding the obtained material into 2000mL of 50wt% wheat starch aqueous solution, ball milling and spray drying, and carbonizing at 800 ℃ for 6 hours under an argon inert atmosphere to obtain the silicon-carbon composite material serving as a core.
S2, preparing a shell:
And vacuumizing the reaction chamber to 100toor ℃ by an atomic vapor deposition method, heating to 300 ℃, gasifying LiAlTiO 3, carrying nitrogen, and pulse-entering the reaction chamber at a flow rate of 100sccm, wherein LiAlTiO 3 is adsorbed on the surface of the inner core until the air pressure of the reaction chamber reaches 20toor, and maintaining for 120s to obtain the core-shell type silicon-carbon composite material.
Comparative example 1
50G of silicon monoxide is added into 10000mL of 10wt% potato starch aqueous solution, ball milling and spray drying are carried out, and then carbonization is carried out for 3 hours at 800 ℃ under the inert atmosphere of argon, thus obtaining the silicon-carbon composite material.
Comparative example 2
100G of corn starch and 10g of asphalt are uniformly mixed by a ball mill, then the mixture is polymerized for 1h at the temperature of 200 ℃ under the inert atmosphere, then carbonized for 3 h at the temperature of 800 ℃ under the protection of inert gas, and cooled to the room temperature after the completion to obtain the hard carbon composite material.
Comparative example 3
S1, preparing a kernel:
s1 is the same as in example 1.
S2, bonding the shell by a solution method:
Taking 100g of the kernel prepared by S1, adding 5g LiNiSO 4 g of asphalt binder and 100mL of butanediol, uniformly mixing and stirring, filtering, transferring into a tube furnace, carbonizing at 800 ℃ for 3h under argon atmosphere, and crushing to obtain the silicon-carbon composite material.
Comparative example 4
The procedure was the same as in example 1 except that 50g of silica was changed to 68.2g of silica (the weight of silicon element added to the system was the same as in example 1), to obtain a core-shell type silicon-carbon composite.
Comparative example 5
The procedure was otherwise identical to example 1 except that no silica was added to obtain a core-shell type silicon-carbon composite.
Comparative example 6
The procedure was as in example 1 except that 50g of silica and 5g of nano-silica powder were replaced with 1g of silica and 50g of nano-silica powder, to obtain a core-shell type silicon-carbon composite.
Performance testing of the materials prepared in the above examples and comparative examples:
(1) SEM test
The core-shell type silicon-carbon composite material prepared in example 1 was subjected to SEM test, and the test results are shown in fig. 1.
As can be seen from FIG. 1, the composite material prepared in example 1 has a granular structure, has a relatively uniform size distribution and has a particle size of 2-10 μm.
(2) Physical and chemical properties and button cell testing
The composite materials prepared in examples 1 to 3 and comparative examples 1 to 6 were subjected to particle size, true density, tap density, specific surface area, ash content and specific capacity tests. The method is tested according to the national standard GBT-24533-2019 lithium ion battery graphite anode material. The test results are shown in Table 1.
TABLE 1
The composite materials in examples 1-3 and comparative examples 1-6 are used as negative electrode materials of lithium ion batteries to be assembled into button batteries, and the specific preparation method of the negative electrode materials is as follows: adding binder, conductive agent and solvent into the composite material, stirring to slurry, coating on copper foil, oven drying, and rolling. The adhesive is LA132 adhesive, the conductive agent SP, the solvent is secondary distilled water, and the composite material is prepared from the following components: SP: LA132: secondary distilled water = 90g:4g:6g:220mL, preparing a negative electrode plate; a metal lithium sheet is used as a positive electrode; the electrolyte adopts LiPF 6/EC+DEC, liPF 6 in the electrolyte is electrolyte, the mixture of EC and DEC with the volume ratio of 1:1 is solvent, and the electrolyte concentration is 1.3mol/L; the diaphragm adopts a composite film of polyethylene PE, polypropylene PP or polyethylene propylene PEP. The button cell assembly was performed in an argon filled glove box. Electrochemical performance was performed on a wuhan blue electric CT2001A type battery tester with a charge-discharge voltage ranging from 0.005V to 2.0V and a charge-discharge rate of 0.1C, and the first discharge capacity and first efficiency of the coin cell battery were tested while the rate performance (5C, 0.1C) and cycle performance (0.5C/0.5C, 200 times) were tested. The test results are shown in Table 2.
TABLE 2
As can be seen from table 1 and table 2, the material prepared by the embodiment of the invention has high specific capacity and first efficiency, and is characterized in that the silicon oxide and silicon doped in the material cooperate to improve the specific capacity of the material, meanwhile, the surface of the material is coated with a fast ion conductor, so that the irreversible capacity loss of the material is reduced, the first efficiency and the multiplying power performance of the material are improved, and the atomic vapor deposition method has the characteristic of high coating density, thereby improving the tap density of the material. Compared with the material prepared by the traditional liquid phase cladding method, the material of the embodiment 1 has high density, low electronic impedance, improved activity, specific capacity and first efficiency, and improved rate performance.
(3) Soft package battery test:
The composite materials in examples 1-3 and comparative examples 1-6 were subjected to slurry mixing and coating to prepare a negative electrode sheet, a ternary material (LiNi 1/3Co1/3Mn1/3O2) was used as a positive electrode, liPF 6 (solvent ec+dec, volume ratio 1:1, electrolyte concentration 1.3 mol/L) was used as an electrolyte, and Celgard2400 membrane was used as a separator to prepare a 1Ah soft-pack battery.
The rate performance of the soft package battery is tested, the charging and discharging voltage ranges from 2.75V to 4.2V, the temperature is 25+/-3.0 ℃, the charging is carried out at 1.0C, 3.0C, 5.0C, 10.0C and 20.C, and the discharging is carried out at 1.0C. The results are shown in Table 3.
TABLE 3 Table 3
As can be seen from table 3, the rate charging performance of the soft pack batteries prepared from the materials of examples 1 to 3 is significantly better than that of comparative examples 1 to 2, i.e., the charging time is shorter, because of the analysis: the migration of lithium ions is needed in the battery charging process, while the surface of the negative electrode material in the embodiment is coated with a fast ion conductor with high lithium ion conductivity, and meanwhile, compared with a solid phase coating method, an atomic vapor deposition method is adopted, and amorphous carbon coated on the surface of a hard carbon material has the characteristics of high density and stable structure, so that the rate capability is improved.
(4) And (3) testing the cycle performance:
The cycle performance test conditions were: the charge and discharge current is 0.5C/1C, the voltage range is 2.5-4.2V, and the cycle times are 1000 times. The test results are shown in Table 4.
TABLE 4 Table 4
It can be seen from Table 4 that the cycle performance of the lithium ion batteries prepared using the composite materials obtained in examples 1 to 3 was significantly better at each stage than that of the comparative example. Experimental results show that the fast ion conductor deposited on the surface of the hard carbon by the atomic vapor deposition method has the characteristics of high density, stable structure and strong ion conductivity, and the expansion of silicon in the process of low-constraint charge and discharge of the hard carbon expansion of the inner core is improved, and the cycle performance is improved.
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (3)
1. The preparation method of the core-shell type silicon-carbon composite material is characterized by comprising the following steps of:
Preparing a core: dispersing silicon oxide, silicon powder and a silane coupling agent in an organic solvent, mixing, spray drying, adding the obtained solid material into a starch aqueous solution, mixing, spray drying, and carbonizing in an inert atmosphere to obtain a core;
And (3) coating a shell: depositing a fast ion conductor on the surface of the inner core by an atomic vapor deposition method to obtain a core-shell silicon-carbon composite material;
The silicon oxide: silicon powder: organic solvent: silane coupling agent: the mass ratio of the starch is 50: (1-10): (100-500): (1-10): (800-1200);
the particle size ratio of the silicon oxide to the silicon powder is 1-5:1, and the particle size of the silicon oxide is 0.5-2 mu m;
The starch is at least one selected from potato starch, corn starch, wheat starch and sweet potato starch;
the carbonization is carried out for 1-6 hours at 800-1200 ℃ in inert atmosphere;
the fast ion conductor is selected from at least one of LiNiSO 4、LiCoMoO4 and liaaltio 3;
The atomic vapor deposition method specifically comprises the following steps: vacuumizing the reaction chamber to 50-100toor, heating to 100-300 ℃, gasifying the fast ion conductor, carrying the fast ion conductor into the reaction chamber by nitrogen at a flow rate of 10-100sccm, adsorbing the fast ion conductor on the surface of the inner core until the air pressure of the reaction chamber reaches 5-20toor, and keeping for 1-120s to realize coating of the fast ion conductor.
2. The method according to claim 1, wherein the silane coupling agent is at least one selected from the group consisting of bis (3-propyltriethoxysilane coupling agent) disulfide, bis (3-propyltriethoxysilane coupling agent) tetrasulfide, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyldimethoxysilane, 3-mercaptopropyl methyldiethoxysilane, 3-mercaptopropyl ethoxybis (tridecyl pentamethyl ether) silane, 3-mercaptopropyl ethoxybis (propyl hexapolypropylene ether) silane, 3-hexanoylthio-1-propyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, and 3-octanoylthio-1-propylethoxy (2-methyl-1, 3-propanediol subunit) silane.
3. The method according to claim 1, wherein the organic solvent is at least one selected from the group consisting of carbon tetrachloride, N-methylpyrrolidone, xylene and cyclohexane.
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