CN112510180B - Silicon oxide-carbon filament active material and preparation method and application thereof - Google Patents
Silicon oxide-carbon filament active material and preparation method and application thereof Download PDFInfo
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- CN112510180B CN112510180B CN202011403814.1A CN202011403814A CN112510180B CN 112510180 B CN112510180 B CN 112510180B CN 202011403814 A CN202011403814 A CN 202011403814A CN 112510180 B CN112510180 B CN 112510180B
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- 239000011149 active material Substances 0.000 title claims abstract description 38
- NCZAACDHEJVCBX-UHFFFAOYSA-N [Si]=O.[C] Chemical compound [Si]=O.[C] NCZAACDHEJVCBX-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 229910052786 argon Inorganic materials 0.000 claims abstract description 22
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical compound C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 238000005524 ceramic coating Methods 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920001289 polyvinyl ether Polymers 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229910013131 LiN Inorganic materials 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011889 copper foil Substances 0.000 abstract description 16
- 229910052593 corundum Inorganic materials 0.000 abstract description 10
- 239000010431 corundum Substances 0.000 abstract description 10
- 238000009830 intercalation Methods 0.000 abstract description 7
- 230000002687 intercalation Effects 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 40
- 238000000498 ball milling Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002848 electrochemical method Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- KYWXBCABTMUGFC-UHFFFAOYSA-N [F-].[NH4+].[Si]=O Chemical compound [F-].[NH4+].[Si]=O KYWXBCABTMUGFC-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/621—Binders
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a silicon oxide-carbon filament active material. The material consists of carbon filaments and silicon oxide, wherein the carbon filaments account for 10-30% of the total mass. The preparation method comprises the following steps: high-energy ball milling of silicon oxide in argon environment for 10-30 hours, placing the obtained precursor in a corundum boat wrapped by copper foil, placing the corundum boat in a chemical vapor deposition device, and vacuumizing to less than or equal to 1.0 multiplied by 10‑2And (3) introducing argon to normal pressure, then starting heating, introducing a protective gas and a reducing gas in the heating process, heating to 1000-1200 ℃, keeping for 1-3 hours, cooling to 900-1100 ℃, introducing a carbon source gas, keeping for 1-3 hours, and naturally cooling to room temperature. According to the invention, the carbon filaments grow on the surface of the silicon oxide, so that the circulation stability of the silicon oxide is improved; and the volume change of the silicon oxide in the processes of lithium intercalation and lithium deintercalation is effectively inhibited, so that the silicon oxide has high cycle stability, first coulombic efficiency and conductivity.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a silicon oxide-carbon filament active material as well as a preparation method and application thereof.
Background
The currently used lithium ion battery cathode material is mainly carbon-based cathode material, and the theoretical specific capacity of the cathode material is only 372mAh/g, which cannot meet the requirement of high specific energy lithium ion batteries required by world development. In various negative electrode materials researched at present, silicon-based negative electrode materials are widely concerned due to the fact that the theoretical specific capacity of silicon reaches 4200mAh/g and the storage capacity of silicon in the earth crust is the second place. However, the silicon-based material has its own disadvantages, which affect the commercial application and popularization of the silicon-based negative electrode material due to large volume deformation (about-300%) caused by intercalation and deintercalation of lithium ions during charge and discharge, and low conductivity of silicon. Compared with a silicon negative electrode, silicon oxide (silicon monoxide (2615mAh/g) and silicon dioxide (1965mAh/g)) generates smaller volume deformation in the charging and discharging processes, but the silicon oxide negative electrode material has low initial coulombic efficiency (ICE: 20-40%), is unstable in circulation and poor in conductivity, and the development of the silicon oxide negative electrode material is influenced by the problems.
In order to solve the problems, the patent CN111584855A adds silicon oxide particles into absolute ethyl alcohol, and ultrasonic dispersion is carried out to obtain dispersion liquid; adding resin into the dispersion liquid, heating to dissolve the resin, stirring and grinding to obtain a mixture; spray drying the mixture to obtain a dried product; and carrying out heat treatment on the dried product to foam the resin and then carbonize the resin, and carrying out carbon deposition on the surface by using a chemical vapor deposition method. The method has complex content, cannot play a good role in the volume change of the silicon monoxide, and cannot effectively improve the first coulombic efficiency and the conductivity of the silicon oxide.
Patent CN110890540A discloses a fluorine-containing silicon monoxide negative electrode material, and a preparation method and application thereof. Mixing and grinding silicon monoxide powder and ammonium fluoride powder to obtain silicon monoxide-ammonium fluoride composite powder; and sintering the silicon monoxide-ammonium fluoride composite powder under the protection of inert gas to obtain the fluorine-containing silicon monoxide negative electrode material. The method is difficult to uniformly distribute the fluorine element on the silicon monoxide surface, and the average grain diameter of the fluorine-containing silicon monoxide material is 10-70 mu m, so that the method is not beneficial to the rapid de-intercalation of lithium ions in the composite cathode material. And does not effectively solve the problem of volume expansion of SiO during the process of intercalation/deintercalation.
Disclosure of Invention
One object of the present invention is to provide a silica-carbon filament active material. The specific technical scheme is as follows:
the silicon oxide-carbon filament active material consists of carbon filaments and SiOx, wherein x is more than or equal to 0 and less than or equal to 2, the carbon filaments account for 10-30% of the total mass, and the particle size of the SiOx is 10nm-10 mu m.
The other purpose of the invention is to provide a preparation method of the silicon oxide-carbon filament active material. The specific technical scheme is as follows:
the preparation method of the silicon oxide-carbon filament active material comprises the following steps: carrying out high-energy ball milling on silicon oxide for 10-30 hours in an argon environment to obtain a precursor; placing the precursor in a chemical vapor deposition device (or placing the precursor in a corundum boat wrapped by copper foil, and then placing the corundum boat in the chemical vapor deposition device), and vacuumizing to less than or equal to 1.0 multiplied by 10-2And (2) introducing argon to normal pressure, then starting heating, introducing 100-500 sccm of protective gas and 20-100 sccm of reducing gas in the heating process, heating to 1000-1200 ℃, keeping for 1-3 hours, then cooling to 900-1100 ℃, introducing 10-100 sccm of carbon source gas, keeping for 1-3 hours at 900-1000 ℃, closing the carbon source gas, and naturally cooling to room temperature to obtain the silicon oxide-carbon filament active material.
Preferably, the protective gas is nitrogen, argon or helium.
Preferably, the reducing gas is any one or a mixture of two or more of ammonia gas, hydrogen gas or hydrogen sulfide.
Preferably, the carbon source gas is CH4、C2H4、C2H2、C2H6、C3H4、C3H6、C3H8、C4H6、C4H8、C4H10Or C7H8Any one or a mixture of two or more of them.
Preferably, the particle size of the silicon oxide is 10nm to 10 μm.
Preferably, the rate of temperature rise is as follows: the temperature rise rate is 8-10 ℃/min at 0-1000 ℃, and the temperature rise rate is 2-5 ℃/min at 1000-1100 ℃; the cooling rate is 2-5 ℃/min.
The invention also aims to provide application of the silicon oxide-carbon filament active material. The specific technical scheme is as follows:
the silicon oxide-carbon filament active material is applied to a lithium ion battery cathode material.
Preferably, the anode material further includes: conductive agents, binders; the conductive agent is at least one or a mixture of more than two of carbon black, acetylene black, natural graphite, carbon nanotubes, graphene and carbon fibers; the binder is one or a mixture of more than two of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer, sodium carboxymethylcellulose and sodium alginate; in the negative electrode material, 50-99.5 wt% of active material, 0.1-40 wt% of conductive agent and 0.1-40 wt% of binder.
Preferably, the lithium ion battery further comprises a positive electrode, a diaphragm and electrolyte; wherein the positive electrode is lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate or lithium composite metal oxide; the diaphragm is any one of an aramid diaphragm, a non-woven fabric diaphragm, a polyethylene microporous film, a polypropylene-polyethylene double-layer or three-layer composite film and a ceramic coating diaphragm; the electrolyte comprises an electrolyte and a solvent, wherein the electrolyte is LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2) Any one or a mixture of two or more of LiBOB, LiCl, LiBr and LiI; the solvent is one or more of Propylene Carbonate (PC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), 1, 2-Dimethoxyethane (DME), Ethylene Carbonate (EC), Butylene Carbonate (BC), diethyl carbonate (DEC), Ethyl Acetate (EA), and ethylene sulfite (GS).
The invention has the advantages of
Firstly, ball-milling silicon oxide for 10-30 hours by a high-energy ball mill until the ball-milling is in a nanometer level, wherein the ball-milled silicon oxide is in an argon environment during ball-milling, carrying out Chemical Vapor Deposition (CVD) treatment on the ball-milled silicon oxide, coating a layer of copper foil on the periphery of the silicon oxide before the CVD treatment, and realizing the growth of carbon filaments on the surface of the silicon oxide by controlling the flow of gas.
The preparation method has simple process, does not need some harmful chemical reagents, and firstly reduces the size of the silicon oxide particles so as to enable lithium ions to have more transportation paths. Before the chemical vapor deposition treatment, if a layer of copper foil is coated around the silicon oxide, the growth of carbon filaments is facilitated, and the first coulombic efficiency and the conductivity of the silicon oxide can be improved. The carbon filaments grow on the surface of the silicon oxide, so that the volume expansion of the silicon oxide can be effectively inhibited, the transmission path of lithium ions is increased, and the cycle stability of the silicon oxide is improved; and the volume change of the silicon oxide in the processes of lithium intercalation and lithium deintercalation is effectively inhibited, so that the silicon oxide has high cycle stability, and the first coulombic efficiency and the conductivity of the silicon oxide are improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of an active material obtained in example 1; FIG. 1a is a SEM of 1 μm unit length, FIGS. 1b and 1c are SEM of 200nm unit length, and FIG. 1d is SEM of 1nm unit length.
Fig. 2a is an electrochemical impedance spectrum of the active material obtained in example 1, and fig. 2b is an electrochemical impedance spectrum of the active material obtained in example 3.
Fig. 3a is a charge and discharge curve of the active material obtained in example 1, and fig. 3b is a charge and discharge curve of the active material obtained in example 2.
Fig. 4a is an electrochemical cycling test curve of the active material obtained in example 1, and fig. 4b is an electrochemical cycling test curve of the active material obtained in example 2.
Fig. 5 is a rate capability test curve of the active material obtained in example 1.
Detailed Description
Example 1
In a glove box filled with argon, silicon monoxide (ball powder ratio is 20:1, and the particle size of the silicon monoxide is more than 100 μm) is filled into a ball milling tank, the ball milling tank is sealed and then is subjected to high-energy ball milling for 10 hours, the ball milled silicon monoxide is uniformly placed into a corundum boat, a copper foil is placed between the corundum boat and the silicon monoxide, a CVD (chemical vapor deposition) device is placed, a vacuum system is opened, and the vacuum degree is reduced to 1.0 x 10- 2And (5) closing the vacuum system when the pressure is Torr, introducing argon into the tube furnace until the air pressure in the tube furnace is recovered to the normal pressure, and opening an air outlet valve. Heating a tubular furnace, wherein the heating rate is 10 ℃/min between 0 and 1000 ℃, the heating rate is 5 ℃/min between 1000 and 1100 ℃, 200sccm of nitrogen and 40sccm of ammonia gas are introduced in the heating process, the temperature is increased to 1150 ℃ for 1h, then acetylene gas is introduced when the temperature is reduced to 1000 ℃ at the cooling rate of 5 ℃/min, the acetylene gas is introduced for 40sccm, the temperature is maintained for 1h at 1000 ℃, then the acetylene gas is closed, and the active material silicon oxide/carbon filament (SiOx/C, x is more than or equal to 0 and less than or equal to 2) is obtained by naturally cooling to room temperature, wherein the particle size is 20 nm-10 mu m.
Uniformly mixing 80 wt% of active material, 10 wt% of carbon nano tube conductive agent and 10 wt% of polyvinylidene fluoride (PVDF) adhesive, uniformly coating the mixture on copper foil by using 1-methyl-2-pyrrolidone as a solvent, and drying the copper foil for 12 hours in a drying oven at 100 ℃. Subsequently, the dried copper foil was cut into electrode pieces (lithium ion battery negative electrodes) having a diameter of 10 mm. The CR2032 button cell used in the electrochemical measurements was assembled in an argon filled glove box with less than 1ppm of water and oxygen. The assembled cell was allowed to stand for 12 hours and electrochemical measurements were taken.
As can be seen from fig. 1a, 1b, 1c, and 1d, the size of the silica particles reaches nanometer level, and at the same time, carbon filaments grow on the surface of the silica, which can inhibit the volume expansion degree of the silica during the lithium intercalation and de-intercalation processes, and provide more transmission paths for lithium ions, thereby improving the lithium ion conductivity of the composite material.
It can be seen from fig. 2a that the resistance of the negative electrode composite is small, indicating that the mobility of lithium ions in the negative electrode composite is high.
The charge-discharge curve in fig. 3a is the charge-discharge curve of the first three circles, and it can be seen that the negative electrode material has high first coulombic efficiency, and the defect of low first coulombic efficiency of oxide is effectively improved by growing carbon filaments on silicon oxide.
As can be seen from fig. 4a, the negative electrode material has high first coulombic efficiency, large specific capacity and good cycling stability.
Fig. 5 is a graph showing the rate capability test of the active material obtained in this example. The negative electrode material is charged and discharged at a current density of 0.05A/g-1.4A/g, and then at a current density of 1.4A/g-0.05A/g, and the negative electrode material has good rate capability as shown in figure 5.
Example 2
In a glove box filled with argon, silicon monoxide (ball powder ratio is 20:1, and the particle size of the silicon monoxide is more than 100 μm) is filled into a ball milling tank, high-energy ball milling is carried out for 30 hours after the ball milling tank is sealed, the ball-milled silicon monoxide is uniformly placed into a corundum boat, a copper foil is placed between the corundum boat and the silicon monoxide, a CVD (chemical vapor deposition) device is placed, a vacuum system is opened, and the vacuum degree is pumped to 1.0 x 10- 2When the temperature is kept below the Torr, argon is introduced into the tubular furnace, the tubular furnace is started to be heated, the heating rate is 10 ℃/min between 0 ℃ and 1000 ℃, the heating rate is 5 ℃/min between 1000 ℃ and 1100 ℃, 100sccm of argon and 20sccm of hydrogen are introduced in the heating process, the temperature is raised to 1100 ℃ and kept for 1h, then when the temperature is reduced to 1000 ℃ at the cooling rate of 5 ℃/min, 20sccm of methane gas is introduced, the methane gas is closed after the temperature is kept for 1h at 1000 ℃, and the temperature is naturally cooled to room temperature, so that the prepared active material silicon oxide/carbon filament (SiOx/C, x is more than or equal to 0 and less than or equal to 2) (the particle size is 10nm-10 mu m) is obtained.
Uniformly mixing 70 wt% of active material, 15 wt% of conductive carbon (super-P) and 15 wt% of sodium alginate adhesive, uniformly coating the mixture on a copper foil by using deionized water as a solvent, and drying the copper foil for 12 hours at a temperature of 50 ℃ in a drying oven. Subsequently, the dried copper foil was cut into electrode pieces (lithium ion battery negative electrodes) having a diameter of 10 mm. The CR2032 button cell used in the electrochemical measurements was assembled in an argon filled glove box with less than 1ppm of water and oxygen. The assembled cell was allowed to stand for 12 hours and electrochemical measurements were taken.
The charge-discharge curve in fig. 3b is the charge-discharge curve of the first three circles, and it can be seen that the negative electrode material has high first coulombic efficiency, and the defect of low first coulombic efficiency of oxide is effectively improved by growing carbon filaments on silicon oxide.
As can be seen from fig. 4b, the negative electrode material has high first coulombic efficiency, large specific capacity, and good cycling stability.
Example 3
In a glove box filled with argon, silicon monoxide (ball powder ratio is 20:1, and the particle size of the silicon monoxide is more than 100 μm) is filled into a ball milling tank, high-energy ball milling is carried out for 30 hours after the ball milling tank is sealed, the ball-milled silicon monoxide is uniformly placed into a corundum boat, a copper foil is placed between the corundum boat and the silicon monoxide, a CVD (chemical vapor deposition) device is placed, a vacuum system is opened, and the vacuum degree is pumped to 1.0 x 10- 2And (5) closing the vacuum system when the pressure is Torr, introducing argon into the tube furnace until the air pressure in the tube furnace is recovered to the normal pressure, and opening an air outlet valve. And (2) starting heating the tubular furnace, wherein the heating rate is 8 ℃/min between 0 and 1000 ℃, the heating rate is 5 ℃/min between 1000 and 1150 ℃, argon gas of 500sccm and ammonia gas of 100sccm are introduced during the heating process, the temperature is increased to 1150 ℃ for 2h, then when the temperature is reduced to 1000 ℃ at the cooling rate of 5 ℃/min, toluene gas of 40sccm is introduced, the temperature is maintained at 1050 ℃ for 1h, the toluene gas is closed, and the material is naturally cooled to room temperature to obtain the prepared active material silicon oxide/carbon filament (SiOx/C, x is more than or equal to 0 and less than or equal to 2) (the particle size is 20nm to 10 mu m).
Uniformly mixing 60 wt% of active material, 20 wt% of carbon nano tube conductive agent and 20 wt% of sodium alginate adhesive, uniformly coating the mixture on copper foil by using deionized water as a solvent, and drying the copper foil for 12 hours in a drying oven at 100 ℃. Subsequently, the dried copper foil was cut into electrode pieces (lithium ion battery negative electrodes) having a diameter of 10 mm. The CR2032 button cell used in the electrochemical measurements was assembled in an argon filled glove box with less than 1ppm of water and oxygen. The assembled cell was allowed to stand for 12 hours and electrochemical measurements were taken. It can be seen from fig. 2b that the resistance of the negative electrode material is small, indicating that the mobility of lithium ions in the negative electrode material is high.
Claims (10)
1. The silicon oxide-carbon filament active material is characterized by comprising carbon filaments and SiOx, wherein x is more than or equal to 0 and less than or equal to 2, the carbon filaments account for 10-30% of the total mass, and the particle size of the SiOx is 10nm-10 μm; the preparation method comprises the following steps of performing high-energy ball milling on silicon oxide for 10-30 hours in an argon environment to obtain a precursor; subjecting the precursor toPlacing the body in a chemical vapor deposition device, and vacuumizing to less than or equal to 1.0 multiplied by 10-2And (2) introducing argon to normal pressure, then starting heating, introducing 100-500 sccm of protective gas and 20-100 sccm of reducing gas in the heating process, heating to 1000-1200 ℃, keeping for 1-3 hours, then cooling to 900-1100 ℃, introducing 10-100 sccm of carbon source gas, keeping for 1-3 hours at 900-1000 ℃, closing the carbon source gas, and naturally cooling to room temperature to obtain the silicon oxide-carbon filament active material.
2. The method of preparing a silica-carbon filament active material according to claim 1, comprising the steps of: carrying out high-energy ball milling on silicon oxide for 10-30 hours in an argon environment to obtain a precursor; placing the precursor in a chemical vapor deposition device, and vacuumizing to be less than or equal to 1.0 multiplied by 10-2And (2) introducing argon to normal pressure, then starting heating, introducing 100-500 sccm of protective gas and 20-100 sccm of reducing gas in the heating process, heating to 1000-1200 ℃, keeping for 1-3 hours, then cooling to 900-1100 ℃, introducing 10-100 sccm of carbon source gas, keeping for 1-3 hours at 900-1000 ℃, closing the carbon source gas, and naturally cooling to room temperature to obtain the silicon oxide-carbon filament active material.
3. The method of preparing a silica-carbon filament active material according to claim 2, wherein the protective gas is nitrogen, argon or helium.
4. The method of producing a silica-carbon filament active material according to claim 2, wherein the reducing gas is any one of or a mixture of two or more of ammonia gas, hydrogen gas, and hydrogen sulfide.
5. The method of preparing a silica-carbon filament active material according to claim 2, wherein the carbon source gas is CH4、C2H4、C2H2、C2H6、C3H4、C3H6、C3H8、C4H6、C4H8、C4H10Or C7H8Any one or a mixture of two or more of them.
6. The method of preparing a silica-carbon filament active material according to claim 2, wherein the silica has a particle size of 10nm to 10 μm.
7. The method for preparing a silica-carbon filament active material according to claim 2, wherein the rate of temperature increase is as follows: the temperature rise rate is 8-10 ℃/min at 0-1000 ℃, and the temperature rise rate is 2-5 ℃/min at 1000-1100 ℃; the cooling rate is 2-5 ℃/min.
8. The silicon oxide-carbon filament active material according to claim 1 is applied to a lithium ion battery negative electrode material.
9. The use of claim 8, wherein the negative electrode material further comprises: conductive agents, binders; the conductive agent is at least one or a mixture of more than two of carbon black, acetylene black, natural graphite, carbon nanotubes, graphene and carbon fibers; the binder is one or a mixture of more than two of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer, sodium carboxymethylcellulose and sodium alginate; in the negative electrode material, 50-99.5 wt% of active material, 0.1-40 wt% of conductive agent and 0.1-40 wt% of binder.
10. The use of claim 8, wherein the lithium ion battery further comprises a positive electrode, a separator, an electrolyte; wherein the positive electrode is lithium iron phosphate or a lithium composite metal oxide; the diaphragm is any one of an aramid diaphragm, a non-woven fabric diaphragm, a polyethylene microporous film, a polypropylene-polyethylene double-layer or three-layer composite film and a ceramic coating diaphragm; the electrolyte comprises electrolyte and solvent, wherein the electrolyte is any one or a mixture of more than two of LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, LiN (CF3SO2), LiBOB, LiCl, LiBr and LiI; the solvent is one or more of Propylene Carbonate (PC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), 1, 2-Dimethoxyethane (DME), Ethylene Carbonate (EC), Butylene Carbonate (BC), diethyl carbonate (DEC), Ethyl Acetate (EA), and ethylene sulfite (GS).
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