WO2023096404A1 - 음극 활물질, 이를 포함하는 음극, 이를 포함하는 이차전지 및 상기 음극 활물질의 제조방법 - Google Patents
음극 활물질, 이를 포함하는 음극, 이를 포함하는 이차전지 및 상기 음극 활물질의 제조방법 Download PDFInfo
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- WO2023096404A1 WO2023096404A1 PCT/KR2022/018843 KR2022018843W WO2023096404A1 WO 2023096404 A1 WO2023096404 A1 WO 2023096404A1 KR 2022018843 W KR2022018843 W KR 2022018843W WO 2023096404 A1 WO2023096404 A1 WO 2023096404A1
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- active material
- negative electrode
- electrode active
- carbon layer
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- 150000003624 transition metals Chemical class 0.000 description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZHGDJTMNXSOQDT-UHFFFAOYSA-N NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O Chemical compound NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O ZHGDJTMNXSOQDT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000705939 Shortia uniflora Species 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- QDDVNKWVBSLTMB-UHFFFAOYSA-N [Cu]=O.[Li] Chemical compound [Cu]=O.[Li] QDDVNKWVBSLTMB-UHFFFAOYSA-N 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000011166 aliquoting Methods 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
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- 238000009831 deintercalation Methods 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
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- 150000004862 dioxolanes Chemical class 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011357 graphitized carbon fiber Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical group [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 239000002296 pyrolytic carbon Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
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- 238000000790 scattering method Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000011866 silicon-based anode active material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
Definitions
- the present invention relates to a negative electrode active material, a negative electrode including the same, a secondary battery including the same, and a method for manufacturing the negative electrode active material.
- lithium secondary batteries are in the limelight as a driving power source for portable devices because they are lightweight and have high energy density. Accordingly, research and development efforts to improve the performance of lithium secondary batteries are being actively conducted.
- a lithium secondary battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, an electrolyte, an organic solvent, and the like.
- active material layers each including a positive electrode active material and a negative electrode active material may be formed on the current collector on the positive electrode and the negative electrode.
- a lithium-containing metal oxide such as LiCoO 2 or LiMn 2 O 4 is used as a cathode active material for the cathode, and a carbon-based active material or a silicon-based active material that does not contain lithium is used as an anode active material for the anode.
- silicon-based active materials have attracted attention in that they have higher capacity than carbon-based active materials and excellent high-speed charging characteristics.
- the silicon-based active material has a high degree of volume expansion/contraction due to charging and discharging, and has a high irreversible capacity, so the initial efficiency is low.
- silicon-based oxide among silicon-based active materials, specifically silicon-based oxide represented by SiO x (0 ⁇ x ⁇ 2)
- SiO x silicon-based oxide represented by SiO x (0 ⁇ x ⁇ 2)
- SiO x silicon-based oxide represented by SiO x (0 ⁇ x ⁇ 2)
- anode active material capable of improving the phase stability of an anode slurry containing silicon-based oxide and improving the charge/discharge efficiency of an anode prepared therefrom.
- Korean Patent Registration No. 10-0794192 relates to a method for manufacturing a carbon-coated silicon-graphite composite anode material for a lithium secondary battery and a method for manufacturing a secondary battery including the same, but has limitations in solving the above-mentioned problems.
- Patent Document 1 Korea Patent Registration No. 10-0794192
- the present invention relates to a negative electrode active material, a negative electrode including the same, a secondary battery including the same, and a method for manufacturing the negative electrode active material.
- An exemplary embodiment of the present invention includes SiO x (0 ⁇ x ⁇ 2) and Li, and silicon-based particles provided with a first carbon layer on at least a portion of the surface; And a negative electrode active material comprising a second carbon layer provided on at least a part of the silicon-based particle, the ratio of the D band peak intensity to the G band peak intensity when analyzed by Raman spectroscopy (D / G band ratio) is 1.0 or more, Provided is an anode active material having (element content of C)/(element content of Li + element content of C) of 0.6 or more when analyzed by X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- An exemplary embodiment of the present invention includes forming silicon-based particles including SiO x (0 ⁇ x ⁇ 2) and Li, and having a first carbon layer on at least a portion of a surface; and forming a second carbon layer on at least a portion of the silicon-based particle.
- One embodiment of the present invention provides an anode including the anode active material.
- One embodiment of the present invention provides a secondary battery including the negative electrode.
- a negative electrode including a negative electrode active material and a secondary battery including the negative electrode according to an exemplary embodiment of the present invention have effects of improving discharge capacity, initial efficiency, resistance performance, and/or lifespan characteristics of the battery.
- the crystallinity of the structure included in the negative electrode active material can be confirmed through X-ray diffraction analysis, and the X-ray diffraction analysis is performed using an X-ray diffraction (XRD) analyzer (product name: D4-endavor, manufacturer: bruker).
- XRD X-ray diffraction
- the presence or absence of elements and the content of elements in the negative electrode active material can be confirmed through ICP analysis, and the ICP analysis can be performed using an inductively coupled plasma emission spectrometer (ICPAES, Perkin-Elmer 7300).
- ICPAES inductively coupled plasma emission spectrometer
- the average particle diameter (D 50 ) may be defined as a particle diameter corresponding to 50% of the cumulative volume in the particle size distribution curve (graph curve of the particle size distribution).
- the average particle diameter (D 50 ) may be measured using, for example, a laser diffraction method.
- the laser diffraction method is generally capable of measuring particle diameters of several millimeters in the submicron region, and can obtain results with high reproducibility and high resolution.
- An exemplary embodiment of the present invention includes SiO x (0 ⁇ x ⁇ 2) and Li, and silicon-based particles provided with a first carbon layer on at least a portion of the surface; And a negative electrode active material comprising a second carbon layer provided on at least a part of the silicon-based particle, the ratio of the D band peak intensity to the G band peak intensity when analyzed by Raman spectroscopy (D / G band ratio) is 1.0 or more, Provided is an anode active material having (element content of C)/(element content of Li + element content of C) of 0.6 or more when analyzed by X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- An anode active material includes silicon-based particles.
- the silicon-based particle may include SiO x (0 ⁇ x ⁇ 2) and Li, and a first carbon layer may be provided on at least a part of a surface.
- the SiO x (0 ⁇ x ⁇ 2) corresponds to a matrix in the silicon-based particle.
- the SiO x (0 ⁇ x ⁇ 2) may include Si and SiO 2 , and the Si may form a phase. That is, the x corresponds to the number ratio of O to Si included in the SiO x (0 ⁇ x ⁇ 2).
- the silicon-based particles include the SiO x (0 ⁇ x ⁇ 2), the discharge capacity of the secondary battery may be improved.
- the silicon-based particles may include Li.
- the Li may exist in the form of at least one of a lithium atom, lithium silicate, lithium silicide, and lithium oxide in the silicon-based particle, and preferably may exist in the form of lithium silicate.
- the Li may correspond to a matrix within the silicon-based particle.
- the silicon-based particles include a Li compound, there is an effect of improving initial efficiency.
- the Li may be distributed on the surface and/or inside the silicon-based particle in a doped form.
- the Li compound may be distributed on the surface and/or inside of the silicon-based particle to control volume expansion/contraction of the silicon-based particle to an appropriate level and prevent damage to the active material.
- the Li may be contained in order to increase the efficiency of the active material by lowering the ratio of the non-reversible phase (eg, SiO 2 ) of the silicon-based oxide particles.
- Li may exist in the form of lithium silicate.
- the lithium silicate is represented by Li a Si b O c (2 ⁇ a ⁇ 4, 0 ⁇ b ⁇ 2, 2 ⁇ c ⁇ 5), and in the silicon-based particle, Li 2 SiO 3 , Li 4 SiO 4 and Li 2 It may exist in the form of at least one type of lithium silicate selected from the group including Si 2 O 5 .
- Li included in the negative active material is 0.01 part by weight to 40 parts by weight, 0.01 part by weight to 20 parts by weight, 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the total amount of the negative electrode active material, or It may be included in 0.02 parts by weight to 9 parts by weight. Specifically, it may be included in 0.1 parts by weight to 9 parts by weight, 1 part by weight to 9 parts by weight, or 4 parts by weight to 9 parts by weight. More specifically, it may be included in 5 parts by weight to 8 parts by weight.
- the Li content increases, the initial efficiency increases, but there is a problem in that the discharge capacity decreases. Therefore, when the above range is satisfied, appropriate discharge capacity and initial efficiency can be implemented.
- the content of the Li element can be confirmed through ICP analysis. Specifically, after aliquoting a sample (about 0.01 g), it is transferred to a platinum crucible and completely decomposed on a hot plate by adding nitric acid, hydrofluoric acid, and sulfuric acid. Then, using an induced plasma emission spectrometer (ICPAES, Perkin-Elmer 7300), a standard calibration curve is prepared by measuring the intensity of the standard solution prepared using the standard solution (5 mg/kg) at the intrinsic wavelength of the element to be analyzed. . Thereafter, the pretreated sample solution and the blank sample are introduced into the instrument, each intensity is measured to calculate the actual intensity, and after calculating the concentration of each component against the calibration curve prepared above, the total sum is converted to the theoretical value. to analyze the elemental content of the sample.
- ICPAES induced plasma emission spectrometer
- Silicon-based particles according to an exemplary embodiment of the present invention is provided with a first carbon layer on at least a part of the surface.
- the first carbon layer may be partially coated on at least a part of the surface, that is, the surface of the particle, or may be coated on the entire surface of the particle.
- Conductivity is imparted to the anode active material by the carbon layer, and initial efficiency, lifespan characteristics, and battery capacity characteristics of a secondary battery may be improved.
- the first carbon layer may include crystalline carbon or amorphous carbon.
- the crystalline carbon may further improve conductivity of the anode active material.
- the crystalline carbon may include at least one selected from the group consisting of florene, carbon nanotubes, and graphene.
- the amorphous carbon can properly maintain the strength of the first carbon layer and suppress expansion of the silicon-based particles.
- the amorphous carbon may be a carbon-based material formed by using at least one carbide selected from the group including tar, pitch, and other organic materials, or a hydrocarbon as a source of chemical vapor deposition.
- the other organic carbide may be an organic carbide selected from carbides of sucrose, glucose, galactose, fructose, lactose, mannose, ribose, aldohexose or ketohexose, and combinations thereof.
- the hydrocarbon may be a substituted or unsubstituted aliphatic or alicyclic hydrocarbon or a substituted or unsubstituted aromatic hydrocarbon.
- the aliphatic or alicyclic hydrocarbon of the substituted or unsubstituted aliphatic or alicyclic hydrocarbon may be metherine, ethane, ethylene, acetylene, propane, butane, butene, pentane, isobutane or hexane.
- Aromatic hydrocarbons of the substituted or unsubstituted aromatic hydrocarbons include benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumaron, pyridine, Anthracene, phenanthrene, etc. are mentioned.
- the first carbon layer is 1 to 5 parts by weight, 2 to 5 parts by weight, 2 to 4.5 parts by weight, or 2 parts by weight based on 100 parts by weight of the total amount of the negative electrode active material. part to 4 parts by weight. More specifically, it may be included in 3 parts by weight to 4 parts by weight. When the above range is satisfied, reduction in capacity and efficiency of the negative electrode active material may be prevented.
- the thickness of the first carbon layer may be 1 nm to 500 nm, specifically 5 nm to 300 nm.
- the conductivity of the negative active material is improved, the volume change of the negative active material is easily suppressed, and the side reaction between the electrolyte and the negative active material is suppressed, thereby improving the initial efficiency and/or lifespan of the battery.
- the first carbon layer may be formed by chemical vapor deposition (CVD) using at least one hydrocarbon gas selected from the group consisting of methane, ethane, propane, and acetylene.
- CVD chemical vapor deposition
- the negative electrode active material includes a second carbon layer provided on at least a part of the silicon-based particle.
- the second carbon layer may partially cover the surface of the silicon-based particle or may cover the entire surface of the particle.
- the negative electrode active material includes a second carbon layer provided on at least a part of the first carbon layer.
- the second carbon layer may partially cover the surface of the first carbon layer or cover the entire particle surface.
- the second carbon layer is further coated on the silicon-based particles containing the Li and the first carbon layer is coated to control the side reaction of unreacted lithium by-products and effectively prevent the slurry from becoming basic. there is.
- the second carbon layer can efficiently passivate silicon-based particles, it prevents elution of lithium by-products included in silicon-based particles, thereby improving water-based processability.
- the second carbon layer has hydrophobicity, the reaction between the negative electrode active material and water in the aqueous slurry can be minimized.
- a lithium compound may exist between the silicon-based particle and the second carbon layer. At this time, the lithium compound means a lithium by-product formed due to unreacted lithium.
- the lithium compound present between the silicon-based particles and the second carbon layer may be included in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the negative electrode active material.
- a lithium compound may exist between the first carbon layer and the second carbon layer. At this time, the lithium compound means a lithium by-product formed due to unreacted lithium.
- a lithium compound that is, a lithium by-product formed due to unreacted lithium, remains near the surface of the silicon-based particle.
- the lithium compound may include at least one selected from the group consisting of Li 2 O, LiOH, and Li 2 CO 3 .
- a lithium compound may be provided on at least a part of the surface of the silicon-based particle provided with the first carbon layer.
- the lithium compound may be located on at least a part of the surface of the silicon-based particle, that is, partially on the surface of the particle, or may be located on the entire surface of the particle.
- the second carbon layer may be provided on at least a part of the silicon-based particle equipped with the lithium compound.
- the particle surface may be partially covered or the entire particle surface may be covered.
- the second carbon layer may be present on at least a portion of the lithium compound provided on the surface of the particle, or may be present on at least a portion of the surface of the silicon-based particle not provided with a lithium compound.
- the second carbon layer may be provided on at least a portion of the lithium compound. That is, the second carbon layer may partially cover at least a portion of the lithium compound, that is, the surface of the lithium compound, or may cover the entire surface of the lithium compound.
- the second carbon layer includes amorphous carbon.
- the second carbon layer may further include crystalline carbon.
- the crystalline carbon may further improve conductivity of the anode active material.
- the crystalline carbon may include at least one selected from the group consisting of florene, carbon nanotubes, and graphene.
- the amorphous carbon may appropriately maintain the strength of the second carbon layer and suppress expansion of the silicon-based particles.
- the amorphous carbon may be a carbon-based material formed by using at least one carbide selected from the group including tar, pitch, and other organic materials, or a hydrocarbon as a source of chemical vapor deposition.
- the other organic carbide may be an organic carbide selected from carbides of sucrose, glucose, galactose, fructose, lactose, mannose, ribose, aldohexose or ketohexose, and combinations thereof.
- the hydrocarbon may be a substituted or unsubstituted aliphatic or alicyclic hydrocarbon or a substituted or unsubstituted aromatic hydrocarbon.
- the aliphatic or alicyclic hydrocarbon of the substituted or unsubstituted aliphatic or alicyclic hydrocarbon may be metherine, etherin, ethylene, acetylene, propane, butane, butene, pentane, isobutane or hexane.
- Aromatic hydrocarbons of the substituted or unsubstituted aromatic hydrocarbons include benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumaron, pyridine, Anthracene, phenanthrene, etc. are mentioned.
- the second carbon layer is 1 part by weight to 5 parts by weight, specifically 1.5 parts by weight to 3 parts by weight, more specifically 2 to 3 parts by weight based on 100 parts by weight of the total amount of the negative electrode active material. It may be included in parts by weight. When the above range is satisfied, reduction in capacity and efficiency of the negative active material can be prevented, and the negative active material can be effectively passivated.
- the thickness of the second carbon layer may be 1 nm to 500 nm, specifically 5 nm to 300 nm.
- the conductivity of the negative active material is improved, the volume change of the negative active material is easily suppressed, and the side reaction between the electrolyte and the negative active material is suppressed, thereby improving the initial efficiency and/or lifespan of the battery.
- the second carbon layer may be formed under a temperature condition of less than 800 °C by chemical vapor deposition (CVD) using at least one hydrocarbon gas selected from the group consisting of methane, ethane, propane, and acetylene.
- CVD chemical vapor deposition
- the Raman spectroscopy is a method for analyzing the structure of the carbon layer, and the peak present in the region of the wave number 1,580 cm -1 in the vicinity of the Raman spectrum of the carbon layer is called the G band, which is the sp2 bond of the carbon layer. As the peak shown, it represents a carbon crystal having no structural defects.
- the peak existing in the region of the wave number 1,360 cm -1 in the Raman spectrum is called the D band, which represents the sp3 bond of the carbon layer, and increases when the atomic bond made of sp2 bonds is broken to form sp3 bonds. .
- Such a D band increases when disorder or defect present in the carbon layer is generated.
- the G band of the Raman spectrum for the carbon layer may be a peak present in the region of wave number 1,550 cm -1 to 1,620 cm -1
- the D band may be a peak present in the region of wave number 1,330 cm -1 to 1,370 cm -1
- the wave number ranges for the G band and D band correspond to ranges that can be shifted according to the laser light source used in the Raman analysis method.
- the crystallinity of the carbon layer can be confirmed by calculating the D / G band ratio according to Raman analysis. Specifically, it can be measured using a Renishaw 2000 Raman microscope system and 532 nm laser excitation, and using a 100x optical lens with a low laser power density and an exposure time of 30 seconds to avoid laser thermal effects. In order to reduce positional deviation, it can be calculated by measuring a total of 25 points in a 5 ⁇ m x 5 ⁇ m area, performing fitting using the Lorentzian function, and calculating the average value of the D band and G band.
- a ratio of D band peak intensity to G band peak intensity may be 1.0 or more.
- the D / G band ratio may be 1.01 or more.
- the upper limit of the D / G band ratio may be 3 or less, 2.5 or less, 2 or less, 1.5 or less, 1.3 or less, or 1.2 or less.
- the degree of amorphization of all carbon included in the first carbon layer and the second carbon layer included in the negative electrode active material increases. That is, since the carbon layer included in the negative electrode active material contains a large number of amorphous carbon and can effectively cover residual lithium by-products, there is an effect of minimizing side reactions with moisture.
- the D / G band ratio is less than 1.0, the degree of amorphization of all carbon included in the first carbon layer and the second carbon layer is reduced, and the crystallinity of the carbon layer is increased.
- the highly crystalline carbon layer is formed at a relatively high temperature, and rather has a disadvantage in that the lifespan performance is deteriorated due to an increase in the grain size of silicon (Si).
- the content of the entire carbon layer (first carbon layer and second carbon layer) included in the negative electrode active material is 2 parts by weight to 10 parts by weight, 2 parts by weight based on 100 parts by weight of the total amount of the negative electrode active material It may be included in parts by weight to 9 parts by weight, 2 parts by weight to 8 parts by weight, or 3 parts by weight to 8 parts by weight. More specifically, it may be included in 4 parts by weight to 7 parts by weight. When the above range is satisfied, reduction in capacity and efficiency of the negative electrode active material may be prevented.
- the negative electrode active material On the surface of the negative electrode active material, little or no lithium compound may exist.
- the two-layer carbon layer as described above, since the content of lithium by-products located on the surface of the negative electrode active material is small or absent, side reactions caused by lithium by-products can be controlled during slurry formation, and the slurry can be effectively prevented from becoming basic.
- the rheological properties of the slurry change as the slurry becomes basic when forming the slurry due to lithium by-products on the surface of the negative electrode active material generated in the process of doping Li after forming the first carbon layer.
- lithium by-product reacts with moisture to generate gas.
- the negative electrode active material when the negative electrode active material is analyzed by X-ray photoelectron spectroscopy (XPS), (C element content)/(Li element content + C element content) is 0.6 or more.
- XPS X-ray photoelectron spectroscopy
- (element content of C)/(element content of Li + element content of C) may be 0.6 or more, 0.63 or more, or 0.65 or more.
- the upper limit of (element content of C)/(element content of Li + element content of C) may be 1 or less, 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, or 0.73 or less.
- the relationship between the element content (atomic%) of C and Li satisfies the above range, the content of lithium by-products located on the surface of the negative electrode active material is significantly less or less, so when forming the slurry, side reactions caused by the lithium compound are controlled, and the slurry is basic can be effectively prevented from occurring.
- (element content of C)/(element content of Li + element content of C) is less than 0.6, since there are many lithium by-products present on the surface of the negative electrode active material, the slurry becomes basic when forming the slurry, and the rheological properties of the slurry are reduced. There is a problem in that the lithium by-product reacts with moisture to generate gas.
- the relationship between the element contents of C and Li can be confirmed by analyzing the negative electrode active material by X-ray photoelectron spectroscopy (XPS). Specifically, it can be checked through the XPS (Nexsa ESCA System, Thermo Fisher Scientific (NEXSA 1)) depth profile, and the depth profile proceeds up to 3000 seconds using monatomic Ar (low current), and then the depth profile at 10 seconds. It can be calculated using the elemental content (atomic%).
- XPS X-ray photoelectron spectroscopy
- the total content of Li included in the negative active material is 0.1 part by weight to 10 parts by weight, 1 part by weight to 10 parts by weight, 5 parts by weight to 10 parts by weight based on 100 parts by weight of the total amount of the negative electrode active material. parts by weight or 6 to 9 parts by weight. Specifically, it may be 6 parts by weight to 8 parts by weight, and more specifically, it may be 7 parts by weight to 8 parts by weight.
- the Li content increases, the initial efficiency increases, but there is a problem in that the discharge capacity decreases. Therefore, when the above range is satisfied, appropriate discharge capacity and initial efficiency can be implemented.
- the negative electrode active material may have a BET specific surface area of 1 m 2 /g to 10 m 2 /g, and specifically, 1 m 2 /g to 5 m 2 /g.
- BET specific surface area 1 m 2 /g to 10 m 2 /g, and specifically, 1 m 2 /g to 5 m 2 /g.
- the average particle diameter (D 50 ) of the negative electrode active material may be 0.1 ⁇ m to 30 ⁇ m, specifically 1 ⁇ m to 20 ⁇ m, and more specifically 1 ⁇ m to 15 ⁇ m.
- An exemplary embodiment of the present invention includes forming silicon-based particles including SiO x (0 ⁇ x ⁇ 2) and Li, and having a first carbon layer on at least a portion of a surface; and forming a second carbon layer on at least a portion of the silicon-based particle.
- the silicon-based particles provided with the first carbon layer are vaporized by heating a mixed powder of Si powder and SiO 2 powder, and then depositing the vaporized mixed gas to form preliminary particles; forming a first carbon layer on the preliminary particles; And it may be formed through a step of heat-treating after mixing the preliminary particles on which the first carbon layer is formed with Li powder.
- the mixed powder of the Si powder and SiO 2 powder may be heat treated at 1400 °C to 1800 °C or 1400 °C to 1600 °C under vacuum.
- the first carbon layer may be formed by using chemical vapor deposition (CVD) using hydrocarbon gas or by carbonizing a material serving as a carbon source.
- CVD chemical vapor deposition
- hydrocarbon gas may be formed by chemical vapor deposition (CVD) at 600 to 1200 °C.
- the hydrocarbon gas may be at least one type of hydrocarbon gas selected from the group consisting of methane, ethane, propane and acetylene, and heat treatment may be performed at 900 °C to 1000 °C.
- Heat treatment after mixing the preliminary particles having the first carbon layer with the Li powder may be performed at 700° C. to 900° C. for 4 hours to 6 hours, and specifically, at 800° C. for 5 hours.
- the silicon-based particles may include the aforementioned Li silicate.
- the particle size of the particles may be adjusted through a method such as a ball mill, jet mill, or air flow classification, but is not limited thereto.
- a lithium compound is provided on at least a part of the surface of the silicon-based particle having the first carbon layer.
- a lithium compound that is, a lithium by-product formed due to unreacted lithium, remains near the surface of the silicon-based particle.
- Forming a second carbon layer on at least a portion of the silicon-based particle may be performed to suppress a side reaction caused by the unreacted lithium compound.
- the second carbon layer provided on at least a part of the silicon-based particle may be formed by using a chemical vapor deposition (CVD) method using a hydrocarbon gas or by carbonizing a material serving as a carbon source.
- CVD chemical vapor deposition
- hydrocarbon gas may be formed by chemical vapor deposition (CVD) at less than 800 °C.
- the hydrocarbon gas may be at least one hydrocarbon gas selected from the group consisting of methane, ethane, propane, and acetylene, and may be heat-treated at less than 600 to 800 °C.
- the heat treatment may be performed at 700° C. for 4 hours in an acetylene or propane gas atmosphere.
- the degree of amorphization of the carbon layer may be increased.
- the degree of amorphization of the carbon layer is low, that is, when the degree of crystallinity is high, since the carbon coating is performed at a relatively high temperature, the grain size of Si is increased, thereby deteriorating lifespan performance.
- a ratio of D band peak intensity to G band peak intensity may be 1.0 or more.
- An anode according to an exemplary embodiment of the present invention may include the anode active material described above.
- the negative electrode may include a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
- the negative active material layer may include the negative active material.
- the negative electrode active material layer may further include a binder and/or a conductive material.
- the negative electrode active material layer may be formed by applying a negative electrode slurry containing a negative electrode active material, a binder, and/or a conductive material to at least one surface of a current collector, followed by drying and rolling.
- the anode slurry includes the anode active material, a binder, and/or a conductive material.
- the anode slurry may further include an additional anode active material.
- a compound capable of reversible intercalation and deintercalation of lithium may be used.
- Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; metallic compounds capable of being alloyed with lithium, such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys, or Al alloys; metal oxides capable of doping and undoping lithium, such as SiO ⁇ (0 ⁇ ⁇ ⁇ 2), SnO 2 , vanadium oxide, lithium titanium oxide, and lithium vanadium oxide; or a composite including the metallic compound and the carbonaceous material, such as a Si—C composite or a Sn—C composite, and any one or a mixture of two or more of these may be used.
- a metal lithium thin film may be used as the anode active material.
- both low crystalline carbon and high crystalline carbon may be used.
- Soft carbon and hard carbon are typical examples of low crystalline carbon
- high crystalline carbon includes amorphous, platy, scaly, spherical or fibrous natural graphite, artificial graphite, or kish graphite.
- High-temperature calcined carbon such as derived cokes is representative.
- the additional anode active material may be a carbon-based anode active material.
- the weight ratio of the negative electrode active material and the additional negative electrode active material included in the negative electrode slurry may be 10:90 to 90:10, specifically 10:90 to 50:50.
- the anode current collector may be any material having conductivity without causing chemical change in the battery, and is not particularly limited.
- the current collector copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel surface-treated with carbon, nickel, titanium, or silver may be used.
- a transition metal that adsorbs carbon well, such as copper and nickel can be used as the current collector.
- the current collector may have a thickness of 6 ⁇ m to 20 ⁇ m, but the thickness of the current collector is not limited thereto.
- the binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride, polyacrylonitrile, polymethylmethacrylate, poly Vinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), It may include at least one selected from the group consisting of sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, and materials in which hydrogen is substituted with Li, Na, or Ca, In addition, various copolymers thereof may be included.
- PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
- SBR styrene
- the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples include graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, ketjen black, channel black, farnes black, lamp black, and thermal black; conductive fibers such as carbon fibers and metal fibers; conductive tubes such as carbon nanotubes; metal powders such as fluorocarbon, aluminum, and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives may be used.
- graphite such as natural graphite or artificial graphite
- carbon black such as acetylene black, ketjen black, channel black, farnes black, lamp black, and thermal black
- conductive fibers such as carbon fibers and metal fibers
- conductive tubes such as carbon nanotubes
- metal powders such as fluorocarbon, aluminum, and nickel powder
- conductive whiskers such as zinc oxide and potassium
- the negative electrode slurry may include a thickener.
- the thickener may be carboxymethyl cellulose (CMC), but is not limited thereto, and thickeners used in the art may be appropriately employed.
- the negative electrode slurry may include a solvent for forming the negative electrode slurry.
- the solvent for forming the anode slurry may include at least one selected from the group consisting of distilled water, ethanol, methanol, and isopropyl alcohol, specifically, distilled water, in terms of facilitating dispersion of components.
- a secondary battery according to an exemplary embodiment of the present invention may include the negative electrode according to the aforementioned exemplary embodiment.
- the secondary battery may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, and the negative electrode is the same as the negative electrode described above. Since the cathode has been described above, a detailed description thereof will be omitted.
- the positive electrode may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector and including the positive electrode active material.
- the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- stainless steel, aluminum, nickel, titanium, fired carbon, or carbon on the surface of aluminum or stainless steel. , those surface-treated with nickel, titanium, silver, etc. may be used.
- the cathode current collector may have a thickness of typically 3 to 500 ⁇ m, and adhesion of the cathode active material may be increased by forming fine irregularities on the surface of the current collector.
- it may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven fabrics.
- the cathode active material may be a commonly used cathode active material.
- the cathode active material may include layered compounds such as lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (LiNiO 2 ), or compounds substituted with one or more transition metals; lithium iron oxides such as LiFe 3 O 4 ; lithium manganese oxides such as Li 1+c1 Mn 2-c1 O 4 (0 ⁇ c1 ⁇ 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 ; lithium copper oxide (Li 2 CuO 2 ); vanadium oxides such as LiV 3 O 8 , V 2 O 5 , and Cu 2 V 2 O 7 ; Formula LiNi 1-c2 M c2 O 2 (where M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and satisfies 0.01 ⁇ c2 ⁇ 0.3) Ni site-type lithium nickel oxide; Formula LiMn 2-c3
- the positive electrode active material layer may include a positive electrode conductive material and a positive electrode binder together with the positive electrode active material described above.
- the positive electrode conductive material is used to impart conductivity to the electrode, and in the configured battery, any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
- any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
- Specific examples include graphite such as natural graphite or artificial graphite; carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, and carbon fiber; metal powders or metal fibers such as copper, nickel, aluminum, and silver; conductive whiskeys such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and the like, and one of them alone or a mixture of two or more may be used.
- the positive electrode binder serves to improve adhesion between particles of the positive electrode active material and adhesion between the positive electrode active material and the positive electrode current collector.
- specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose (CMC) ), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and the like, and one type alone or a mixture of two or more types thereof may be used.
- PVDF polyvinylidene fluoride
- PVDF-co-HFP vinylidene flu
- the separator separates the negative electrode and the positive electrode and provides a passage for lithium ion movement. If it is normally used as a separator in a secondary battery, it can be used without particular limitation. It is desirable Specifically, a porous polymer film, for example, a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these A laminated structure of two or more layers of may be used.
- a porous polymer film for example, a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these A laminated structure of two or more layers of may be used.
- porous non-woven fabrics for example, non-woven fabrics made of high-melting glass fibers, polyethylene terephthalate fibers, and the like may be used.
- a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be selectively used in a single-layer or multi-layer structure.
- electrolyte examples include, but are not limited to, organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in manufacturing a lithium secondary battery.
- the electrolyte may include a non-aqueous organic solvent and a metal salt.
- non-aqueous organic solvent for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyllolactone, 1,2-dimethine Toxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxorane, formamide, dimethylformamide, dioxorane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid Triester, trimethoxy methane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, propionic acid
- An aprotic organic solvent such as ethyl may be used.
- ethylene carbonate and propylene carbonate which are cyclic carbonates
- an electrolyte having high electrical conductivity can be made and can be used more preferably.
- the metal salt may be a lithium salt, and the lithium salt is a material that is easily soluble in the non-aqueous electrolyte.
- the anion of the lithium salt is F - , Cl - , I - , NO 3 - , N (CN ) 2 - , BF 4 - , ClO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3
- the electrolyte may include, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides for the purpose of improving battery life characteristics, suppressing battery capacity decrease, and improving battery discharge capacity.
- haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides
- Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imida
- One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be further included.
- a battery module including the secondary battery as a unit cell and a battery pack including the same are provided. Since the battery module and the battery pack include the secondary battery having high capacity, high rate and cycle characteristics, a medium or large-sized device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system can be used as a power source for
- the formed negative electrode active material was prepared.
- An anode active material was prepared in the same manner as in Example 1, except that the first carbon layer was reacted for 3 hours.
- An anode active material was prepared in the same manner as in Example 1, except that the first carbon layer was reacted for 4 hours and the second carbon layer was reacted for 4 hours.
- An anode active material was prepared in the same manner as in Example 1, except that the second carbon layer was reacted for 4 hours.
- An anode active material was prepared in the same manner as in Example 1, except that the second carbon layer was not formed.
- An anode active material was prepared in the same manner as in Example 1, except that the temperature for forming the second carbon layer was 900 °C and the reaction was performed for 3 hours.
- An anode active material was prepared in the same manner as in Example 1, except that the silicon-based particles were acid-washed using 0.1 M HCl without forming a second carbon layer.
- composition of the negative electrode active materials of Examples 1 to 4 and Comparative Examples 1 to 3 was measured as follows and shown in Table 1 below.
- the contents of the first carbon layer and the second carbon layer were analyzed using a CS-analyzer (CS-800, Eltra), and the content of the second carbon layer was determined by "content of all carbon layers-content of the first carbon layer”. It was confirmed by calculation.
- the average particle diameter (D 50 ) of the negative electrode active material particles was measured by Microtrac's laser scattering method.
- the BET specific surface area of the anode active material was determined by degassing at 200° C. for 8 hours using a BET measuring instrument (BEL-SORP-MAX, Nippon Bell), and N 2 adsorption/desorption at 77K. desorption) was measured.
- the content of Li atoms included in the negative electrode active material was confirmed through ICP analysis using an inductively coupled plasma emission spectrometer (ICP-OES, AVIO 500, manufactured by Perkin-Elmer 7300).
- the crystallinity of the entire carbon layer included in the negative electrode active material was confirmed by calculating the D/G ratio according to Raman analysis.
- the C/Li ratio of the negative electrode active material was confirmed through XPS (Nexsa ESCA System, Thermo Fisher Scientific (NEXSA 1)) depth profile. Specifically, the depth profile was conducted up to 3,000 seconds using monatomic Ar (low current), and the depth profile (element content of C) / (element content of Li + C using the element content (atomic%) at 10 seconds Elemental content of) was calculated.
- Measurement and data processing conditions are as follows.
- CAE Constant Analyzer Energy
- a negative electrode and a battery were manufactured using the negative electrode active materials of Examples and Comparative Examples, respectively.
- anode material a mixture of the anode active material prepared in Example 1 and graphite (average particle diameter (D50): 20 ⁇ m) at a weight ratio of 15:85 was used as a carbon-based active material.
- the negative electrode material styrene-butadiene rubber (SBR) as a binder, Super C65 as a conductive material, and carboxymethylcellulose (CMC) as a thickener were mixed in a weight ratio of 96:2:1:1, and this was used as a solvent for forming a negative electrode slurry It was added to distilled water to prepare a negative electrode slurry.
- SBR styrene-butadiene rubber
- CMC carboxymethylcellulose
- a negative electrode current collector As a negative electrode current collector, one surface of a copper current collector (thickness: 15 ⁇ m) was coated with the negative electrode slurry at a loading amount of 3.6 mAh/cm 2 , rolled, and dried in a vacuum oven at 130 ° C. for 10 hours. An anode was prepared by forming an anode active material layer (thickness: 50 ⁇ m). (Thickness of cathode: 65 ⁇ m).
- the negative electrode active materials of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, except that the negative electrode active materials of Examples 2 to 4 and Comparative Examples 1 to 3 were respectively used instead of the negative electrode active material of Example 1. Negative electrodes were prepared respectively.
- a lithium metal foil was prepared as an anode.
- a porous polyethylene separator was interposed between the negative electrode and the positive electrode of Examples 1 to 4 and Comparative Examples 1 to 3 prepared above, and an electrolyte solution was injected to prepare coin-type half cells, respectively.
- the electrolyte solution is a solution in which ethyl methyl carbonate (EMC) and ethylene carbonate (EC) are mixed at a volume ratio of 7:3, vinylene carbonate (VC) is dissolved at 0.5% by weight, and LiPF 6 is dissolved at a concentration of 1M. used
- Discharge capacity, initial efficiency, and cycle capacity retention rate of the secondary batteries prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated using an electrochemical charger and discharger.
- the cycle capacity retention rate was performed at a temperature of 25 ° C, the first cycle and the second cycle were charged and discharged at 0.1 C, and the third cycle was charged and discharged at 0.5 C (charging conditions: CC / CV, 5 mV / 0.005 C cut-off, discharge condition: CC, 1.5V cut off).
- the capacity retention rate was calculated as follows.
- Capacity retention rate (%) ⁇ (discharge capacity at the Nth cycle)/(discharge capacity at the first cycle) ⁇ ⁇ 100
- N is an integer greater than or equal to 1.
- the 50th cycle capacity retention rate (%) is shown in Table 2 below.
- the negative electrode active material according to the present invention is characterized in that it includes a first carbon layer and a second carbon layer, and the second carbon layer effectively covers the lithium by-product so that the lithium by-product does not exist on the surface of the negative electrode active material.
- a phenomenon in which physical properties of the slurry are deteriorated by reacting with water in the slurry can be prevented.
- by increasing the degree of amorphization of the carbon layer residual lithium byproducts can be effectively covered, and the crystal grain size of Si can be effectively controlled to improve the stability of the electrode state and/or charge/discharge capacity.
- Comparative Example 1 did not include the second carbon layer and had a low (C element content)/(Li element content + C element content). From this, it can be seen that the content of lithium by-products present on the surface of the negative electrode active material is high due to the absence of the second carbon layer. I was able to confirm.
- Comparative Example 2 has a high crystallinity of the carbon layer because the coating of the second carbon layer is performed at a relatively high temperature, which can be confirmed from the fact that the D / G band ratio is 0.91. Therefore, it was confirmed that the lifespan performance was greatly deteriorated due to the increase in the grain size of Si in the negative electrode active material due to the carbon coating at high temperature.
- Comparative Example 3 the lithium by-product on the silicon-based particles was acid-washed after the first carbon layer was coated. During acid washing, Li was eluted from the Li compound (lithium silicate) contained in the silicon-based particles in the negative electrode active material, and the surface structure of the negative electrode active material collapsed. Therefore, it was confirmed that the efficiency and capacity retention rate were lowered.
- Li compound lithium silicate
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Abstract
Description
음극 활물질 총 100 중량부 기준 | 음극 활물질의 D50(㎛) | 음극 활물질의 비표면적 (m2/g) | D/G band ratio | C/(Li +C)*100 (%) |
||||
제1 탄소층의 중량부 | 제2 탄소층의 중량부 | 전체 탄소층의 중량부 | 음극 활물질에 포함된 Li의 총 중량부 | |||||
실시예 1 | 4 | 2 | 6 | 7.8 | 6.5 | 1.7 | 1.09 | 65.4 |
실시예 2 | 2 | 2 | 4 | 7.7 | 6.5 | 1.7 | 1.13 | 66.8 |
실시예 3 | 3 | 3 | 6 | 7.7 | 6.5 | 1.8 | 1.05 | 72.5 |
실시예 4 | 4 | 3 | 7 | 7.5 | 6.5 | 1.9 | 1.01 | 70.9 |
비교예 1 | 4 | - | 4 | 7.9 | 6.5 | 1.6 | 0.81 | 50.4 |
비교예 2 | 4 | 3 | 7 | 7.7 | 6.5 | 1.5 | 0.91 | 72.3 |
비교예 3 | 4 | - | 4 | 5.5 | 6.5 | 1.1 | 0.81 | 55.2 |
전지 | 방전 용량(mAh/g) | 초기 효율(%) | 용량 유지율(%) |
실시예 1 | 509 | 91.8 | 93.6 |
실시예 2 | 509 | 92 | 93.5 |
실시예 3 | 509 | 91.8 | 93.8 |
실시예 4 | 508 | 91.8 | 94.5 |
비교예 1 | 509 | 90.5 | 80.1 |
비교예 2 | 508 | 91.5 | 72.5 |
비교예 3 | 509 | 88.6 | 72.6 |
Claims (12)
- SiOx(0<x<2) 및 Li을 포함하고, 표면의 적어도 일부에 제1 탄소층이 구비된 실리콘계 입자; 및상기 실리콘계 입자 상의 적어도 일부에 구비된 제2 탄소층을 포함하는 음극 활물질로서,라만 분광법에 의한 분석 시 G 밴드 피크 세기 대비 D 밴드 피크 세기의 비(D/G band ratio)는 1.0 이상이고,X선 광전자 분광법(XPS)에 의한 분석 시 (C의 원소 함량)/(Li의 원소 함량 + C의 원소 함량)이 0.6 이상인 것인 음극 활물질.
- 청구항 1에 있어서, 상기 Li은 리튬 실리케이트 형태로 존재하는 것인 음극 활물질.
- 청구항 1에 있어서, 상기 실리콘계 입자 및 제2 탄소층 사이에 리튬 화합물이 존재하는 것인 음극 활물질.
- 청구항 3에 있어서, 상기 리튬 화합물은 Li2O, LiOH 및 Li2CO3를 포함하는 군에서 선택된 1 이상을 포함하는 것인 음극 활물질.
- 청구항 1에 있어서, 상기 음극 활물질에 포함된 Li의 총 함량은 상기 음극 활물질 총 100 중량부를 기준으로 5 중량부 내지 10 중량부인 것인 음극 활물질.
- 청구항 1에 있어서, 상기 제1 탄소층은 상기 음극 활물질 총 100 중량부를 기준으로 1 중량부 내지 5 중량부로 포함되는 것인 음극 활물질.
- 청구항 3에 있어서, 상기 리튬 화합물은 상기 음극 활물질 총 100 중량부를 기준으로 0.1 중량부 내지 3 중량부로 포함되는 것인 음극 활물질.
- 청구항 1에 있어서, 상기 제2 탄소층은 상기 음극 활물질 총 100 중량부를 기준으로 1 중량부 내지 5 중량부로 포함되는 것인 음극 활물질.
- 청구항 1에 있어서, 상기 음극 활물질에 포함된 전체 탄소층(제1 탄소층 및 제2 탄소층)의 함량은 상기 음극 활물질 총 100 중량부를 기준으로 2 중량부 내지 10 중량부인 것인 음극 활물질.
- SiOx(0<x<2) 및 Li을 포함하고, 표면의 적어도 일부에 제1 탄소층이 구비된 실리콘계 입자를 형성하는 단계; 및상기 실리콘계 입자 상의 적어도 일부에 제2 탄소층을 형성하는 단계를 포함하는 청구항 1 내지 9 중 어느 한 항에 따른 음극 활물질의 제조방법.
- 청구항 1 내지 9 중 어느 한 항에 따른 음극 활물질을 포함하는 음극.
- 청구항 11에 따른 음극을 포함하는 이차전지.
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JP2016091915A (ja) * | 2014-11-10 | 2016-05-23 | 信越化学工業株式会社 | 非水電解質二次電池用負極材及びその製造方法並びに非水電解質二次電池 |
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WO2021236485A1 (en) * | 2020-05-18 | 2021-11-25 | Nanograf Corporation | Graphene-containing metalized silicon oxide composite materials |
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- 2022-11-25 WO PCT/KR2022/018843 patent/WO2023096404A1/ko active Application Filing
- 2022-11-25 EP EP22899086.7A patent/EP4336589A1/en active Pending
- 2022-11-25 JP JP2023573445A patent/JP2024520546A/ja active Pending
- 2022-11-25 KR KR1020220160461A patent/KR20230078563A/ko unknown
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KR100794192B1 (ko) | 2006-09-08 | 2008-01-14 | 한국과학기술연구원 | 리튬 이차 전지용 탄소 피복 실리콘-흑연 복합 음극 소재의 제조 방법 및 이를 포함하는 이차 전지의 제조방법 |
KR20150027236A (ko) * | 2012-06-27 | 2015-03-11 | 제이엔씨 주식회사 | 이차 전지용 부극 활성 물질과 그 제조 방법, 이를 이용한 부극 및 리튬 이온 전지 |
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KR20210107115A (ko) * | 2019-09-26 | 2021-08-31 | 비티알 뉴 머티리얼 그룹 코., 엘티디. | 실리콘 복합물 음극 재료 및 그 제조 방법과 리튬 이온 전지 |
KR20210053059A (ko) * | 2019-11-01 | 2021-05-11 | 주식회사 엘지화학 | 음극 활물질, 이의 제조방법, 이를 포함하는 음극 및 이차전지 |
WO2021236485A1 (en) * | 2020-05-18 | 2021-11-25 | Nanograf Corporation | Graphene-containing metalized silicon oxide composite materials |
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