WO2022149767A1 - 리튬 이차전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차전지 - Google Patents
리튬 이차전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차전지 Download PDFInfo
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- WO2022149767A1 WO2022149767A1 PCT/KR2021/019664 KR2021019664W WO2022149767A1 WO 2022149767 A1 WO2022149767 A1 WO 2022149767A1 KR 2021019664 W KR2021019664 W KR 2021019664W WO 2022149767 A1 WO2022149767 A1 WO 2022149767A1
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- graphene
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- secondary battery
- lithium secondary
- crumple
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on 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
- H01M4/36—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/58—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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive 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 cathode active material for a lithium secondary battery, a manufacturing method thereof, and a lithium secondary battery comprising the same. Specifically, the present invention relates to a cathode active material for a lithium secondary battery comprising a lithium transition metal oxide having a crumble graphene-derived coating layer formed thereon, a manufacturing method thereof, and a lithium secondary battery including the same.
- a lithium transition metal oxide is used as a cathode active material for a lithium secondary battery, and among them, lithium cobalt oxide of LiCoO 2 having a high operating voltage and excellent capacity characteristics is mainly used.
- LiCoO 2 has very poor thermal properties due to destabilization of the crystal structure due to lithium removal and is expensive, so there is a limit to its mass use as a power source in fields such as electric vehicles.
- As a material for replacing LiCoO 2 lithium manganese oxide (LiMnO 2 or LiMn 2 O 4 , etc.), lithium iron phosphate compound (LiFePO 4 etc.), or lithium nickel oxide (LiNiO 2 etc.), etc. have been developed.
- LiNiO 2 has poor thermal stability compared to LiCoO 2 , and when an internal short circuit occurs in a charged state due to external pressure, etc., the positive active material itself is decomposed to cause rupture and ignition of the battery.
- LiNiO 2 has lower electrical conductivity than LiCoO 2 and is vulnerable to moisture.
- Patent Document 1 Republic of Korea Patent Publication No. 10-2017-0119973
- the present invention provides a cathode active material for a lithium secondary battery capable of improving the functionality of a cathode active material and improving battery performance when applied to a lithium secondary battery by thinly and uniformly coating crumble graphene on a lithium transition metal oxide, and a method for manufacturing the same And to provide a lithium secondary battery including the same.
- the present invention provides a cathode active material for a lithium secondary battery comprising a lithium transition metal oxide having a crumble graphene-derived coating layer formed thereon.
- the crumble graphene has a thickness of 0.1 to 10 nm.
- the crumble graphene has a BET specific surface area of greater than 400 m 2 /g.
- the crumble graphene contains 0.1 to 3% by weight of oxygen based on the total weight of the crumble graphene.
- the crumble graphene has a size of 50 to 500 nm.
- the crumble graphene-derived coating layer has an I D /I G value of 0.1 to 0.2.
- the crumble graphene-derived coating layer has a thickness of 1 to 500 nm.
- the lithium transition metal oxide on which the crumble graphene-derived coating layer is formed has an electrical conductivity of 1.0 ⁇ 10 ⁇ 2 to 1.0 ⁇ 10 S/cm.
- the lithium transition metal oxide on which the crumble graphene-derived coating layer is formed has a BET specific surface area of 2 to 10 m 2 /g.
- the present invention provides a method for producing the above-described positive active material for a lithium secondary battery, comprising the step of coating the crumple graphene on a lithium transition metal oxide to form a crumble graphene-derived coating layer on the lithium transition metal oxide.
- the I D /I G value of the crumble graphene-derived coating layer is 30 to 70% of the I D /I G value of the crumble graphene.
- the crumble graphene is coated on lithium transition metal oxide by mechanofusion method.
- the cathode active material for a lithium secondary battery according to the present invention has a structure in which a thin and uniform crumble graphene-derived coating layer is formed on a lithium transition metal oxide by coating a thin-walled crumple graphene on a lithium transition metal oxide.
- the thin and uniform crumble graphene-derived coating layer effectively imparts electrical conductivity to the lithium transition metal oxide.
- the performance of the lithium secondary battery is improved.
- FIG. 1 is an SEM image of exemplary crumple graphene
- FIG. 1A is an image observed at a magnification ( ⁇ 100,000)
- FIG. 1B is an image observed at a magnification ( ⁇ 10,000).
- Example 3 is a SEM image of the positive active material according to Example 1.
- the present invention provides a cathode active material for a lithium secondary battery comprising a lithium transition metal oxide having a crumble graphene-derived coating layer formed thereon.
- the “crumple graphene” is a raw material used before coating on lithium transition metal oxide, and has a structure in which thin plate-shaped graphene is crumpled in a zigzag manner. Since the crumble graphene may exist in the coating layer in a collapsed state according to the coating method, in the present specification, the coating layer formed using crumble graphene as a raw material is expressed as a “crumple graphene-derived coating layer”. .
- graphene is prepared in a top-down method, specifically, low-cost graphite is chemically exfoliated in a strong acid solvent by an intercalation mechanism, and shear force ( A graphene sheet is prepared by mechanically exfoliating it using shear force).
- a graphene sheet is prepared by mechanically exfoliating it using shear force.
- Crumple graphene according to the present invention is manufactured by a bottom-up method rather than a top-down method, and specifically, other substrates or catalysts using methane gas as a raw material as shown in the following Chemical Formula 1 Without the use of a single-step thermal plasma process, self-standing growth, and finally, crumple graphene having a crumpled structure in a zigzag form of a small growth unit is produced .
- Crumple graphene prepared in this way has no mutual aggregation phenomenon in the powder phase, not the solution phase, so its dispersibility is greatly improved even when used as a powder itself, and the sp2 structure unique to high-quality graphene is well developed without surface defects. Therefore, the electrical conductivity is also excellent.
- the crumble graphene has a thickness of 0.1 to 10 nm, preferably 0.5 to 5 nm, more preferably 1 to 3 nm.
- the crumple graphene can easily maintain a zigzag crumpled structure as the thickness is thin as in the above-described range.
- the crumble graphene has a BET specific surface area of more than 400 m 2 /g, preferably 400 to 2,000 m 2 /g, more preferably 400 to 1,600 m 2 /g.
- the crumple graphene has a relatively large BET specific surface area because it has a zigzag crumpled structure with a thin thickness.
- the crumble graphene is 0.1 to 3% by weight, preferably 0.1 to 1.5% by weight, more preferably 0.1 to 1% by weight of oxygen based on the total weight of the crumble graphene contains
- crumple graphene is manufactured by a single-stage thermal plasma process without the use of other substrates or catalysts using methane gas as a raw material, compared to plate-shaped graphene produced in a general oxidation process, low oxygen content.
- the crumble graphene has a size of 50 to 500 nm, preferably 100 to 300 nm, more preferably 100 to 200 nm.
- the size means the length of the major axis of which the straight-line distance from any one point of the crumple graphene to another point is the longest based on one piece of the crumple graphene.
- the crumble graphene uses methane gas as a raw material and is instantaneously prepared by a single-step thermal plasma process without the use of other substrates or catalysts, so it has a short growth unit and has a relatively small size. Thin flaky graphene is observed as a zigzag crumpled structure. The structure is confirmed through the SEM image of the exemplary crumble graphene of FIGS. 1A and 1B.
- the crumble graphene has an I D /I G value of 0.3 to 0.5, preferably 0.3 to 0.4.
- the I D /I G value represents the relative intensity ratio of the D-band and G-band peaks in the Raman spectrum, and each band is due to the sp3 and sp2 bond structures of carbon atoms. It indicates that the fin layered structure has excellent crystallinity without defects.
- the crumple graphene has an I D /I G value that is somewhat larger than that of plate-shaped graphene and much smaller than that of carbon black.
- the crumble graphene is 1.0 ⁇ 10 2 to 1.0 ⁇ 10 3 S/cm, preferably 1.0 ⁇ 10 2 to 5.0 ⁇ 10 2 S/cm, more preferably 1.0 ⁇ It has an electrical conductivity of 10 2 to 3.0 ⁇ 10 2 S/cm.
- Carbon-based materials such as graphene and carbon black basically have high electrical conductivity and contribute to the improvement of the electrical conductivity of lithium transition metal oxide with low electrical conductivity, but the electrical conductivity of carbon-based materials is reflected in lithium transition metal oxide as it is. Therefore, it is important that the carbon-based material be uniformly coated on the lithium transition metal oxide in order to effectively improve electrical conductivity.
- the lithium transition metal oxide functions as a substantial positive active material for exchanging electrons in the positive electrode of a lithium secondary battery
- the transition metal in the lithium transition metal oxide is Li 1+x M y O 2 +Z (0 ⁇ x ⁇ 5, 0 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 2), where M is Ni, Co, Mn, Fe, P, Al, Mg, Ca, Zr, Zn, It is selected from the group consisting of Ti, Ru, Nb, W, B, Si, Na, K, Mo, V, and combinations thereof, and is not particularly limited within the above range.
- the crumble graphene is coated on a lithium transition metal oxide.
- a coating method capable of forming mechanochemical bonding in order to increase the bonding strength between the lithium transition metal oxide and the coating layer may be used.
- the mixture is coated on a lithium transition metal oxide by a mechanofusion method capable of applying a high shear force.
- the crumple graphene When the crumple graphene is coated on the lithium transition metal oxide by the mechanofusion method, the crumple graphene has a zigzag crumpled structure partially or entirely collapsed, so that it can be coated thinly and uniformly on the surface of the lithium transition metal oxide.
- Crumple graphene is coated on lithium transition metal oxide to form a crumble graphene-derived coating layer on lithium transition metal oxide.
- the crumble graphene-derived coating layer has a thickness of 1 to 500 nm, preferably 1 to 300 nm, more preferably 1 to 100 nm.
- the structure of crumple graphene may be collapsed by a coating method such as mechanofusion method, so that the crumble graphene may be coated thinly and uniformly on the surface of the lithium transition metal oxide.
- the crumble graphene-derived coating layer has an I D /I G value of 0.1 to 0.2, preferably 0.15 to 0.2. As described above, considering that the crumpled graphene before coating has an I D /I G value of 0.3 to 0.5, the I D /I G value is reduced by a significant proportion by the coating. According to one embodiment of the present invention, the I D /I G value of the crumble graphene-derived coating layer is 30 to 70%, preferably 35 to 65%, of the I D /I G value of the crumble graphene. Preferably it is 40 to 60%.
- the decrease in the I D /I G value means that the zigzag crumple graphene coating goes beyond the simple physical adhesion level to the active material surface.
- the sp2 structure on the plane is developed as the structural stress of the zigzag form is resolved.
- the structural defects of carbon atoms inside the crumple graphene may mean that a mechanically and chemically stronger and stronger carbon coating layer is formed.
- the lithium transition metal oxide with the crumble graphene-derived coating layer formed thereon is 1.0 ⁇ 10 -2 to 1.0 ⁇ 10 S/cm, preferably 1.0 ⁇ 10 -2 to 1.0 ⁇ 10 -1 It has an electrical conductivity of S/cm, more preferably 5.0 ⁇ 10 -2 to 1.0 ⁇ 10 -1 S/cm. Since the thin and uniform crumble graphene-derived coating layer effectively imparts electrical conductivity to the lithium transition metal oxide, it has higher electrical conductivity compared to the case of coating other carbon-based materials.
- the lithium transition metal oxide on which the crumble graphene-derived coating layer is formed is 2 to 10 m 2 /g, preferably 2 to 7.5 m 2 /g, more preferably 2 to 5 m 2 /g has a BET specific surface area of .
- the crumple graphene material itself has a high BET specific surface area of more than 400 m 2 /g, but during the coating process, the crumpled zigzag structure of the crumple graphene collapses partially or entirely, , the specific surface area after coating decreases relatively significantly compared to before coating.
- the positive active material for a lithium secondary battery according to the present invention effectively imparts electrical conductivity to the lithium transition metal oxide by forming a thin and uniform graphene coating layer using crumple graphene as a raw material on the lithium transition metal oxide.
- the performance of the lithium secondary battery, particularly, the discharge capacity at a high C-rate may be improved.
- the present invention provides a lithium secondary battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte.
- the positive electrode and the negative electrode are positioned to face each other, and the separator is interposed between the positive electrode and the negative electrode.
- the electrode assembly of the positive electrode, the negative electrode, and the separator is accommodated in a battery container, and the battery container is filled with an electrolyte.
- the positive electrode includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector and including the above-described positive electrode active material.
- the positive electrode current collector is not particularly limited as long as it has conductivity without causing a chemical change in the battery, for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. , nickel, titanium, silver or the like surface-treated may be used.
- the positive electrode current collector may typically have a thickness of 3 to 500 ⁇ m, and may increase the adhesion of the positive electrode active material by forming fine irregularities on the surface of the positive electrode current collector.
- it may be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a non-woven body.
- the positive active material layer may include a conductive material and a binder together with the above-described positive active material.
- the conductive material is used to impart conductivity to the electrode, and in the configured battery, it can be used without any particular limitation as long as it has electronic conductivity without causing chemical change.
- Specific examples include graphite such as natural graphite and artificial graphite; carbon-based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, single-walled or multi-walled carbon nanotubes, carbon fibers, graphene, activated carbon, and activated carbon fibers; metal powders or metal fibers such as copper, nickel, aluminum, and silver; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or a conductive polymer such as a polyphenylene derivative, and the like, and any one of them or a mixture of two or more thereof may be used.
- the conductive material may be included in an amount of 1 to 30 wt% based on the total weight of the positive active material layer.
- the binder serves to improve adhesion between the positive active material particles and adhesion between the positive active material and the positive electrode current collector.
- Specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC) ), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and any one of them or a mixture of two or more thereof may be used.
- the binder may be included in an amount of 1 to 30% by weight based on the total weight of the positive active material layer.
- the positive electrode may be manufactured according to a conventional positive electrode manufacturing method except for using the above-described positive electrode active material. Specifically, it may be prepared by applying the above-described positive active material and, optionally, a composition for forming a positive electrode active material layer including a binder and a conductive material on a positive electrode current collector, followed by drying and rolling. In this case, the types and contents of the positive electrode active material, the binder, and the conductive material are as described above.
- the solvent may be a solvent generally used in the art, dimethyl sulfoxide (DMSO), isopropyl alcohol (isopropyl alcohol), N-methylpyrrolidone (NMP), acetone (acetone) or water and the like, and any one of them or a mixture of two or more thereof may be used.
- the amount of the solvent used is enough to dissolve or disperse the positive electrode active material, the conductive material and the binder in consideration of the application thickness of the slurry and the production yield, and to have a viscosity capable of exhibiting excellent thickness uniformity during application for the production of the positive electrode thereafter. do.
- the positive electrode may be prepared by casting the composition for forming the positive electrode active material layer on a separate support, and then laminating a film obtained by peeling it from the support on the positive electrode current collector.
- the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
- the anode active material layer optionally includes a binder and a conductive material together with the 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; metal compounds capable of alloying with lithium, such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, or Al alloy; metal oxides capable of doping and dedoping lithium, such as SiO ⁇ (0 ⁇ 2), SnO 2 , vanadium oxide, and lithium vanadium oxide; Alternatively, a composite including the above-mentioned metallic compound and a carbonaceous material such as a Si-C composite or a Sn-C composite may be used, and any one or a mixture of two or more thereof may be used.
- a metal lithium thin film may be used as the negative active material.
- both low crystalline carbon and high crystalline carbon may be used.
- low crystalline carbon soft carbon and hard carbon are representative, and as high crystalline carbon, natural or artificial graphite of amorphous, plate-like, flaky, spherical or fibrous shape, and Kish graphite (Kish) graphite), pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, liquid crystal pitches (Mesophase pitches), and petroleum and coal tar pitch (petroleum or coal tar pitch) High-temperature calcined carbon such as derived cokes) is a representative example.
- the binder, the conductive material, and the negative electrode current collector may be selected with reference to the above-described configuration of the positive electrode, but is not limited thereto.
- the method of forming the negative electrode active material layer on the negative electrode current collector is similar to the positive electrode by a known coating method and is not particularly limited.
- the separator separates the negative electrode and the positive electrode and provides a passage for lithium ions to move, and as long as it is used as a separator in a lithium secondary battery, it can be used without particular limitation, and in particular, it is low in ion movement of the electrolyte. It is preferable that it is excellent in the electrolytic solution moisture content while being resistance.
- a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, or these
- a laminated structure of two or more layers of may be used.
- a conventional porous nonwoven fabric for example, a nonwoven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, etc. may be used.
- a coated separator containing a ceramic component or a polymer material may be used, and may optionally be used in a single-layer or multi-layer structure.
- Examples of the electrolyte used in the present invention include organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, molten inorganic electrolytes, and the like, which can be used in the manufacture of lithium secondary batteries. not.
- the electrolyte may include an organic solvent and a lithium salt.
- the organic solvent may be used without any particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
- ester solvents such as methyl acetate, ethyl acetate, ⁇ -butyrolactone, ⁇ -caprolactone
- ether-based solvents such as dibutyl ether or tetrahydrofuran
- ketone solvents such as cyclohexanone
- aromatic hydrocarbon solvents such as benzene and fluorobenzene
- alcohol solvents such as ethyl alcohol and isopropyl alcohol
- nitriles such as R-CN (R is a C2 to C20 linear, branched or cyclic hydro
- a carbonate-based solvent is preferable, and a cyclic carbonate (eg, ethylene carbonate or propylene carbonate, etc.) having high ionic conductivity and high dielectric constant capable of increasing the charge/discharge performance of the battery, and a low-viscosity linear carbonate-based compound (for example, a mixture of ethylmethyl carbonate, dimethyl carbonate or diethyl carbonate, etc.) is more preferable.
- the cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1:1 to about 1:9, the electrolyte may exhibit excellent performance.
- the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
- the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN(C 2 F 5 SO 3 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2 .
- LiCl, LiI, or LiB(C 2 O 4 ) 2 , etc. may be used.
- the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has appropriate conductivity and viscosity, excellent electrolyte performance may be exhibited, and lithium ions may move effectively.
- haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, tri 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 taxdine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol or aluminum trichloride may be further included. In this case, the additive may be included in an amount of 0.1 to 5% by weight based on the total weight of the electrolyte.
- the lithium secondary battery including the positive electrode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics and capacity retention rate, so portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles ( It is useful in the field of electric vehicles such as hybrid electric vehicle, HEV).
- a battery module including the lithium secondary battery as a unit cell and a battery pack including the same are provided.
- the battery module or battery pack is a power tool (Power Tool); electric vehicles, including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Alternatively, it may be used as a power source for any one or more medium and large-sized devices in a system for power storage.
- Power Tool Power Tool
- electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs);
- PHEVs plug-in hybrid electric vehicles
- Crumple graphene (manufacturer: Nanointegris Technologies, product: PureWave Graphene, average thickness: 2.4 nm, BET specific surface area: more than 400 m/g, size: 150-200 nm, oxygen content: 1%) was mixed with LiNi 0.6 Co 0.2 Mn After mixing with 0.2 O 2 (NCM 622) and a weight ratio of 1:99, it was put into a mechanofusion device (manufacturer: Hosokawa Micron, product: Nobilta NOB-130), and then driven at 3,000 rpm, 10 minutes. , A cathode active material coated with crumple graphene was prepared.
- a cathode active material coated with carbon black was prepared in the same manner as in Example 1, except that carbon black (manufacturer: Imerys, product: Super C65) was used instead of crumple graphene.
- SEM Scanning electron microscopy
- the I D /I G value was measured by analyzing a Raman spectrum with an Ar-ion laser having a wavelength of 514.5 nm through a Raman spectrometer (manufacturer: Jasco, product: NRS-2000B).
- I D /I G value change rate (%) I D /I G value after coating / I D /I G value before coating ⁇ 100
- each of the positive electrode active materials were mixed with a carbon black conductive material and a PVDF binder in an N-methylpyrrolidone solvent in a weight ratio of 97.5:1:1.5 (positive electrode active material:conductive material:binder) to produce a positive electrode.
- a positive electrode was prepared by preparing a slurry of an active material, applying it on one surface of an aluminum current collector (loading amount: 10 to 12 mg/cm 2 ), drying at 130° C., and rolling.
- Lithium metal was used for the negative electrode, and a separator of porous polyethylene was interposed between the positive electrode and the negative electrode to prepare an electrode assembly.
- an electrolyte was injected into the case to prepare a lithium secondary battery.
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Abstract
Description
탄소계 물질 | 코팅 조건 | 전기 전도도 (S/cm) |
BET 비표면적 (㎡/g) |
ID/IG 값 | ID/IG 값 변화율 (%) |
크럼플 그래핀 | 코팅 전 | 2.22×102 | 402 | 0.37 | - |
실시예 1의 코팅 후 | 5.61×10-2 | 3.83 | 0.18 | 48.6 | |
비교예 1의 코팅 후 | 8.38×10-3 | 5.08 | 0.34 | 91.9 | |
판상형 그래핀 | 코팅 전 | 1.84×103 | 51 | 0.22 | - |
비교예 2의 코팅 후 | 4.62×10-3 | 0.63 | 0.17 | 77.3 | |
비교예 3의 코팅 후 | 2.32×10-3 | 0.78 | 0.21 | 95.5 | |
카본 블랙 | 코팅 전 | 1.76×10 | 115 | 1.09 | - |
비교예 4의 코팅 후 | 3.58×10-3 | 1.59 | 1.05 | 96.3 | |
비교예 5의 코팅 후 | 2.49×10-3 | 1.84 | 1.08 | 99.1 |
리튬 이차전지의 양극 활물질 | 2.0 C 방전 용량비 (%) |
실시예 1 | 94.8 |
비교예 1 | 89.6 |
비교예 2 | 91.5 |
비교예 3 | 78.4 |
비교예 4 | 74.9 |
비교예 5 | 75.3 |
Claims (15)
- 크럼플 그래핀 유래 코팅층이 형성된 리튬 전이금속 산화물을 포함하고,상기 크럼플 그래핀은 0.1 내지 10nm의 두께를 가지는 리튬 이차전지용 양극 활물질.
- 청구항 1에 있어서,상기 크럼플 그래핀은 400㎡/g 초과의 BET 비표면적을 가지는 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 청구항 1에 있어서,상기 크럼플 그래핀은 크럼플 그래핀 총 중량을 기준으로 하여 0.1 내지 3 중량%의 산소를 함유하는 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 청구항 1에 있어서,상기 크럼플 그래핀은 50 내지 500nm의 크기를 가지는 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 청구항 1에 있어서,상기 리튬 전이금속 산화물은 LiCoO2, LiNiO2, LiMnO2, Li2MnO3, LiMn2O4, Li(NiaCobMnc)O2(0<a<1, 0<b<1, 0<c<1, a+b+c=1), LiNi1-yCoyO2(O<y<1), LiCo1-yMnyO2, LiNi1-yMnyO2(O<y<1), Li(NiaCobMnc)O4(0<a<2, 0<b<2, 0<c<2, a+b+c=2), LiMn2-zNizO4(0<z<2), LiMn2-zCozO4(0<z<2) 및 이의 조합으로부터 선택되는 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 청구항 1에 있어서,상기 크럼플 그래핀 유래 코팅층은 0.1 내지 0.2의 ID/IG 값을 가지는 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 청구항 1에 있어서,상기 크럼플 그래핀 유래 코팅층은 1 내지 500nm의 두께를 가지는 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 청구항 1에 있어서,상기 크럼플 그래핀 유래 코팅층이 형성된 리튬 전이금속 산화물은 1.0×10-2 내지 1.0×10 S/cm의 전기 전도도를 가지는 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 청구항 1에 있어서,상기 크럼플 그래핀 유래 코팅층이 형성된 리튬 전이금속 산화물은 2 내지 10㎡/g의 BET 비표면적을 가지는 것을 특징으로 하는 리튬 이차전지용 양극 활물질.
- 크럼플 그래핀을 리튬 전이금속 산화물에 코팅하여 리튬 전이금속 산화물 상에 크럼플 그래핀 유래 코팅층을 형성하는 단계를 포함하고,상기 크럼플 그래핀은 0.1 내지 10nm의 두께를 가지는 청구항 1에 따른 리튬 이차전지용 양극 활물질의 제조방법.
- 청구항 10에 있어서,상기 크럼플 그래핀은 400㎡/g 초과의 BET 비표면적을 가지는 것을 특징으로 하는 리튬 이차전지용 양극 활물질의 제조방법.
- 청구항 10에 있어서,상기 크럼플 그래핀은 크럼플 그래핀 총 중량을 기준으로 하여 0.1 내지 3 중량%의 산소를 함유하는 것을 특징으로 하는 리튬 이차전지용 양극 활물질의 제조방법.
- 청구항 10에 있어서,상기 크럼플 그래핀은 50 내지 500nm의 크기를 가지는 것을 특징으로 하는 리튬 이차전지용 양극 활물질의 제조방법.
- 청구항 10에 있어서,상기 크럼플 그래핀 유래 코팅층의 ID/IG 값은 크럼플 그래핀의 ID/IG 값의 30 내지 70 %인 것을 특징으로 하는 리튬 이차전지용 양극 활물질의 제조방법.
- 청구항 10에 있어서,상기 크럼플 그래핀은 리튬 전이금속 산화물에 메카노퓨전법에 의해 코팅되는 것을 특징으로 하는 리튬 이차전지용 양극 활물질의 제조방법.
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