WO2023200083A1 - 안전성이 향상된 리튬 이차전지 - Google Patents
안전성이 향상된 리튬 이차전지 Download PDFInfo
- Publication number
- WO2023200083A1 WO2023200083A1 PCT/KR2023/000443 KR2023000443W WO2023200083A1 WO 2023200083 A1 WO2023200083 A1 WO 2023200083A1 KR 2023000443 W KR2023000443 W KR 2023000443W WO 2023200083 A1 WO2023200083 A1 WO 2023200083A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- secondary battery
- lithium secondary
- active material
- cathode
- Prior art date
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- 239000007774 positive electrode material Substances 0.000 claims abstract description 53
- -1 iron phosphate compound Chemical class 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 88
- 239000002131 composite material Substances 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
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- 239000003792 electrolyte Substances 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
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Images
Classifications
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- H—ELECTRICITY
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- 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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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
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- 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
- H01M2004/027—Negative electrodes
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a lithium secondary battery with improved safety due to internal short circuit.
- secondary batteries have been widely applied not only to small devices such as portable electronic devices, but also to medium-to-large devices such as battery packs of hybrid vehicles or electric vehicles or power storage devices.
- lithium nickel metal oxide increases in capacity as the nickel (Ni) content increases, but exhibits low chemical and structural stability, so exothermic reactions are prone to occur.
- the exothermic reaction of the cathode active material can be induced when a short-circuit current flows inside the battery, that is, when an internal short-circuit occurs.
- lithium nickel metal oxide has a low on-set point, so once the exothermic reaction begins, There is a problem with low safety because it can cause ignition by rapidly increasing the temperature inside the battery.
- the purpose of the present invention is to provide a positive electrode containing a ternary compound containing nickel (Ni), which has high energy density and improved safety problems due to internal short circuit, and a lithium secondary battery containing the same.
- the first positive electrode composite layer in contact with the surface of the positive electrode current collector includes a first positive electrode active material containing a lithium complex metal oxide represented by the following formula (1),
- the second to n-th positive electrode mixture layers disposed on the first positive electrode mixture layer include a first positive electrode active material containing a lithium complex metal oxide represented by Formula 1 and an iron phosphate compound represented by Formula 2 below.
- a positive electrode for a lithium secondary battery containing a positive electrode active material is a positive electrode active material containing a lithium complex metal oxide represented by Formula 1 and an iron phosphate compound represented by Formula 2 below.
- M 1 is W, Cu, Fe, V, Cr, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, and It is one or more elements selected from the group consisting of Mo,
- M 2 is W, Cu, Fe, V, Cr, CO, Ni, Mn, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb , Mg, B, and Mo, at least one element selected from the group consisting of,
- X is one or more selected from the group consisting of P, Si, S, As and Sb,
- a 0 ⁇ a ⁇ 0.5.
- the concentration of the second positive electrode active material in each positive electrode mixture layer may increase as the location of the individual positive electrode mixture layers changes from the second positive electrode mixture layer to the n-th positive electrode mixture layer.
- the second positive electrode active material may be included in an amount of less than 10% by weight based on the total weight of the positive electrode mixture layer, and the second positive electrode active material may be included in an individual positive electrode mixture layer in an amount of 0.5 to 20% by weight based on the weight of each positive electrode mixture layer. there is.
- the second positive electrode active material may have an average particle size of 0.5 ⁇ m to 5 ⁇ m, and the average particle size may increase as the position of the individual positive electrode mixture layer changes from the second positive electrode mixture layer to the n-th positive electrode mixture layer. there is.
- the n positive electrode mixture layers may have a total thickness of 50 ⁇ m to 200 ⁇ m, and the thickness of the first positive electrode mixture layer may be 10% to 60% of the total thickness of the positive electrode mixture layers.
- the anode according to the invention described above cathode; And it provides an electrode assembly for a lithium secondary battery including a separator interposed between the positive electrode and the negative electrode.
- the negative electrode includes a negative electrode mixture layer on the negative electrode current collector, and the negative electrode mixture layer is made of natural graphite, artificial graphite, expanded graphite, hard carbon, soft carbon, carbon fiber, carbon black, carbon nanotubes, fullerene, and activated carbon. , may include one or more carbon-based negative electrode active materials among acetylene black and Ketjen black.
- a lithium secondary battery including an electrolyte composition injected into a battery case together with an electrode assembly is provided.
- the lithium secondary battery may be a prismatic secondary battery.
- the positive electrode for a lithium secondary battery according to the present invention not only has excellent energy density by containing a ternary compound containing nickel (Ni), cobalt (Co), manganese (Mn), etc. as a positive electrode active material, but also has excellent energy density based on the positive electrode current collector. Containing an iron phosphate compound in the outermost layer has the advantage of improving safety due to internal short circuit of the secondary battery.
- Figure 1 is a cross-sectional view showing the structure of a positive electrode for a lithium secondary battery according to the present invention.
- the present invention in one embodiment, the present invention
- the first positive electrode composite layer in contact with the surface of the positive electrode current collector includes a first positive electrode active material containing a lithium complex metal oxide represented by the following formula (1),
- the second to n-th positive electrode mixture layers disposed on the first positive electrode mixture layer include a first positive electrode active material containing a lithium complex metal oxide represented by Formula 1 and an iron phosphate compound represented by Formula 2 below.
- a positive electrode for a lithium secondary battery containing a positive electrode active material is a positive electrode active material containing a lithium complex metal oxide represented by Formula 1 and an iron phosphate compound represented by Formula 2 below.
- M 1 is W, Cu, Fe, V, Cr, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, and It is one or more elements selected from the group consisting of Mo,
- M 2 is W, Cu, Fe, V, Cr, CO, Ni, Mn, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb , Mg, B, and Mo, at least one element selected from the group consisting of,
- X is one or more selected from the group consisting of P, Si, S, As and Sb,
- a 0 ⁇ a ⁇ 0.5.
- the positive electrode for a lithium secondary battery according to the present invention includes a positive electrode current collector and a positive electrode composite layer with a multi-layer structure in which two or more individual composite layers are stacked on the positive electrode current collector.
- the positive electrode mixture layer has a structure in which n (where n ⁇ 2) individual positive electrode mixture layers are stacked on a positive electrode current collector, as shown in FIG. 1.
- the positive electrode mixture layer 20 laminated on the surface in contact with the positive electrode current collector 10 is the first positive electrode mixture layer 21a, and the second positive electrode mixture layer to the nth positive electrode are formed on the first positive electrode mixture layer 21a.
- the composite layers 21b are sequentially stacked to form n individual positive electrode composite layers on the positive electrode current collector.
- the positive electrode composite layer has a structure of two or more layers
- the number of layers is not particularly limited, but specifically, it is 2 to 10 layers; 2nd to 8th floors; 2nd to 6th floors; Or it could be the 2nd or 4th floor.
- the present invention can improve the energy density of the electrode while preventing a decrease in the manufacturing efficiency of the positive electrode by adjusting the number of stacks of the positive electrode composite layer within the above range, and at the same time, heat generated during charging and discharging of the battery can be effectively discharged to the outside.
- the positive electrode composite layer is manufactured by applying, drying, and pressing a slurry containing a positive electrode active material capable of reversibly intercalating and deintercalating lithium ions during charging and discharging of the battery, and the positive electrode active material is of different types in each layer. may be included.
- the positive electrode according to the present invention includes a first positive electrode active material containing a lithium complex metal oxide represented by the following formula (1) in a positive electrode mixture layer, and a positive electrode mixture layer spaced apart from the positive electrode current collector, that is, the first positive electrode mixture.
- the second to n-th positive electrode mixture layers disposed on the layer further include a second positive electrode active material containing an iron phosphate compound represented by Chemical Formula 2:
- M 1 is W, Cu, Fe, V, Cr, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, and It is one or more elements selected from the group consisting of Mo,
- M 2 is W, Cu, Fe, V, Cr, CO, Ni, Mn, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb , Mg, B, and Mo, at least one element selected from the group consisting of,
- X is one or more selected from the group consisting of P, Si, S, As and Sb,
- a 0 ⁇ a ⁇ 0.5.
- the lithium composite metal oxide represented by Formula 1 is a ternary lithium oxide containing nickel (Ni), cobalt (Co), and manganese (Mn) as main components. It has a high energy density and is suitable for electric vehicles (EVs) in terms of performance such as output. ) has the advantage of being suitable for medium to large-sized secondary batteries for power storage such as transportation fields or energy storage systems (ESS).
- ESS energy storage systems
- the capacity of the lithium composite metal oxide increases as the nickel (Ni) content increases, but it exhibits low chemical and structural stability, so an exothermic reaction is likely to occur, and thus there is a high possibility of ignition occurring. there is.
- the exothermic reaction can be induced when a short-circuit current flows inside the battery, that is, when an internal short-circuit occurs.
- the short-circuit current of the battery occurs when a short circuit occurs inside the secondary battery due to penetration of a needle-shaped object, etc., or when an electronic circuit connected to the secondary battery occurs.
- a short circuit may occur in devices, etc.
- the present invention includes a lithium complex metal oxide represented by Chemical Formula 1 throughout the multi-layered positive electrode mixture layer as a first positive electrode active material, and a lithium complex metal oxide represented by Chemical Formula 2 in the second to nth positive electrode mixture layers spaced apart from the positive electrode current collector.
- a lithium complex metal oxide represented by Chemical Formula 1 throughout the multi-layered positive electrode mixture layer as a first positive electrode active material
- Chemical Formula 2 in the second to nth positive electrode mixture layers spaced apart from the positive electrode current collector.
- an iron phosphate compound as a second positive electrode active material
- the first positive electrode active material that generates heat during charging and discharging of the battery can be distributed in a location adjacent to the positive electrode current collector where heat is easily transferred to the outside, thereby improving the heat resistance of the positive electrode.
- the rigidity of the positive electrode surface can be increased due to the second positive electrode active material, thereby reducing the risk of internal short circuit due to external force or penetration of a needle-like object.
- the first positive electrode active material containing the lithium composite metal oxide represented by Formula 1 is a metal oxide containing lithium, nickel (Ni), cobalt (Co), and manganese (Mn), and in some cases, other transition metals.
- (M 1 ) may have a doped form.
- the lithium composite metal oxide is Li(Ni 0.6 Co 0.2 Mn 0.2 )O 2 , Li(Ni 0.7 Co 0.15 Mn 0.15 )O 2 , Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 , Li(Ni 0.9 Co 0.05 Mn 0.05 )O 2 , Li(Ni 0.6 Co 0.2 Mn 0.1 Zr 0.1 )O 2 , Li(Ni 0.6 Co 0.2 Mn 0.15 Zr 0.05 )O 2 and Li(Ni 0.7 Co 0.1 Mn 0.1 Zr 0.1 )O 2 It may include one or more species selected from the group consisting of.
- the particle size of the first positive electrode active material is not particularly limited, but may have an average particle size of 0.5 to 5 ⁇ m, more specifically 0.8 to 1.5 ⁇ m; 1.0 to 3.0 ⁇ m; 1.2 to 1.8 ⁇ m; Alternatively, it may have an average particle size of 1.5 to 2.5 ⁇ m.
- the iron phosphate compound represented by Formula 2 is a lithium phosphate containing iron, and may be doped with another transition metal (M 2 ) depending on the case.
- the iron phosphate compound may include LiFePO 4 , LiFe 0.8 Mn 0.2 PO 4 , LiFe 0.5 Mn 0.5 PO 4 , etc.
- the second positive electrode active material containing the iron phosphate compound may have an average particle size of 0.5 to 5 ⁇ m, specifically 0.5 to 1.0 ⁇ m; 0.8 to 1.2 ⁇ m; 1.0 to 2.0 ⁇ m; 1.5 to 3.0 ⁇ m; 2.0 to 3.0 ⁇ m; Alternatively, it may have an average particle size of 2.5 to 4.0 ⁇ m.
- the second positive electrode active material shows a tendency for the average particle size of the second positive electrode active material contained in each positive electrode mixture layer to increase as the position of the individual positive electrode mixture layers changes from the second positive electrode mixture layer to the n-th positive electrode mixture layer. You can.
- the second positive electrode active material included in the second positive electrode mixture layer may have an average particle size of 0.5 to 1.2 ⁇ m
- the second positive electrode active material included in the nth positive electrode mixture layer (however, n ⁇ 2) may have an average particle size of 1.3 to 1.2 ⁇ m. It may have an average particle size of 3.0 ⁇ m.
- the second positive electrode active material included in the second positive electrode mixture layer may have an average particle size of 0.8 to 1.0 ⁇ m
- the second positive electrode active material included in the third positive electrode composite layer may have an average particle size of 1.2 to 1.5 ⁇ m.
- the second positive electrode active material included in the second positive electrode mixture layer may have an average particle size of 0.6 to 0.8 ⁇ m, and the second positive electrode active material included in the third positive electrode mixture layer may have an average particle size of 1.5 to 1.8 ⁇ m.
- the second positive electrode active material included in the fourth positive electrode composite layer may have an average particle size of 2.0 to 2.2 ⁇ m.
- the positive electrode of the present invention can further increase the rigidity of the positive electrode surface by increasing the average particle size of the second positive electrode active material as the position of the individual positive electrode mixture layers changes from the second positive electrode mixture layer to the n-th positive electrode mixture layer.
- the second positive electrode active material may be included in an amount of less than 10% by weight based on the weight of the entire positive electrode mixture layer, and specifically, 0.1 to 9.9% by weight based on the weight of the entire positive electrode mixture layer; 0.5 to 8.0% by weight; 0.5 to 6.0% by weight; 0.1 to 5.0% by weight; 0.1 to 3.0% by weight; 1.0 to 3.0% by weight; 2.5 to 5.0% by weight; 4.0 to 8.0% by weight; Alternatively, it may be included at 6.0 to 9.9% by weight.
- the second positive electrode active material containing the lithium composite metal oxide represented by Formula 2 may be included in each positive electrode mixture layer in an amount of 0.5 to 20% by weight based on the weight of each positive electrode mixture layer. 1 to 18% by weight; 1 to 15% by weight; 1 to 12% by weight; 1 to 10% by weight; 1 to 8% by weight; 1 to 5% by weight; 0.5 to 1% by weight; 0.5 to 5% by weight; 2 to 6% by weight; 0.5 to 0.9% by weight; 5 to 16% by weight; 7 to 15% by weight; Alternatively, it may be included at 8 to 12% by weight.
- the present invention controls the content of the second positive electrode active material within the above range with respect to the weight of the entire positive electrode composite layer and the individual positive electrode composite layer, thereby preventing insufficient rigidity on the positive electrode surface due to the insignificant content, while preventing excessive
- the second positive electrode active material can prevent the electrical performance of the battery from deteriorating due to an increase in electrode resistance on the positive electrode surface.
- the second positive electrode active material is included in the second positive electrode mixture layer to the n-th positive electrode mixture layer, wherein the n-th positive electrode mixture layer is furthest from the first positive electrode mixture layer in the second positive electrode mixture layer in contact with the first positive electrode mixture layer.
- concentration may tend to increase.
- 'concentration increases' may mean that the content or content ratio of the second positive electrode active material increases based on the total weight of the individual positive electrode composite layer.
- the redox reaction of the second cathode active material progresses relatively more slowly compared to the first cathode active material, so the concentration is increased closer to the outermost side of the cathode compound layer, thereby reducing the risk of fire or fire in the event of a short circuit inside the battery. This has the advantage of lowering the possibility of explosion.
- the positive electrode for a lithium secondary battery according to the present invention may further include a conductive material, binder, and other additives in the positive electrode composite layer, if necessary.
- the first and second positive electrode active materials contained in each positive electrode mixture layer may be included in an amount of 85 parts by weight or more, specifically, 90 parts by weight or more, 93 parts by weight, or 95 parts by weight or more based on the weight of each positive electrode mixture layer. You can.
- the conductive material is used to improve the electrical performance of the anode, and those commonly used in the industry can be applied, but specifically, natural graphite, artificial graphite, carbon black, acetylene black, Denka black, and Ketjen black. , Super-P, channel black, furnace black, lamp black, summer black, graphene, and carbon nanotubes.
- the conductive material may be included in an amount of 0.1 to 5 parts by weight based on the weight of each positive electrode mixture layer, and specifically, 0.1 to 4 parts by weight; 2 to 4 parts by weight; 1.5 to 5 parts by weight; 1 to 3 parts by weight; 0.1 to 2 parts by weight; Alternatively, it may be included in 0.1 to 1 part by weight.
- the binder serves to bind the positive electrode active material, positive electrode additive, and conductive material to each other, and any binder that has this function may be used without particular restrictions.
- the binder includes polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP), polyvinylidenefluoride (PVdF), polyacrylonitrile, and polymethyl methacryl. It may contain one or more resins selected from the group consisting of polymethylmethacrylate and copolymers thereof.
- the binder may include polyvinylidenefluoride.
- the binder may be included in an amount of 1 to 10 parts by weight based on the weight of each positive electrode composite layer, and specifically, 2 to 8 parts by weight; Alternatively, it may contain 1 to 5 parts by weight of the conductive material.
- the total thickness of the positive electrode mixture layer is not particularly limited, but may be specifically 50 ⁇ m to 300 ⁇ m, more specifically 100 ⁇ m to 200 ⁇ m; 80 ⁇ m to 150 ⁇ m; 120 ⁇ m to 170 ⁇ m; 150 ⁇ m to 300 ⁇ m; 200 ⁇ m to 300 ⁇ m; Or it may be 150 ⁇ m to 190 ⁇ m.
- the thickness of the first positive electrode compound layer in contact with the positive electrode current collector may be adjusted to a certain range.
- the thickness of the first positive electrode mixture layer may be 10% to 60% of the total thickness of the positive electrode mixture layer, and more specifically, 10% to 40% of the total thickness of the positive electrode mixture layer; 30% to 50%; 10% to 20%; Or it may be 40% to 60%.
- the present invention not only prevents the energy density of the electrode from being reduced by adjusting the total and individual thicknesses of the positive electrode compound layer within the above range, but also can achieve high adhesion between the positive electrode current collector and the positive electrode compound layer.
- the positive electrode current collector provided in the positive electrode can be one that has high conductivity without causing chemical changes in the battery.
- stainless steel, aluminum, nickel, titanium, calcined carbon, etc. can be used, and in the case of aluminum or stainless steel, surface treatment with carbon, nickel, titanium, silver, etc. can also be used.
- the average thickness of the current collector can be appropriately applied in the range of 5 to 500 ⁇ m considering the conductivity and total thickness of the positive electrode to be manufactured.
- the anode according to the invention described above cathode; And it provides an electrode assembly for a lithium secondary battery including a separator interposed between the positive electrode and the negative electrode.
- the electrode assembly for a lithium secondary battery according to the present invention is equipped with the positive electrode of the present invention described above, has high energy density of the battery, has excellent output performance, and transfers heat to the outside through the first positive electrode active material that generates heat when charging and discharging the battery. Since it can be easily distributed in a location adjacent to the positive electrode current collector, the heat resistance of the positive electrode is improved, while the rigidity of the positive electrode surface can be increased due to the second positive electrode active material, so there is a risk of internal short circuit due to external force or penetration of needle-shaped objects, etc. There is a low advantage.
- the positive electrode has the same structure as the positive electrode for a lithium secondary battery of the present invention described above, a description of the detailed structure is omitted.
- the negative electrode has a negative electrode mixture layer manufactured by applying, drying, and pressing a negative electrode active material on a negative electrode current collector in the same manner as the positive electrode, and optionally additional conductive materials, binders, and other electrolyte additives as needed. It can be included.
- the negative electrode active material may be one commonly used in the industry, but specifically, natural graphite, artificial graphite, expanded graphite, hard carbon, soft carbon, carbon fiber, carbon black, carbon nanotubes, fullerene, activated carbon. , may include one or more carbon-based negative electrode active materials among acetylene black and Ketjen black.
- the negative electrode mixture layer may provide adhesion to the negative electrode current collector and may include a binder so that the negative electrode active material, conductive material, and other additives can be bonded to each other.
- binders include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, and carboxymethylcellulose ( CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene.
- PVDF polyvinylidene fluoride
- PVDF-co-HFP vinylidene fluoride-hexafluoropropylene copolymer
- CMC carboxymethylcellulose
- EPDM ethylene-propy
- Examples include butadiene rubber (SBR), fluorine rubber, and various copolymers thereof, and one type of these may be used alone or a mixture of two or more types may be used.
- the binder may be included in an amount of 1 to 10 parts by weight based on the weight of the negative electrode mixture layer, and specifically, 2 to 8 parts by weight; Alternatively, it may contain 1 to 5 parts by weight of the conductive material.
- the negative electrode mixture layer may have an average thickness of 100 ⁇ m to 200 ⁇ m, specifically 100 ⁇ m to 180 ⁇ m, 100 ⁇ m to 150 ⁇ m, 120 ⁇ m to 200 ⁇ m, 140 ⁇ m to 200 ⁇ m, or 140 ⁇ m to 140 ⁇ m. It can have an average thickness of 160 ⁇ m.
- the negative electrode may include a negative electrode current collector having high conductivity without causing chemical changes in the battery.
- a negative electrode current collector having high conductivity without causing chemical changes in the battery.
- copper, stainless steel, nickel, titanium, calcined carbon, etc. can be used as the negative electrode current collector, and in the case of copper or stainless steel, surface treatment with carbon, nickel, titanium, silver, etc. can be used.
- the negative electrode current collector can form fine irregularities on the surface to strengthen the bonding force with the negative electrode active material, and can come in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven fabrics. possible.
- the average thickness of the negative electrode current collector may be appropriately applied in the range of 3 to 500 ⁇ m considering the conductivity and total thickness of the negative electrode being manufactured.
- the separator is sandwiched between the anode and the cathode, and a thin insulating film with high ion permeability and mechanical strength is used.
- the separator is not particularly limited as long as it is commonly used in the art, and specifically includes chemical resistant and hydrophobic polypropylene; glass fiber; Alternatively, sheets or non-woven fabrics made of polyethylene, etc. may be used, and in some cases, a composite separator in which inorganic particles/organic particles are coated with an organic binder polymer on a porous polymer substrate such as the sheet or non-woven fabric may be used.
- a solid electrolyte such as a polymer
- the solid electrolyte may also serve as a separator.
- the pore diameter of the separator may be on average 0.01 to 10 ⁇ m, and the thickness may be 5 to 300 ⁇ m on average.
- a lithium secondary battery including an electrolyte composition injected into a battery case together with an electrode assembly is provided.
- the lithium secondary battery according to the present invention includes an electrode assembly including the positive electrode of the present invention described above, and the electrode assembly may have a structure that is inserted into the battery case together with the electrolyte composition.
- the electrolyte composition includes, but is not limited to, organic liquid electrolyte, inorganic liquid electrolyte, solid polymer electrolyte, gel-type polymer electrolyte, solid inorganic electrolyte, and molten inorganic electrolyte that can be used when manufacturing a lithium secondary battery.
- the electrolyte may include an organic solvent and a lithium salt.
- the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
- the organic solvent includes ester solvents such as methyl acetate, ethyl acetate, ⁇ -butyrolactone, and ⁇ -caprolactone; Ether-based solvents such as dibutyl ether or tetrahydrofuran; Ketone-based solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethylcarbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate (propylene carbonate) Carbonate-based solvents such as PC); Alcohol-based solvents such as ethyl alcohol and isopropyl alcohol; nitriles such as R-CN (R is a C2 to C20 straight-
- carbonate-based solvents are preferable, and cyclic carbonates (e.g., ethylene carbonate or propylene carbonate, etc.) with high ionic conductivity and high dielectric constant that can improve the charge/discharge performance of the battery, and low-viscosity linear carbonate-based compounds ( For example, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, etc.) are more preferable.
- cyclic carbonate and chain carbonate in a volume ratio of about 1:1 to 9 can result in excellent electrolyte performance.
- the lithium salt may be used without particular limitation as long as it is a compound that can provide lithium ions used in lithium secondary batteries.
- 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 may be used.
- the concentration of the lithium salt can be used within the range of 0.1M to 2.0M.
- the electrolyte has appropriate conductivity and viscosity, so excellent electrolyte performance can be achieved and lithium ions can move effectively.
- the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate for the purpose of improving battery life characteristics, suppressing battery capacity reduction, and improving battery discharge capacity; or pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexanoic acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N -One or more additives such as substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol, or aluminum trichloride may be further included. At this time, the additive may be included in an amount of 0.1% to 5% by weight based on the total weight of the electrolyte.
- haloalkylene carbonate-based compounds such as difluoroethylene carbonate for the purpose of improving battery life characteristics, suppress
- the lithium secondary battery containing the positive electrode according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity maintenance rate, and is therefore used in portable devices such as mobile phones, laptop computers, digital cameras, and hybrid electric vehicles (hybrid electric vehicles). It is useful in the field of electric vehicles such as electric vehicle (HEV).
- HEV electric vehicle
- the lithium secondary battery according to the present invention is not limited in appearance depending on the use of the battery, and the shape can be adopted according to a case commonly used in the industry.
- the lithium secondary battery may be a battery including a cylindrical or square-shaped battery case using a can, a pouch-shaped battery, or a coin-shaped battery case.
- the lithium secondary battery may be a prismatic secondary battery including a prismatic can as a battery case.
- N-methylpyrrolidone solvent was injected into a homo mixer, and LiNi 0.8 Co 0.1 Mn 0.1 O 2 (hereinafter, 'NCM', average particle size: approximately 2 ⁇ m), LiFePO 4 (hereinafter referred to as 'LFP') as the second positive electrode active material, carbon black as a conductive material, and polyvinylidene fluoride (PVdF) as a binder were added, respectively. Then, they were mixed at 3,000 rpm for 60 minutes to prepare a slurry for forming a first positive electrode mixture layer, a slurry for forming a second positive electrode mixture layer, and a slurry for forming a third positive electrode mixture layer, respectively.
- 'NCM' LiNi 0.8 Co 0.1 Mn 0.1 O 2
- PVdF polyvinylidene fluoride
- the slurry prepared to form each positive electrode composite layer was prepared to contain 48.5% by weight of the positive electrode active material, 1% by weight of the conductive material, and 0.5% by weight of the binder based on solid content, and the first positive electrode active material and the second positive electrode contained in each slurry were prepared.
- the content ratio of the active material (unit: parts by weight) and the average particle size (unit: ⁇ m) of the second positive electrode active material were adjusted as shown in Table 1.
- an aluminum sheet (average thickness: 12 ⁇ m) as a positive electrode current collector, sequentially cast the slurry for forming the first to third positive electrode composite layers prepared previously on the prepared aluminum sheet, and then dry in a vacuum oven at 130°C.
- a positive electrode was manufactured by rolling. At this time, the total thickness of the rolled positive electrode mixture layer was 150 ⁇ m, and the thickness of the individual positive electrode mixture layers was 50 ⁇ m for the three-layer structure and 75 ⁇ m for the two-layer structure.
- An electrode assembly was manufactured by opposing the manufactured cathode to the anode prepared in each of the examples and comparative examples as shown in Table 2 below, and interposing a separator made of 18 ⁇ m polypropylene between them.
- Each manufactured electrode assembly was inserted into a prismatic battery case, an electrolyte composition was injected into the battery case, and the case was sealed to manufacture a prismatic lithium secondary battery.
- Example 8 Anode prepared in Example 1
- Example 9 Anode prepared in Example 2
- Example 10 Anode prepared in Example 3
- Example 11 Anode prepared in Example 4
- Example 12 Anode prepared in Example 5
- Example 13 Anode prepared in Example 6
- Example 14 Anode prepared in Example 7 Comparative Example 3 Anode prepared in Comparative Example 1 Comparative Example 4 Anode prepared in Comparative Example 2
- the lithium secondary batteries manufactured in Examples and Comparative Examples were fully charged at 0.1 C-rate at room temperature (22°C). Then, the initial discharge capacity was measured while discharging the fully charged lithium secondary batteries at a rate of 0.1C. Afterwards, each lithium secondary battery was fully charged at 0.1C-rate and discharged at 1.0C, 2.0C, 5.0C, and 9.0C rates, respectively, and the relative discharge capacity ratio based on the initial discharge capacity for each discharge rate was measured, and the results were reported. It is shown in Table 3 below.
- the lithium secondary batteries manufactured in Examples and Comparative Examples were fully charged at 0.1 C-rate at room temperature (22°C). Then, a secondary battery impact test was performed on fully charged lithium secondary batteries according to the UN1642DL impact certification standard. At this time, the weight of the weight used was 9 kg, and the experiment was performed by dropping it on a round bar with a diameter of 16 mm placed in a secondary battery cell. The results are shown in Table 4 below.
- Example 8 46 ⁇ 1°C 37 ⁇ 1°C 6P/6T 6.7mm ⁇ Example 9 53 ⁇ 1°C 42 ⁇ 1°C 6P/6T 6.9mm ⁇ Example 10 44 ⁇ 1°C 36 ⁇ 1°C 6P/6T 5.9 mm ⁇ Example 11 43 ⁇ 1°C 35 ⁇ 1°C 6P/6T 5.8 mm ⁇ Example 12 42 ⁇ 1°C 34 ⁇ 1°C 6P/6T 5.5mm ⁇ Example 13 46 ⁇ 1°C 37 ⁇ 1°C 6P/6T 6.9mm ⁇ Example 14 48 ⁇ 1°C 38 ⁇ 1°C 6P/6T 6.5mm ⁇ Comparative Example 3 63 ⁇ 1°C 54 ⁇ 1°C 1P/6T 16.5mm ⁇ Comparative Example 4 41 ⁇ 1°C 32 ⁇ 1°C 6P/6T 5.1mm ⁇
- the positive electrode for a lithium secondary battery according to the present invention not only has high energy density, but is also excellent in improving the safety of the battery.
- the secondary batteries of the examples according to the present invention showed that the discharge capacity ratio was maintained at more than 88% even when discharging at a high rate of 5.0C rate or higher. This means that the output of the lithium secondary battery including the positive electrode of the example is excellent.
- the positive electrode of the example showed low internal and external battery temperatures of less than 54°C and less than 43°C when overcharged, respectively, and it was confirmed that no ignition occurred during the nail penetration test and impact test. This means that the safety of the secondary battery including the positive electrode is high.
- the positive electrode according to the present invention not only has excellent energy density by containing a ternary compound containing nickel (Ni), cobalt (Co), manganese (Mn), etc., but also has an outermost layer based on the positive electrode current collector. It can be seen that the safety due to internal short circuit of the secondary battery is improved by containing the iron phosphate compound.
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Abstract
Description
합재층 구조 |
제1 양극 합재층 | 제2 양극 합재층 | 제3 양극 합재층 | |||||||
NCM 함량 | LFP 함량 | LFP 입도 | NCM 함량 | LFP 함량 | LFP 입도 | NCM 함량 | LFP 함량 | LFP 입도 | ||
실시예 1 | 2층 | 75 | - | - | 67.5 | 7.5 | 1.5 | - | - | - |
실시예 2 | 3층 | 50 | - | - | 49.5 | 0.5 | 0.8 | 49 | 1 | 1.5 |
실시예 3 | 3층 | 50 | - | - | 47.5 | 2.5 | 0.8 | 45 | 5 | 1.5 |
실시예 4 | 3층 | 50 | - | - | 45.5 | 4.5 | 0.8 | 41 | 9 | 1.5 |
실시예 5 | 3층 | 50 | - | - | 42.5 | 7.5 | 0.8 | 35 | 15 | 1.5 |
실시예 6 | 3층 | 50 | - | - | 47.5 | 2.5 | 1.5 | 45 | 5 | 1.5 |
실시예 7 | 3층 | 50 | - | - | 46.25 | 3.75 | 0.8 | 46.25 | 3.75 | 1.5 |
비교예 1 | 1층 | 150 | - | - | - | - | - | - | - | - |
비교예 2 | 1층 | - | 150 | 1.5 | - | - | - | - | - | - |
사용된 양극의 종류 | |
실시예 8 | 실시예 1에서 제조된 양극 |
실시예 9 | 실시예 2에서 제조된 양극 |
실시예 10 | 실시예 3에서 제조된 양극 |
실시예 11 | 실시예 4에서 제조된 양극 |
실시예 12 | 실시예 5에서 제조된 양극 |
실시예 13 | 실시예 6에서 제조된 양극 |
실시예 14 | 실시예 7에서 제조된 양극 |
비교예 3 | 비교예 1에서 제조된 양극 |
비교예 4 | 비교예 2에서 제조된 양극 |
C rate 방전용량 대비 상대 방전 용량 비율 [%] | ||||
1.0C | 2.0C | 5.0C | 9.0C | |
실시예 8 | 99.2 | 98.5 | 91.3 | 81.8 |
실시예 9 | 99.7 | 99.0 | 92.6 | 84.7 |
실시예 10 | 99.5 | 98.7 | 91.7 | 82.7 |
실시예 11 | 99.3 | 98.4 | 90.5 | 81.2 |
실시예 12 | 99.1 | 97.5 | 88.3 | 79.9 |
실시예 13 | 99.1 | 98.3 | 90.7 | 82.0 |
실시예 14 | 99.0 | 98.4 | 91.2 | 82.1 |
비교예 3 | 99.9 | 99.0 | 93.2 | 86.5 |
비교예 4 | 99.1 | 96.3 | 87.7 | 67.9 |
과충전 시 전지 온도 | 네일 관통 시 발화여부 (Pass/Test) |
임팩트 시험 | |||
내부 | 표면 | 환봉 평균 눌림폭 | 발화여부 | ||
실시예 8 | 46±1℃ | 37±1℃ | 6P/6T | 6.7 mm | Х |
실시예 9 | 53±1℃ | 42±1℃ | 6P/6T | 6.9 mm | Х |
실시예 10 | 44±1℃ | 36±1℃ | 6P/6T | 5.9 mm | Х |
실시예 11 | 43±1℃ | 35±1℃ | 6P/6T | 5.8 mm | Х |
실시예 12 | 42±1℃ | 34±1℃ | 6P/6T | 5.5 mm | Х |
실시예 13 | 46±1℃ | 37±1℃ | 6P/6T | 6.9 mm | Х |
실시예 14 | 48±1℃ | 38±1℃ | 6P/6T | 6.5 mm | Х |
비교예 3 | 63±1℃ | 54±1℃ | 1P/6T | 16.5 mm | ○ |
비교예 4 | 41±1℃ | 32±1℃ | 6P/6T | 5.1 mm | Х |
Claims (12)
- 양극 집전체 상에 n개(단, n≥2)의 양극 합재층이 위치하되,상기 양극 집전체 표면에 맞닿는 제1 양극 합재층은 하기 화학식 1로 나타내는 리튬 복합 금속 산화물을 포함하는 제1 양극활물질을 포함하고,상기 제1 양극 합재층 상에 배치되는 제2 양극 합재층 내지 제n 양극 합재층은 화학식 1로 나타내는 리튬 복합 금속 산화물을 포함하는 제1 양극활물질 및 하기 화학식 2로 나타내는 인산철 화합물을 포함하는 제2 양극활물질을 포함하는 리튬 이차전지용 양극:[화학식 1]Lix[NiyCozMnwM1 v]O2[화학식 2]LiFeaM2 1-aXO4상기 화학식 1 및 화학식 2에서,M1은 W, Cu, Fe, V, Cr, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, 및 Mo로 이루어진 군에서 선택되는 1종 이상의 원소이고,x, y, z, w 및 v는 각각 1.0≤x≤1.30, 0.1≤y<1, 0≤z≤1, 0≤w≤1, 0≤v≤0.1이되, y+z+w+v=1이며,M2는 W, Cu, Fe, V, Cr, CO, Ni, Mn, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, 및 Mo로 이루어진 군에서 선택되는 1종 이상의 원소이고,X는 P, Si, S, As 및 Sb로 이루어진 군에서 선택되는 1종 이상이며,a 는 0≤a≤0.5이다.
- 제1항에 있어서,제2 양극활물질은 제2 양극 합재층에서 제n 양극 합재층으로 개별 양극 합재층의 위치가 변화됨에 따라 각 양극 합재층 내 농도가 증가하는 리튬 이차전지용 양극.
- 제1항에 있어서,제2 양극활물질은 양극 합재층 전체 중량에 대하여 10 중량% 미만으로 포함되는 리튬 이차전지용 양극.
- 제1항에 있어서,제2 양극활물질은 각 양극 합재층의 중량에 대하여 0.5 내지 20 중량%로 개별 양극 합재층에 포함되는 리튬 이차전지용 양극.
- 제1항에 있어서,제2 양극활물질은 제2 양극 합재층에서 제n 양극 합재층으로 개별 양극 합재층의 위치가 변화됨에 따라 각 양극 합재층에 함유된 제2 양극활물질의 평균 입도가 증가하는 리튬 이차전지용 양극.
- 제1항에 있어서,제2 양극활물질은 0.5㎛ 내지 5㎛의 평균 입도를 갖는 리튬 이차전지용 양극.
- 제1항에 있어서,양극 합재층의 총 두께는 50㎛ 내지 200㎛인 리튬 이차전지용 양극.
- 제1항에 있어서,제1 양극 합재층의 두께는 양극 합재층 총 두께의 10% 내지 60%인 리튬 이차전지용 양극.
- 제1항에 따른 양극; 음극; 및 상기 양극과 음극 사이에 개재된 분리 막을 포함하는 리튬 이차전지용 전극 조립체.
- 제9항에 있어서,음극은 음극 집전체 상에 음극 합재층을 포함하고,상기 음극 합재층은 천연 흑연, 인조 흑연, 팽창 흑연, 하드 카본, 소프트 카본, 탄소섬유, 카본 블랙, 카본나노튜브, 플러렌, 활성탄, 아세틸렌블랙 및 케첸블랙 중 1종 이상의 탄소계 음극활물질을 포함하는 리튬 이차전지용 전극 조립체.
- 제9항에 따른 전극 조립체;상기 전극 조립체가 삽입되는 전지 케이스; 및전극 조립체와 함께 전지 케이스에 주입되는 전해질 조성물을 포함하는 리튬 이차전지.
- 제11항에 있어서,리튬 이차전지는 각형 이차전지인 것을 특징으로 하는 리튬 이차전지.
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JP2020095842A (ja) * | 2018-12-12 | 2020-06-18 | 三洋電機株式会社 | 二次電池 |
KR20190088942A (ko) * | 2019-07-19 | 2019-07-29 | 인천대학교 산학협력단 | 멀티 레이어 구조를 포함하는 이차전지 전극 및 그의 제조방법 |
KR20220045874A (ko) | 2020-10-06 | 2022-04-13 | 주식회사 샛별교육연구 | 교육용 빛소화기 체험키트 |
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KR20230146891A (ko) | 2023-10-20 |
EP4318645A1 (en) | 2024-02-07 |
CN117256055A (zh) | 2023-12-19 |
US20240145682A1 (en) | 2024-05-02 |
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