WO2013157873A1 - 이차전지용 전극 및 이를 포함하는 이차전지 - Google Patents
이차전지용 전극 및 이를 포함하는 이차전지 Download PDFInfo
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- WO2013157873A1 WO2013157873A1 PCT/KR2013/003311 KR2013003311W WO2013157873A1 WO 2013157873 A1 WO2013157873 A1 WO 2013157873A1 KR 2013003311 W KR2013003311 W KR 2013003311W WO 2013157873 A1 WO2013157873 A1 WO 2013157873A1
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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
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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
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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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- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention is an electrode for secondary batteries in which an electrode mixture including an electrode active material, a binder, and a conductive material is coated on a current collector, wherein the electrode active material is a positive electrode active material and / or a negative electrode active material, and the positive electrode active material is represented by the following Chemical Formula 1 Including an oxide, wherein the negative electrode active material includes an oxide of the formula (2), the conductive material is a secondary battery electrode and a secondary battery comprising the same 0.1 to 15% based on the total weight of the electrode mixture It is about.
- M is at least one element selected from the group consisting of Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Ti and Bi Is;
- A is -1 or -divalent one or more anions.
- M ' is at least one element selected from the group consisting of Ti, Sn, Cu, Pb, Sb, Zn, Fe, In, Al and Zr; a and b are 0.1 ⁇ a ⁇ 4; Determined according to the oxidation number of M 'in the range of 0.2 ⁇ b ⁇ 4; c is determined depending on the oxidation number in the range of 0 ⁇ c ⁇ 0.2; A is -1 or -divalent one or more anions.
- a lithium secondary battery has a structure in which a lithium electrolyte is impregnated into an electrode assembly including a cathode including a lithium transition metal oxide, a cathode including a carbon-based active material, and a porous separator.
- the positive electrode is prepared by coating a positive electrode mixture containing a lithium transition metal oxide on an aluminum foil
- the negative electrode is prepared by coating a negative electrode mixture including a carbon-based active material on a copper foil.
- a conductive material is added to the positive electrode mixture and the negative electrode mixture in order to improve the electrical conductivity of the active material.
- a conductive material is essentially added to the positive electrode mixture.
- conductive materials conventionally used to increase the conductivity of the positive electrode mixture have a disadvantage in that the loading density is not increased in the compression process to reduce the thickness of the positive electrode mixture.
- the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
- the inventors of the present application can achieve a desired effect when using an electrode for secondary batteries coated with an electrode mixture containing a predetermined amount of a predetermined electrode active material and a conductive material. It was confirmed that the present invention was completed.
- the present invention is an electrode for secondary batteries, the electrode mixture comprising an electrode active material, a binder and a conductive material is applied to the current collector, the electrode active material is a positive electrode active material and / or negative electrode active material, the positive electrode active material is represented by the formula Including an oxide to be displayed, The anode active material comprises an oxide of the formula (2), The conductive material provides a secondary battery electrode, characterized in that 0.1 to 15% based on the total weight of the electrode mixture.
- M is at least one element selected from the group consisting of Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Ti and Bi Is;
- A is -1 or -divalent one or more anions.
- M ' is at least one element selected from the group consisting of Ti, Sn, Cu, Pb, Sb, Zn, Fe, In, Al and Zr; a and b are 0.1 ⁇ a ⁇ 4; Determined according to the oxidation number of M 'in the range of 0.2 ⁇ b ⁇ 4; c is determined depending on the oxidation number in the range of 0 ⁇ c ⁇ 0.2; A is -1 or -divalent one or more anions.
- the conductive material may include 1 to 50% by weight based on the total weight of the electrode mixture, it is preferable that 15 to 25% is included in order to exhibit a more preferable electrical conductivity improvement effect.
- the inventors of the present invention by using a predetermined material having a very high electrical conductivity as a conductive material, even if 0.1 to 15% of the material contained in the positive electrode mixture to improve the electrical conductivity, even if a relatively small amount of conductive material It confirmed that it showed the outstanding output characteristic.
- Such predetermined material may be carbon nanotubes (CNT) or graphene.
- CNT carbon nanotubes
- graphene graphene
- the carbon nanotubes are not limited as long as they are known in the art, and in detail, those having a mean particle size of 5 to 50 nm and a length of 0.5 to 10 ⁇ m may be used, and more specifically, an average particle diameter of 5 to 20 nm. And having a length of 0.5 to 5 ⁇ m can be used.
- the oxide of Formula 1 may be represented by the following Formula 3.
- the oxide of Formula 3 may be LiNi 0.5 Mn 1.5 O 4 or LiNi 0.4 Mn 1.6 O 4 .
- the average particle diameter (D50) of the oxide of Formula 1 may be 5 to 30 ⁇ m and specifically 8 to 20 ⁇ m.
- the average particle diameter of the oxide in the present invention means, in detail, the particle diameter when a plurality of particles are aggregated to form one combination agent.
- the positive electrode active material tends to aggregate each oxide unit with each other according to the set conditions of the manufacturing process to form one combination, and such agglomeration combination exhibits desirable active material properties by itself. Therefore, the average particle diameter of the oxide specifically means the particle diameter of such agglomeration combination.
- the oxide of Formula 2 may be an oxide represented by the following Formula 4.
- a and b are 0.1 ⁇ a ⁇ 4; 0.2 ⁇ b ⁇ 4.
- the oxide of Formula 4 may be Li 1.33 Ti 1.67 O 4 or LiTi 2 O 4 .
- the present invention also provides a secondary battery comprising the electrode for secondary batteries.
- the secondary battery according to the present invention includes a cathode prepared by applying a mixture of a cathode active material, a conductive material, and a binder on a cathode current collector, followed by drying and pressing, and a cathode manufactured using the same method, in which case, In some cases, a filler may be further added to the mixture.
- the positive electrode current collector is generally made to a thickness of 3 to 500 ⁇ m. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery. For example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like may be used.
- the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- the conductive material may further include the aforementioned carbon nanotube or graphene new material.
- Such materials may be added in an amount of 1 to 20% by weight based on the weight of the positive electrode mixture including the positive electrode active material, and are not particularly limited as long as they are conductive without causing chemical changes in the battery.
- natural graphite Graphite such as artificial graphite
- Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black
- Conductive fibers such as carbon fibers and metal fibers
- Metal powders such as carbon fluoride powder, aluminum powder and nickel powder
- Conductive whiskeys such as zinc oxide and potassium titanate
- Conductive metal oxides such as titanium oxide
- Conductive materials such as polyphenylene derivatives and the like can be used.
- the binder is a component that assists in bonding the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 50 wt% based on the total weight of the mixture including the positive electrode active material.
- binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
- the filler is optionally used as a component for inhibiting expansion of the positive electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
- the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
- the negative electrode current collector is generally made of a thickness of 3 ⁇ 500 ⁇ m.
- a negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy, and the like can be used.
- fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
- the negative electrode active material may be a material defined above, for example, carbon, such as non-graphitized carbon, graphite carbon; Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3;1 ⁇ z8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and metal oxides such as Bi 2 O 5 ; Conduct
- the secondary battery may have a structure in which a lithium salt-containing electrolyte is impregnated in an electrode assembly having a separator interposed between a positive electrode and a negative electrode.
- the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
- the pore diameter of the separator is generally from 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
- a separator for example, olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
- a solid electrolyte such as a polymer
- the solid electrolyte may also serve as a separator.
- the lithium salt-containing electrolyte solution is composed of an electrolyte solution and a lithium salt, and the electrolyte solution, but non-aqueous organic solvent, organic solid electrolyte, inorganic solid electrolyte and the like are used, but are not limited thereto.
- non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxorone, formamide, dimethylformamide, dioxolon , Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbo Aprotic organic solvents such as nate derivatives, tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymerizers containing ionic dissociating groups and the like can be used.
- Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates, and the like of Li, such as Li 4 SiO 4 —LiI-LiOH, Li 3 PO 4 —Li 2 S-SiS 2 , and the like, may be used.
- the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide.
- pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
- a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included. Carbonate), PRS (Propene sultone) may be further included.
- a lithium salt such as LiPF 6 , LiClO 4 , LiBF 4 , LiN (SO 2 CF 3 ) 2
- a lithium salt is a linear form of cyclic carbonate of EC or PC, which is a highly dielectric solvent, and DEC, DMC, or EMC, which is a low viscosity solvent.
- the lithium salt-containing non-aqueous electrolyte can be prepared by adding to a mixed solvent of carbonate.
- the present invention also provides a battery module including the secondary battery as a unit cell, and provides a battery pack including the battery module.
- the battery pack may be used as a power source for medium and large devices requiring high temperature stability, long cycle characteristics, high rate characteristics, and the like.
- Examples of the medium-to-large device include a power tool that is driven by an electric motor; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts; Power storage systems and the like, but is not limited thereto.
- Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like
- Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts; Power storage systems and the like, but is not limited thereto.
- LiNi 0.5 Mn 1.5 O 4 anode active material
- carbon nanotubes conductive agent having a length of 1 ⁇ m and 5% by weight of PVdF (binder)
- the positive electrode mixture was coated on an aluminum current collector, dried, and pressed to prepare a positive electrode for a secondary battery.
- Example 1 85% by weight of LiNi 0.5 Mn 1.5 O 4 (anode active material), an average particle diameter of 10 nm, 10% by weight of carbon nanotube (conductive agent) having a length of 1 ⁇ m and 5% by weight of PVdF (binder) were used.
- a positive electrode for a secondary battery was manufactured in the same manner as in Example 1 except for the foregoing.
- a positive electrode for a secondary battery was manufactured in the same manner as in Example 2, except that the positive electrode mixture was manufactured by using Super-P instead of the carbon nanotubes as the conductive agent in Example 2.
- the negative electrode mixture was prepared by adding the positive electrode prepared in Examples 1, 2 and Comparative Example 1, 90 wt% of Li 1.33 Ti 1.67 O 4 , 5 wt% of Super-C (conductor) and 5 wt% of PVdF (binder) to NMP. After the preparation, the electrode assembly was prepared using a porous separator made of a negative electrode and a polypropylene prepared by coating, drying and pressing on an aluminum current collector. Thereafter, the electrode assembly was placed in a pouch and the lead wires were connected. Then, 1 M of LiPF 6 salt was dissolved in a volume ratio of 1: 1 ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC). ) was injected into the electrolyte, and then sealed to assemble a lithium secondary battery. Relative capacity reduction rate according to the size of the secondary battery C-rate is shown in Figure 1 below.
- the batteries of Examples 1 and 2 have a relatively small capacity reduction rate even when the size of C-rate is larger than that of Comparative Example 1.
- the electrode for secondary batteries according to the present invention includes a predetermined conductive material, and includes 0.1 to 15% of the conductive material based on the total weight of the electrode mixture, thereby improving the electrical conductivity while using a small amount of C-rate. Even if the size increases, the relative capacity decrease rate is small, and as a result, it is possible to exhibit excellent output characteristics and charging speed of the secondary battery including the same.
Abstract
Description
Claims (14)
- 전극 활물질, 바인더 및 도전재를 포함하는 전극 합제가 집전체에 도포되어 있는 이차전지용 전극으로서, 상기 전극 활물질은 양극 활물질 및/또는 음극 활물질이고, 상기 양극 활물질은 하기 화학식 1로 표시되는 산화물을 포함하고, 상기 음극 활물질은 하기 화학식 2의 산화물을 포함하며, 상기 도전재는 전극 합제 총 중량을 기준으로 0.1 내지 15 %가 포함되어 있는 것을 특징으로 하는 이차전지용 전극:LixMyMn2-yO4-zAz (1)상기 식에서, 0.9≤x≤1.2, 0<y<2, 0≤z<0.2이고,M은 Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Ti 및 Bi로 이루어진 군에서 선택되는 하나 이상의 원소이며;A는 -1 또는 -2가의 하나 이상의 음이온이다.LiaM'bO4-cAc (2)상기 식에서, M'은 Ti, Sn, Cu, Pb, Sb, Zn, Fe, In, Al 및 Zr로 이루어진 군에서 선택되는 하나 이상의 원소이고; a 및 b는 0.1≤a≤4; 0.2≤b≤4의 범위에서 M'의 산화수(oxidation number)에 따라 결정되며; c는 0≤c<0.2의 범위에서 산화수에 따라 결정되고; A는 -1 또는 -2가의 하나 이상의 음이온이다.
- 제 1 항에 있어서, 상기 도전재는 전극 합제 총 중량을 기준으로 1 내지 10 %가 포함되어 있는 것을 특징으로 이차전지용 전극.
- 제 1 항에서 상기 도전재는 카본 나노 튜브 (Carbonnanotube, CNT) 또는 그래핀(Graphene)인 것을 특징으로 하는 이차전지용 전극.
- 제 3 항에 있어서, 상기 카본 나노 튜브는 5 내지 50 nm의 평균 입경을 가지며 0.5 내지 10 ㎛의 길이를 가지는 것을 특징으로 하는 이차전지용 전극.
- 제 1 항에 있어서, 상기 화학식 1의 산화물은 하기 화학식 3으로 표시되는 것을 특징으로 하는 이차전지용 전극.LixNiyMn2-yO4 (3)상기 식에서, 0.9≤x≤1.2, 0.4≤y≤0.5이다.
- 제 5 항에 있어서, 상기 산화물은 LiNi0.5Mn1.5O4 또는 LiNi0.4Mn1.6O4 인 것을 특징으로 하는 이차전지용 전극.
- 제 1 항에 있어서, 상기 화학식 2의 산화물은 하기 화학식 4로 표시되는 것을 특징으로 하는 이차전지용 전극:LiaTibO4 (4)상기 식에서 a 및 b는 0.1≤a≤4; 0.2≤b≤4이다.
- 제 7 항에 있어서, 상기 화학식 4의 산화물은 Li1.33Ti1.67O4 또는 LiTi2O4로 표시되는 것을 특징으로 하는 이차전지용 전극.
- 제 1 항 내지 제 8 항 중 어느 한 항에 따른 이차전지용 전극을 포함하는 것을 특징으로 하는 이차전지.
- 제 9 항에 있어서, 상기 이차전지는 리튬 이차전지인 것을 특징으로 하는 이차전지.
- 제 10 항에 따른 이차전지를 단위전지로 포함하는 것을 특징으로 하는 전지모듈.
- 제 11 항에 따른 전지모듈을 포함하는 것을 특징으로 하는 전지팩.
- 제 12 항에 따른 전지팩을 포함하는 것을 특징으로 하는 디바이스.
- 제 13 항에 있어서, 상기 디바이스는 전기자동차, 하이브리드 전기자동차, 플러그-인 하이브리드 전기자동차, 또는 전력저장용 시스템인 것을 특징으로 하는 디바이스.
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EP13778277.7A EP2811552B1 (en) | 2012-04-18 | 2013-04-18 | Electrode for secondary battery, and secondary battery comprising same |
CN201380015003.6A CN104185915A (zh) | 2012-04-18 | 2013-04-18 | 二次电池用电极和包含所述电极的二次电池 |
US14/485,913 US9508993B2 (en) | 2012-04-18 | 2014-09-15 | Electrode for secondary battery and secondary battery including the same |
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KR102563808B1 (ko) * | 2019-07-29 | 2023-08-03 | 주식회사 엘지에너지솔루션 | 집전체의 양면에 서로 다른 조성의 활물질을 포함하는 음극 합제들이 형성되어 있는 음극을 포함하는 젤리-롤형 전극조립체, 이를 포함하는 이차전지, 및 이차전지를 포함하는 디바이스 |
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EP2811552A1 (en) | 2014-12-10 |
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KR20130117351A (ko) | 2013-10-25 |
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CN107134578A (zh) | 2017-09-05 |
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JP5944572B2 (ja) | 2016-07-05 |
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