WO2012141503A2 - Matière active d'électrode positive, son procédé de préparation et électrode positive et batterie au lithium l'utilisant - Google Patents

Matière active d'électrode positive, son procédé de préparation et électrode positive et batterie au lithium l'utilisant Download PDF

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WO2012141503A2
WO2012141503A2 PCT/KR2012/002772 KR2012002772W WO2012141503A2 WO 2012141503 A2 WO2012141503 A2 WO 2012141503A2 KR 2012002772 W KR2012002772 W KR 2012002772W WO 2012141503 A2 WO2012141503 A2 WO 2012141503A2
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active material
group
cathode active
carbon
positive electrode
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WO2012141503A3 (fr
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김윤미
최동웅
최규범
김동일
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Dongjin Semichem Co Ltd
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • 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
    • 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

  • a positive electrode active material a manufacturing method thereof, and a positive electrode and a lithium battery employing the same.
  • the olivine positive electrode active material is excellent in high temperature stability as LiCoO 2 as a phosphate.
  • LiFePO 4 is structurally stable without structural change during charge and discharge, and does not have side reactions such as oxygen generation and is inexpensive. However, LiFePO 4 has low conductivity and low energy capacity .
  • One aspect is to provide a positive electrode active material having improved conductivity.
  • Another aspect is to provide a method for producing the cathode active material.
  • Another aspect is to provide a positive electrode including the positive electrode active material.
  • Another aspect is to provide a lithium battery employing the positive electrode.
  • a core comprising a material having an olivine structure
  • It includes a carbon-based coating layer formed on at least a portion of the core surface
  • cathode active material including one or more carbon-based coating layers selected from the group consisting of conductive metal materials and nonmetallic hetero elements belonging to Groups 15 to 17 of the Periodic Table of the Elements.
  • Preparing a mixture by mixing a material having an olivine structure, a carbon precursor, and optionally one or more precursors selected from the group consisting of nonmetallic hetero elements and conductive metal materials belonging to Groups 15-17 of the Periodic Table of Elements; And
  • It is provided with a method for producing a positive electrode active material comprising a; firing the mixture in an inert atmosphere.
  • a cathode including the cathode active material is provided.
  • a lithium battery employing the positive electrode.
  • a cathode active material with improved conductivity by including a cathode active material with improved conductivity, high rate characteristics of a lithium battery may be improved.
  • FIG. 1 is a transmission electron microscope (TEM) image of a cathode active material prepared in Example 3.
  • FIG. 1 is a transmission electron microscope (TEM) image of a cathode active material prepared in Example 3.
  • FIG. 2 is a scanning electron microscope (SEM) image of the cathode active material prepared in Example 3.
  • SEM scanning electron microscope
  • FIG. 3 is an EDAX spectrum of the cathode active material prepared in Example 3.
  • FIG. 4 is a Nyquist plot of the impedance measurement results of the cathode active materials prepared in Examples 1 and 3.
  • FIG. 4 is a Nyquist plot of the impedance measurement results of the cathode active materials prepared in Examples 1 and 3.
  • FIG. 5 is a schematic diagram of a lithium battery according to an exemplary embodiment.
  • a cathode active material includes a core including a material having an olivine structure; And a carbon-based coating layer formed on at least a portion of the core surface, wherein the carbon-based coating layer includes at least one selected from the group consisting of a conductive metal material and a nonmetallic hetero element belonging to Groups 15 to 17 of the Periodic Table of the Elements.
  • the cathode active material may have improved conductivity.
  • the carbon-based coating layer formed on the surface of the core including the material having the olivine structure may have high conductivity, robustness, and excellent thermal stability by additionally including a conductive metal material and / or a nonmetallic dissimilar element. . Therefore, the surface conductivity of the material core having the olivine structure can be improved.
  • the nonmetallic dissimilar element may be at least one selected from the group consisting of P, S, F, Cl, Br, I, and O.
  • the carbon-based coating layer may include one or more substituents and / or ions selected from the group consisting of PO 4 , SO 4 , F, Cl, Br, and I, but are not necessarily limited thereto.
  • any one capable of improving the conductivity of the carbon-based coating layer is possible.
  • the material having the olivine structure may also include at least one of the conductive metal material and the nonmetallic dissimilar element.
  • the content of the nonmetallic dissimilar element may be 0.05 to 5% by weight based on the total weight of the positive electrode active material.
  • the content of the nonmetallic dissimilar element may be 5 to 50000 ppm based on the total weight of the positive electrode active material. If the content of the non-metallic dissimilar element is too low, high rate characteristics may be lowered. If the content of the non-metallic dissimilar element is too high, discharge capacity may be reduced.
  • the conductive metal material may be at least one selected from the group consisting of alkali metals, alkaline earth metals, transition metals, metalloids, and metals belonging to groups 13 to 15 of the periodic table of the elements.
  • the conductive metal material may be at least one selected from the group consisting of Ni, Co, Fe, Mo, Cr, B, Al, Ga, Si, Sn, Na, K, Mg, and Ca, but is not limited thereto.
  • any metal material capable of improving conductivity of the cathode active material is possible.
  • the content of the conductive metal material in the positive electrode active material may be 0.1 to 10% by weight of the total weight of the positive electrode active material. If the content of the conductive metal material is too low, the conductivity of the positive electrode active material may be lowered. If the content of the conductive metal material is too high, the discharge capacity may be reduced.
  • an average particle diameter of the conductive metal material may be 0.1 nm to 100 nm.
  • the average particle diameter of the conductive metal material may be 0.5 nm to 50 nm.
  • the average particle diameter of the conductive metal material may be 1 nm to 10 nm.
  • the conductive metal material may be a particulate powder. If the average particle diameter of the conductive metal material is too small, an increase in electrode volume may occur due to the lower density of the metal material during electrode production, and thus the capacity per volume may be reduced. If the average particle diameter of the conductive metal material is too large, the electrode is homogeneous. One slurry can be difficult to form.
  • the carbon-based coating layer covering the conductive metal material in the cathode active material may be a carbon film that is a fired product of a carbon source such as glucose.
  • the carbon source is not particularly limited as long as it can provide a carbon film by firing in the art.
  • the carbon source may be a monomer, oligomer, natural polymer, synthetic polymer, or the like.
  • the carbon source may be glucose, sucrose, starch, oligosaccharide, polyoligosaccharide, fructose, cellulose, polymer of furfuryl alcohol, block copolymer of ethylene and ethylene oxide, vinyl resin, cellulose resin, phenolic It may be at least one selected from the group consisting of resin, pitch resin and tar resin.
  • various natural materials may also be used.
  • cotton wool, paper, textiles, wood, pollen, sugar beet, grass, insect wings, egg shells, hair, squid bones, chitin, algae, sea urchins and the like can also be used.
  • the carbon-based coating layer including the conductive metal material and / or the nonmetallic heterogeneous element belonging to Groups 15 to 17 of the Periodic Table of the Elements may have a crystal spacing d 002 of 3.45 ⁇ or more or amorphous.
  • the gap d 002 between the crystal planes of the carbon-based coating layer may be composed of low crystalline carbon or amorphous carbon of 3.45 kPa to 3.70 kPa.
  • the carbon-based coating layer When the carbon-based coating layer has a high crystallinity, it may act as a kind of graphite and may react with the electrolyte at the surface.
  • the low crystalline or amorphous carbon film can achieve high charge and discharge efficiency because the carbon film does not react with the electrolyte during charging and discharging, thereby preventing decomposition of the electrolyte.
  • the carbon-based coating layer is so close that it blocks the contact between the core and the electrolyte solution can prevent the reaction between the electrolyte and the core. That is, the carbon film may act as a reaction prevention layer to block contact between the electrolyte and the material having the olivine structure.
  • the average thickness of the carbon-based coating layer in the positive electrode active material may be 1 nm to 5 ⁇ m.
  • the thickness of the carbon-based coating layer may be 2 nm to 100 nm. If the average thickness is less than 1 nm, conductivity may decrease. If the average thickness is more than 20 ⁇ m, the density of the positive electrode active material may decrease.
  • the thickness of the carbon-based coating layer is best maintained uniformly over the entire area around the core, but there may be a dispersion of the thickness or may be coated only on a portion of the core.
  • an average particle diameter of the core including the material having the olivine structure may be 10 nm to 20 ⁇ m.
  • the average particle diameter of the core may be 50 nm to 10 ⁇ m.
  • the average particle diameter of the core may be 50 nm to 1000 nm.
  • the core may be a particulate powder. If the average particle diameter of the core is less than 10 nm, a problem may occur in the capacity implementation, and if the average particle diameter of the core is more than 20 ⁇ m, a problem may occur in the diffusion of lithium.
  • a material having the olivine structure may be represented by Formula 1 below:
  • Me is at least one selected from the group consisting of Fe, Mn, Ni and Co
  • M is one or more selected from the group consisting of Mg, Ca, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al and Si
  • X is at least one selected from the group consisting of S and F.
  • the material having the olivine structure may be at least one selected from the group consisting of LiFePO 4 , LiFe 1-a Mn a PO 4 (0 ⁇ a ⁇ 1) and LiMnPO 4 .
  • a method of manufacturing a cathode active material is performed by mixing one or more precursors selected from the group consisting of a material having an olivine structure, a carbon precursor, and optionally a nonmetallic hetero element and a conductive metal material belonging to Groups 15 to 17 of the Periodic Table Preparing a mixture; And calcining the mixture in an inert atmosphere.
  • a carbon-based coating layer is formed on part or all of the surface of the material having the olivine structure.
  • the carbon precursor may be a complex of a hydrocarbon and a metal salt.
  • it may include one or more selected from the group consisting of glucophosphate disodium salt, glucophosphate magnesium salt, and glucophosphate iron salt. That is, the carbon precursor includes functional groups having ion conductivity and / or conductivity in precursor molecules. Therefore, by firing the carbon precursor, the carbon-based coating layer may include a component having ion conductivity and / or conductivity, thereby improving conductivity.
  • the carbon precursor may further include a conventional general carbon precursor.
  • the carbon source may be a monomer, oligomer, natural polymer, synthetic polymer, or the like.
  • the carbon source may be glucose, sucrose, starch, oligosaccharide, polyoligosaccharide, fructose, cellulose, polymer of furfuryl alcohol, block copolymer of ethylene and ethylene oxide, vinyl resin, cellulose resin, phenolic It may be at least one selected from the group consisting of resin, pitch resin and tar resin.
  • various natural materials may also be used. For example, cotton wool, paper, textiles, wood, pollen, sugar beet, grass, insect wings, egg shells, hair, squid bones, chitin, algae, sea urchins and the like can also be used.
  • the precursor of the nonmetallic heterogeneous element belonging to Groups 15 to 17 of the periodic table of the elements is phosphoric acid (H 3 PO 4 ), ammonium chloride (NH 4 Cl) and sulfuric acid (H 2 SO 4 ) It may be one or more selected from, but is not limited to these, any precursor that can leave the ion conductive and / or conductive components in the carbon-based coating layer by firing in the art.
  • the precursor of the conductive metal material may be one or more selected from the group consisting of FeCl 2 , MgCl 2 , NiCl 2, and CoCl 2 , but is not limited thereto, and forms a conductive metal material by firing in the art. Any precursor that can be made is possible.
  • the material having the olivine structure may be represented by the following formula (1):
  • Me is at least one selected from the group consisting of Fe, Mn, Ni and Co
  • M is one or more selected from the group consisting of Mg, Ca, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al and Si
  • X is at least one selected from the group consisting of S and F.
  • the material having the olivine structure may be at least one selected from the group consisting of LiFePO 4 , LiFe 1-a Mn a PO 4 (0 ⁇ a ⁇ 1) and LiMnPO 4 .
  • the firing temperature may be 500 to 1000 ° C., but is not necessarily limited to the above temperature range, and may be appropriately selected within a range capable of achieving the object of the present invention.
  • the temperature may be 500 ⁇ 800 °C.
  • the temperature may be 600 to 750 ° C. If the firing temperature is too low, the crystallinity of the fired product may be insufficient or the specific surface area may be large, and the tap density may be low. In addition, the improvement of crystallinity may not be sufficient and the material may not be sufficiently stabilized, such that discharge capacity, life characteristics, and the like may be lowered. If the firing temperature is too high, phase decomposition may occur. Therefore, the cathode active material having further improved physical properties at a firing temperature of a predetermined range in the cathode active material manufacturing method may be manufactured.
  • the firing time may be 1 to 10 hours.
  • the firing time may be 1 to 20 hours.
  • the firing time may be 3 to 15 hours. If the firing time is too short, the crystallinity of the fired product may be insufficient or the specific surface area may be large, and the tap density may be low. In addition, the improvement of crystallinity may not be sufficient and the material may not be sufficiently stabilized, such that discharge capacity, life characteristics, and the like may be lowered. If the firing time is too long, manufacturing efficiency may decrease. Therefore, the cathode active material may be manufactured having more improved physical properties in a predetermined range of firing time in the cathode active material manufacturing method.
  • the positive electrode includes the positive electrode active material described above.
  • the positive electrode may be manufactured by a method in which a positive electrode active material composition including the positive electrode active material and a binder is molded into a predetermined shape or the positive electrode active material composition is applied to a current collector such as copper foil or aluminum foil. Can be.
  • a cathode active material composition in which the cathode active material, the conductive material, the binder, and the solvent are mixed is prepared.
  • the positive electrode active material composition is directly coated on a metal current collector to prepare a positive electrode plate.
  • the cathode active material composition may be cast on a separate support, and then a film peeled from the support may be laminated on a metal current collector to prepare a cathode plate.
  • the anode is not limited to the above enumerated forms and may be in any form other than the foregoing.
  • Carbon black, graphite fine particles and the like may be used as the conductive material, but is not limited thereto, and any conductive material may be used as long as it can be used as a conductive material in the art.
  • graphite such as natural graphite and 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 may be vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene and mixtures thereof, or styrene butadiene rubber polymers. It may be used, but is not limited to these may be used as long as it can be used as a binder in the art.
  • PVDF polyvinylidene fluoride
  • N-methylpyrrolidone N-methylpyrrolidone, acetone, or water
  • any solvent may be used as long as it can be used in the art.
  • the content of the positive electrode active material, the conductive material, the binder, and the solvent is at a level commonly used in lithium batteries. At least one of the conductive material, the binder, and the solvent may be omitted according to the use and configuration of the lithium battery.
  • a lithium battery employs a cathode including the cathode active material.
  • the lithium battery may be manufactured by the following method.
  • a positive electrode is manufactured according to the above positive electrode manufacturing method.
  • a negative electrode active material composition is prepared by mixing a negative electrode active material, a conductive material, a binder, and a solvent.
  • the negative electrode active material composition is directly coated and dried on a metal current collector to prepare a negative electrode plate.
  • the negative electrode active material composition may be cast on a separate support, and then a film peeled from the support may be laminated on a metal current collector to prepare a negative electrode plate.
  • the negative electrode active material is generally used in this field, and is not particularly limited. More specifically, lithium metal, a metal alloyable with lithium, a transition metal oxide, a transition metal sulfide, a material capable of doping and undoping lithium, Materials capable of reversibly inserting and detaching lithium ions, conductive polymers, and the like may be used.
  • the transition metal oxide may be, for example, tungsten oxide, molybdenum oxide, titanium oxide, lithium titanium oxide, vanadium oxide, lithium vanadium oxide, or the like.
  • Group I metal compounds such as CuO, Cu 2 O, Ag 2 O, CuS, CuSO 4 , Group IV metal compounds such as TiS 2 , SnO, V 2 O 5 , V 6 O 12 , VO x (0 ⁇ x ⁇ 6), Group V metal compounds such as Nb 2 O 5 , Bi 2 O 3 , Sb 2 O 3 , Group VI such as CrO 3 , Cr 2 O 3 , MoO 3 , MoS 2 , WO 3 , SeO 2 Group VII metal compounds such as metal compounds, MnO 2 , Mn 2 O 3 , Fe 2 O 3 , FeO, Fe 3 O 4 , Ni 2 O 3 , Group VIII metal compounds such as NiO, CoO 3 , CoO, and general formula Li x MN y X 2 (M, N is a metal of Groups I
  • Materials capable of doping and undoping lithium include, for example, Si, SiO x (0 ⁇ x ⁇ 2), Si-Y alloys (wherein Y is an alkali metal, an alkaline earth metal, an element of Group 13, an element of Group 14, and a transition). Metals, rare earth elements or combinations thereof, not Si), Sn, SnO 2 , Sn-Y (wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof) Combination element, not Sn), and at least one of them and SiO 2 may be mixed and used.
  • a carbon-based material may be used as long as it is a carbon-based negative electrode active material generally used in lithium batteries.
  • the crystalline carbon is, for example, amorphous, plate-like, flake, spherical or fibrous natural graphite; Or artificial graphite, and the amorphous carbon may be, for example, soft carbon (low temperature calcined carbon) or hard carbon, mesophase pitch carbide, calcined coke, or the like.
  • the conductive polymer may be a disulfide-based, polyethlyenedioxythiophene (PEDOT), polypyrrole, polyaniline, polyparaphenylene, polyacetylene, polyacene-based material, or the like.
  • PEDOT polyethlyenedioxythiophene
  • PAN polyethlyenedioxythiophene
  • polypyrrole polypyrrole
  • polyaniline polyaniline
  • polyparaphenylene polyacetylene
  • polyacene-based material or the like.
  • the same conductive material, binder, and solvent may be used as the positive electrode active material composition.
  • a plasticizer may be further added to the cathode active material composition and / or the anode active material composition to form pores inside the electrode plate.
  • the amount of the negative electrode active material, the conductive material, the binder, and the solvent is at a level commonly used in lithium batteries. At least one of the conductive material, the binder, and the solvent may be omitted according to the use and configuration of the lithium battery.
  • the separator may be used as long as it is commonly used in lithium batteries.
  • a low resistance to the ion migration of the electrolyte and excellent in the ability to hydrate the electrolyte can be used.
  • it is selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) or a combination thereof, and may be in a nonwoven or woven form.
  • PTFE polytetrafluoroethylene
  • a rollable separator such as polyethylene or polypropylene may be used for a lithium ion battery, and a separator having excellent organic electrolyte impregnation ability may be used for a lithium ion polymer battery.
  • the separator may be manufactured according to the following method.
  • a separator composition is prepared by mixing a polymer resin, a filler, and a solvent.
  • the separator composition may be directly coated and dried on the electrode to form a separator.
  • a separator film separated from the support may be laminated on the electrode to form a separator.
  • the polymer resin used to manufacture the separator is not particularly limited, and any materials used for the binder of the electrode plate may be used.
  • any materials used for the binder of the electrode plate may be used.
  • vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate or mixtures thereof and the like can be used.
  • the electrolyte may be an organic electrolyte.
  • the organic electrolyte may be prepared by dissolving lithium salt in an organic solvent.
  • the organic solvent may be used as long as it can be used as an organic solvent in the art.
  • Any lithium salt may be used as long as it can be used as a lithium salt in the art.
  • the electrolyte may be a solid electrolyte such as an organic solid electrolyte or an inorganic solid electrolyte.
  • the solid electrolyte may also serve as a separator.
  • organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymers containing ionic dissociating groups and the like can be used.
  • the inorganic solid electrolyte may be, for example, boron oxide, lithium oxynitride, and the like, but is not limited thereto. Any inorganic solid electrolyte may be used as the solid electrolyte in the art.
  • the solid electrolyte may be formed on the negative electrode by sputtering or the like.
  • the lithium battery 1 includes a positive electrode 3, a negative electrode 2, and a separator 4.
  • the positive electrode 3, the negative electrode 2, and the separator 4 described above are wound or folded to be accommodated in the battery case 5. Subsequently, an organic electrolyte is injected into the battery case 5 and sealed with a cap assembly 6 to complete the lithium battery 1.
  • the battery case may be cylindrical, rectangular, thin film, or the like.
  • the lithium battery may be a thin film battery.
  • the lithium battery may be a lithium ion battery.
  • a separator may be disposed between the positive electrode and the negative electrode to form a battery structure.
  • the battery structure is stacked in a bi-cell structure, and then impregnated in an organic electrolyte, and the resultant is accommodated in a pouch and sealed to complete a lithium ion polymer battery.
  • a plurality of battery structures are stacked to form a battery pack connected in series, and the battery pack may be used in any device requiring high capacity and high power.
  • the battery pack may be used in any device requiring high capacity and high power.
  • it can be used in notebooks, smartphones, power tools, electric vehicles and the like.
  • the lithium battery has excellent high temperature cycling characteristics and high temperature stability, and thus is suitable for medium and large energy storage devices.
  • EV electric vehicle
  • PHEV plug-in hybrid electric vehicle
  • the slurry was prepared to have a weight ratio of 8: 8.
  • the slurry was applied using a doctor blade to a 100 ⁇ m gap on an aluminum current collector and dried at 120 ° C. to prepare a positive electrode plate.
  • a lithium metal is used as a counter electrode, and a solution in which a PE separator and 1.3 M LiPF 6 are dissolved in EC (ethylene carbonate) + DEC (diethylene carbonate) (3: 7 volume ratio) is used as an electrolyte. 2032 standard coin cell was used.
  • a carbon-based coating layer was formed on the olivine core.
  • the thickness of the coating layer was about 5 nm.
  • the particle size of the cathode active material was about 200 nm.
  • the lattice size of LiFePO 4 was calculated from XRD diffraction patterns for the positive electrode active material powders prepared in Examples 1 to 8 and Comparative Example 1.
  • the cathode active material of Examples reduced the lattice size compared to Comparative Example 1. That is, since the lattice size is reduced by the addition of the conductive metal material and / or the nonmetallic dissimilar element, it is determined that the conductive metal material and / or the nonmetallic dissimilar element also exist in the olivine core of the cathode active material.
  • Example 1 10.301 5.991 4.684 289.065
  • Example 2 10.305 5.992 4.686 289.349
  • Example 3 10.315 5.995 4.690 290.022
  • Example 4 10.320 5.998 4.692 290.432
  • Example 5 10.298 5.989 4.684 288.884
  • Example 6 10.299 5.991 4.683 288.947
  • Example 7 10.325 6.004 4.693 290.925
  • Example 8 10.326 6.005 4.693 291.002 Comparative Example 1 10.336 6.006 4.695 291.456
  • the coin cell to which the cathode active materials prepared in Example 1 and Comparative Example 1 were applied was measured by a 2-probe method using PARSTAT 2273 for impedance analysis.
  • the frequency range was 10 4 Hz to 10 MHz.
  • the Nyquist plot obtained from the impedance measurement is shown in FIG. 4.
  • the cathode active material of Example 1 has improved impedance compared to the cathode active material of Comparative Example 1, thereby improving conductivity.
  • the lithium batteries of Examples 9 to 16 significantly improved high rate characteristics compared to the lithium batteries of Comparative Example 2.
  • the coin cell prepared in Examples 9 to 16 and Comparative Example 2 was charged and discharged at a constant current of 1.0 C-rate up to 100 cycles in a voltage range of 2.0 to 4.0 V relative to lithium metal at room temperature, and then the discharge capacity was measured. Capacity retention rate was calculated from Equation 1 and the results are shown in Table 3 below.
  • the lithium batteries of Examples 9 to 16 at high rates have improved life characteristics compared to the lithium batteries of Comparative Example 2.

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  • Electrochemistry (AREA)
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Abstract

L'invention concerne une matière active d'électrode positive, comprenant : un noyau contenant une matière ayant une structure d'olivine ; et une couche de revêtement à base de carbone, formée sur au moins une partie de la surface du noyau, la couche de revêtement à base de carbone contenant au moins l'un choisi dans un groupe consistant en une matière métallique conductrice et les éléments hétérogènes non métalliques des groupes 15 à 17 du tableau périodique des éléments. L'invention concerne également un procédé de préparation de la matière active d'électrode positive et une électrode active et une batterie au lithium utilisant la matière active d'électrode positive.
PCT/KR2012/002772 2011-04-14 2012-04-12 Matière active d'électrode positive, son procédé de préparation et électrode positive et batterie au lithium l'utilisant Ceased WO2012141503A2 (fr)

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KR10-2011-0034865 2011-04-14

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CN116598448A (zh) * 2023-05-06 2023-08-15 浙江中哲新能源有限公司 一种聚阴离子型硫酸盐正极材料及其制备方法
WO2023225836A1 (fr) * 2022-05-24 2023-11-30 宁德时代新能源科技股份有限公司 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et appareil électrique
CN117461167B (zh) * 2022-05-24 2026-04-03 宁德时代新能源科技股份有限公司 正极活性材料、正极极片、二次电池、电池模块、电池包和用电装置

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EP2874227B1 (fr) 2012-11-21 2017-09-06 LG Chem, Ltd. Batterie secondaire au lithium
KR20140066050A (ko) 2012-11-22 2014-05-30 주식회사 엘지화학 리튬 이차전지용 전해액 및 이를 포함하는 리튬 이차전지
WO2015053446A1 (fr) * 2013-10-11 2015-04-16 주식회사 엘앤에프신소재 Matériau actif d'anode pour batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium comprenant celle-ci
KR20240083584A (ko) 2022-12-05 2024-06-12 에스케이이노베이션 주식회사 리튬 이차 전지용 양극 활물질 및 이를 포함하는 리튬 이차 전지
KR20240100834A (ko) * 2022-12-23 2024-07-02 재단법인 포항산업과학연구원 리튬 이차 전지용 올리빈계 양극 활물질 및 이의 제조방법

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JP5716269B2 (ja) * 2008-11-04 2015-05-13 株式会社Ｇｓユアサ 非水電解質二次電池用正極材料
KR101063214B1 (ko) * 2008-11-28 2011-09-07 전자부품연구원 리튬이차전지용 구형 양극 활물질 제조방법

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CN114762149A (zh) * 2019-12-05 2022-07-15 Sm研究所股份有限公司 正极活性材料、所述正极活性材料的制备方法以及具有包括所述正极活性材料的正极的锂二次电池
CN114762149B (zh) * 2019-12-05 2024-04-05 Sm研究所股份有限公司 正极活性材料、所述正极活性材料的制备方法以及具有包括所述正极活性材料的正极的锂二次电池
WO2023225836A1 (fr) * 2022-05-24 2023-11-30 宁德时代新能源科技股份有限公司 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et appareil électrique
CN117461167A (zh) * 2022-05-24 2024-01-26 宁德时代新能源科技股份有限公司 正极活性材料、正极极片、二次电池、电池模块、电池包和用电装置
CN117461167B (zh) * 2022-05-24 2026-04-03 宁德时代新能源科技股份有限公司 正极活性材料、正极极片、二次电池、电池模块、电池包和用电装置
CN116598448A (zh) * 2023-05-06 2023-08-15 浙江中哲新能源有限公司 一种聚阴离子型硫酸盐正极材料及其制备方法

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