WO2019066585A1 - Méthode de préparation de matériau actif de cathode pour batterie secondaire, matériau actif de cathode ainsi préparé, et batterie secondaire au lithium le contenant - Google Patents

Méthode de préparation de matériau actif de cathode pour batterie secondaire, matériau actif de cathode ainsi préparé, et batterie secondaire au lithium le contenant Download PDF

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WO2019066585A1
WO2019066585A1 PCT/KR2018/011579 KR2018011579W WO2019066585A1 WO 2019066585 A1 WO2019066585 A1 WO 2019066585A1 KR 2018011579 W KR2018011579 W KR 2018011579W WO 2019066585 A1 WO2019066585 A1 WO 2019066585A1
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lithium
active material
coating
metal oxide
carbide
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PCT/KR2018/011579
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English (en)
Korean (ko)
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안동준
조문규
박성순
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주식회사 엘지화학
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Priority claimed from KR1020180115214A external-priority patent/KR102143101B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2020506194A priority Critical patent/JP6890874B2/ja
Priority to CN201880008691.6A priority patent/CN110225887B/zh
Priority to US16/481,718 priority patent/US11189827B2/en
Publication of WO2019066585A1 publication Critical patent/WO2019066585A1/fr
Priority to US17/459,344 priority patent/US11888153B2/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/991—Boron carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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 method for producing a cathode active material for a secondary battery, a cathode active material thus prepared, and a lithium secondary battery comprising the cathode active material.
  • the lithium secondary battery has a structure in which an organic electrolyte or a polymer electrolyte is filled between a positive electrode and a negative electrode, which are made of an active material capable of intercalating and deintercalating lithium ions, and oxidized when lithium ions are inserted / And electrical energy is produced by the reduction reaction.
  • lithium cobalt oxide LiCoO 2
  • lithium nickel oxide LiNiO 2
  • lithium manganese oxide LiMnO 2 or LiMn 2 O 4
  • lithium iron phosphate compound LiFePO 4
  • LiNi 1 - ⁇ Co ⁇ O 2 0.1 ⁇ 0.3
  • nickel is partially replaced by cobalt
  • a nickel manganese-based lithium composite metal oxide in which a part of nickel (Ni) is substituted with manganese (Mn) excellent in thermal stability and a nickel-cobalt manganese-based lithium composite metal oxide in which manganese (Mn) (Hereinafter referred to as " NCM-based lithium oxide ") has an advantage in that it has excellent cycle characteristics and thermal stability.
  • a cathode active material for high voltage and high voltage secondary batteries which suppresses side reaction with an electrolyte under high voltage and formation of a solid electrolyte interface (SEI) film on the surface of a cathode active material, and has improved resistance characteristics and life characteristics.
  • SEI solid electrolyte interface
  • the present invention provides a method of manufacturing a lithium secondary battery including: providing a lithium transition metal oxide; Mixing the lithium transition metal oxide, a coating polymer, and a carbide to form a mixture; And heat-treating the mixture to form a coating layer comprising a carbonated coating polymer and a carbide on the surface of the lithium transition metal oxide.
  • the present invention also provides a method of manufacturing a cathode active material for a secondary battery.
  • the present invention also relates to a lithium transition metal oxide; And a coating layer formed on the particle surface of the lithium-transition metal oxide, wherein the coating layer is in the form of a film, and the coating layer comprises a carbonated coating polymer and a carbide.
  • the present invention also provides a positive electrode and a lithium secondary battery including the positive electrode active material.
  • a cathode active material for high voltage and high voltage secondary batteries can be produced which suppresses a side reaction with an electrolyte and a solid electrolyte interface (SEI) film formation on the surface of a cathode active material under a high voltage and has improved resistance characteristics and life characteristics.
  • SEI solid electrolyte interface
  • the positive electrode active material for a secondary battery according to the present invention can prevent mechanical damage of a positive electrode active material generated by repetition of charging / discharging in a high voltage state.
  • uniform coating can be performed on the entire surface of the cathode active material particles, and the initial resistance and the rate of resistance increase can be reduced by securing excellent electrical conductivity.
  • Example 1 and 2 are SEM (Scanning Electron Microscope) photographs of a cathode active material manufactured according to Example 1 of the present invention.
  • FIGS. 3 and 4 are SEM (Scanning Electron Microscope) photographs of the cathode active material prepared according to Comparative Example 2 on an enlarged scale.
  • a method of manufacturing a cathode active material for a secondary battery according to the present invention includes the steps of: providing a lithium transition metal oxide; Mixing the lithium transition metal oxide, a coating polymer, and a carbide to form a mixture; And heat-treating the mixture to form a coating layer comprising a carbonated coating polymer and carbide on the surface of the lithium transition metal oxide particle.
  • the present invention relates to a method of coating a lithium transition metal oxide particle by using a mixture of a coating polymer and a carbide to suppress side reactions with an electrolyte and formation of a solid electrolyte interface (SEI) film on the surface of a cathode active material under high voltage, And life characteristics can be improved.
  • SEI solid electrolyte interface
  • a polymer for coating a soft material it is possible to prevent mechanical breakage of a cathode active material generated by repetition of charging / discharging in a high voltage state, and by using a carbide excellent in electrical conductivity, And the resistance increase rate can be reduced.
  • the coating polymer may be carbonized through heat treatment during the coating process to ensure additional electrical conductivity.
  • a lithium transition metal oxide is provided.
  • the lithium transition metal oxide may be a lithium transition metal oxide which is typically used as a cathode active material and more preferably at least one transition metal selected from the group consisting of nickel (Ni), cobalt (Co) and manganese (Mn)
  • Ni nickel
  • Co cobalt
  • Mn manganese
  • the cathode active material may include a lithium-transition metal composite oxide represented by the following general formula (1).
  • M a is at least one element selected from the group consisting of Mn, Al and Zr and M b is at least one element selected from the group consisting of Al, Zr, Ti, Mg, Ta, Nb, Mo, W and Cr Or more, and 0.9? P? 1.5, 0? X? 0.5, 0? Y? 0.5, and 0? Z? More preferably 0? X + y? 0.7, and most preferably 0 ⁇ x + y?
  • the cathode active material is more preferably LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0 . 9 Co 0 . 05 Mn 0 . 05 O 2 , or LiNi 0 . 6 Co 0 . 2 Mn 0 . 2 O 2 Or a high-Ni NCM-based lithium transition metal oxide.
  • the lithium transition metal oxide, the polymer for coating and the carbide are mixed to form a mixture.
  • the coating polymer can be used as long as it can coat the particle surface of the lithium transition metal oxide and does not deteriorate the electrochemical performance.
  • the polymer include polyvinylidene fluoride (PVDF), polyvinyl pyrrolidone Polyvinylpyrrolidone), polyethylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, epoxy resin, amino resin, phenol resin and polyester resin, and more preferably at least one of polyvinylidene At least one selected from the group consisting of polyvinylpyrrolidone (PVDF) and polyvinylpyrrolidone, polyethylene terephthalate and polyvinylidene chloride may be used.
  • PVDF polyvinylidene fluoride
  • PVDF polyvinyl pyrrolidone
  • Polyvinylpyrrolidone Polyvinylpyrrolidone
  • polyethylene polystyrene
  • the polymer for coating of a soft material By using the polymer for coating of a soft material, it is possible to prevent mechanical breakage of the positive electrode active material generated by repeating charging / discharging in a high voltage state.
  • the formation of the coating layer through the conventional dry coating method of metal oxide is difficult to coat uniformly in the form of an island and is difficult to coat uniformly in the form of an island.
  • the coating polymer in which the coating is coated with a mixture of the polymer for coating and a carbide It is possible to easily form a film-like uniform coating layer through temperature control during the coating process based on the melting point of the polymer for coating, and the carbide mixed with the coating polymer can uniformly coat the surface of the cathode active material particle Can be distributed.
  • the coating polymer may be carbonized through a heat treatment during the coating process, thereby providing additional electrical conductivity.
  • the polymer for coating may be included in an amount of 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the lithium-transition metal oxide contained in the mixture.
  • the coating polymer is mixed in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the lithium-transition metal oxide, whereby a coating layer can be uniformly formed on the entire surface of the cathode active material particle. It is possible to prevent mechanical breakage of the positive electrode active material that occurs while repeating the above-described process.
  • the carbide is a compound composed of carbon and one element.
  • the carbide is covalently bonded to carbon and other elements and has a relatively high melting point and can remain as it is without being decomposed into CO 2 or CO even during high temperature heat treatment in an oxidizing atmosphere during the coating process, It can be coated with the polymer for uniform distribution on the surface of the cathode active material particles. As a result, excellent electrical conductivity can be ensured and excellent electrical conductivity can be secured to reduce initial resistance and resistance increase rate.
  • the carbide may be included in an amount of 0.001 to 10 parts by weight, more preferably 0.002 to 2 parts by weight, based on 100 parts by weight of the lithium-transition metal oxide contained in the mixture. Since the carbide is mixed in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the lithium transition metal oxide, it can be uniformly distributed over the surface of the positive electrode active material particles, and the initial resistance and the rate of increase in resistance can be decreased have.
  • the mixture may be prepared by adding and stirring a polymer for coating to a lithium-transition metal oxide, then adding and stirring the carbide, and simultaneously adding a coating polymer and a carbide, And the order of the manufacturing process is not particularly limited.
  • a stirring process can be selectively performed, and the stirring speed may be 2,000 rpm at 100 rpm.
  • the mixture may contain the coating polymer and the carbide in a weight ratio of 1:99 to 99: 1, more preferably 20:80 to 80:20.
  • a uniform film-like coating layer can be formed on the entire surface of the cathode active material particle, and the carbide can be uniformly distributed.
  • SEI solid electrolyte interface
  • the mixture is subjected to heat treatment to form a coating layer containing a carbonated coating polymer and a carbide on the surface of the lithium transition metal oxide.
  • the heat treatment for forming the coating layer may be performed in an oxidizing atmosphere such as air or oxygen or an inert atmosphere such as nitrogen, but may be performed in an oxidizing atmosphere.
  • the heat treatment may be performed at 200 to 800 ° C for 0.5 to 5 hours, more preferably at 300 to 600 ° C for 0.5 to 5 hours.
  • the cathode active material for a secondary battery of the present invention thus produced is a lithium transition metal oxide; And a coating layer formed on the particle surface of the lithium transition metal oxide, wherein the coating layer is in the form of a film, and the coating layer comprises a carbonated coating polymer and a carbide.
  • the coating polymer used in the coating process can be formed into a carbonized form through heat treatment during the coating process.
  • the carbonized coating polymer can ensure additional electrical conductivity.
  • the carbide may remain as it is without being decomposed into CO 2 or CO even during high-temperature heat treatment in an oxidizing atmosphere during the coating process.
  • a coating layer may be formed together with the coating polymer and may be uniformly distributed on the surface of the cathode active material particle. have.
  • the coating layer may contain 0.001 to 10 parts by weight, more preferably 0.002 to 2 parts by weight, of the carbide relative to 100 parts by weight of the lithium-transition metal oxide particles.
  • Carbide is not decomposed and removed even during the heat treatment during the coating process so that the above content can be satisfied and carbide is contained within the above range to secure excellent electrical conductivity and reduce initial resistance and resistance increase rate, And can be suitably applied as a high-voltage positive electrode active material.
  • the coating polymer and the carbide are applied in the same manner as described above for the method of manufacturing the cathode active material for a secondary battery of the present invention.
  • the coating layer is in the form of a film surrounding the particle surface of the lithium transition metal oxide, and the thickness of the coating layer may be 5 to 2,000 nm, more preferably 10 to 500 nm. If the thickness of the coating layer is less than 5 nm, the coating layer may be too thin to form a uniform coating layer. If the thickness of the coating layer is more than 2,000 nm, the ion conductivity may be lowered.
  • a cathode active material for a secondary battery manufactured by coating a coating polymer and a carbide as a hybrid coating suppresses a side reaction with an electrolyte under a high voltage and forms a solid electrolyte interface (SEI) film on the surface of the cathode active material And thus, it is possible to remarkably improve the high-voltage undervoltage resistance characteristic and the life characteristic.
  • SEI solid electrolyte interface
  • a positive electrode and a lithium secondary battery for a secondary battery including the positive electrode active material.
  • the positive electrode includes a positive electrode collector and a positive electrode active material layer formed on the positive electrode collector and including the positive electrode active material.
  • the cathode current collector is not particularly limited as long as it has conductivity without causing a chemical change in the battery, and for example, a metal such as stainless steel, aluminum, nickel, titanium, sintered carbon, , Nickel, titanium, silver, or the like may be used.
  • the cathode current collector may have a thickness of 3 to 500 ⁇ , and fine unevenness may be formed on the surface of the cathode current collector to increase the adhesive force of the cathode active material.
  • it can 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 cathode active material layer may include a conductive material and a binder together with the cathode active material described above.
  • the conductive material is used for imparting conductivity to the electrode.
  • the conductive material can be used without particular limitation as long as it has electron conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; And polyphenylene derivatives. These may be used alone or in admixture of two or more.
  • the conductive material may be typically contained in an amount of 1 to 30% by weight based on the total weight of the cathode active material layer.
  • the binder serves to improve adhesion between the positive electrode active material particles and adhesion between the positive electrode active material and the positive electrode collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose ), Starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, and various copolymers thereof.
  • the binder may be included in an amount of 1 to 30% by weight based on the total weight of the cathode active material layer.
  • the positive electrode may be manufactured according to a conventional positive electrode manufacturing method, except that the positive electrode active material described above is used. Specifically, the composition for forming a cathode active material layer containing the above-mentioned cathode active material and optionally a binder and a conductive material may be coated on the cathode current collector, followed by drying and rolling. At this time, the types and contents of the cathode active material, the binder, and the conductive material are as described above.
  • the solvent examples include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, and the like. Water and the like, and one kind or a mixture of two or more kinds can be used.
  • the amount of the solvent to be used is sufficient to dissolve or disperse the cathode active material, the conductive material and the binder in consideration of the coating thickness of the slurry and the yield of the slurry, and then to have a viscosity capable of exhibiting excellent thickness uniformity Do.
  • the positive electrode may be produced by casting the composition for forming the positive electrode active material layer on a separate support, then peeling off the support from the support, and laminating the obtained film on the positive electrode current collector.
  • an electrochemical device including the anode.
  • the electrochemical device may be specifically a battery or a capacitor, and more specifically, may be a lithium secondary battery.
  • the lithium secondary battery includes a positive electrode, a negative electrode disposed opposite to the positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, as described above.
  • the lithium secondary battery may further include a battery container for storing the positive electrode, the negative electrode and the electrode assembly of the separator, and a sealing member for sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • the negative electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, Carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like may be used.
  • the negative electrode collector may have a thickness of 3 to 500 ⁇ , and similarly to the positive electrode collector, fine unevenness may be formed on the surface of the collector to enhance the binding force of the negative electrode active material.
  • it can 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 anode active material layer optionally includes a binder and a conductive material together with the anode active material.
  • the negative electrode active material layer may be formed by applying and drying a composition for forming a negative electrode including a negative electrode active material on the negative electrode collector and, optionally, a binder and a conductive material, or by casting the composition for forming a negative electrode on a separate support , And a film obtained by peeling from the support may be laminated on the negative electrode collector.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples thereof include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber and amorphous carbon;
  • Metal compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys; SiO ⁇ (0 ⁇ ⁇ 2 ), SnO 2, vanadium oxide, which can dope and de-dope a lithium metal oxide such as lithium vanadium oxide;
  • a composite containing the metallic compound and the carbonaceous material such as Si-C composite or Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the negative electrode active material.
  • the carbon material may be both low-crystalline carbon and high-crystallinity carbon.
  • Examples of the low-crystalline carbon include soft carbon and hard carbon.
  • Examples of the highly crystalline carbon include natural graphite, artificial graphite, artificial graphite or artificial graphite, Kish graphite graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar coke derived cokes).
  • binder and the conductive material may be the same as those described above for the anode.
  • the separator separates the negative electrode and the positive electrode and provides a moving path of lithium ions.
  • the separator can be used without any particular limitation as long as it is used as a separator in a lithium secondary battery. Particularly, It is preferable to have a low resistance and an excellent ability to impregnate the electrolyte.
  • porous polymer films such as porous polymer films made of polyolefin-based polymers such as ethylene homopolymers, propylene homopolymers, ethylene / butene copolymers, ethylene / hexene copolymers and ethylene / methacrylate copolymers, May be used.
  • a nonwoven fabric made of a conventional porous nonwoven fabric for example, glass fiber of high melting point, polyethylene terephthalate fiber, or the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used, and may be optionally used as a single layer or a multilayer structure.
  • Examples of the electrolyte used in the present invention include an organic-based liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte that can be used in the production of a lithium secondary battery. It is not.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without limitation as long as it can act as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • examples of the organic solvent include ester solvents such as methyl acetate, ethyl acetate,? -Butyrolactone and?
  • Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethyl carbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate PC) and the like; Alcohol solvents such as ethyl alcohol and isopropyl alcohol; R-CN (R is a straight, branched or cyclic hydrocarbon group of C2 to C20, which may contain a double bond aromatic ring or an ether bond); Amides such as dimethylformamide; Dioxolanes such as 1,3-dioxolane; Or sulfolane may be used.
  • Ether solvents such as dibutyl ether or tetrahydrofuran
  • Ketone solvents such as cyclohexanone
  • a carbonate-based solvent is preferable, and a cyclic carbonate (for example, ethylene carbonate or propylene carbonate) having a high ionic conductivity and a high dielectric constant, for example, such as ethylene carbonate or propylene carbonate, For example, ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate) is more preferable.
  • a cyclic carbonate for example, ethylene carbonate or propylene carbonate
  • ethylene carbonate or propylene carbonate for example, ethylene carbonate or propylene carbonate
  • ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate
  • the lithium salt can be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt 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 is preferably in the range of 0.1 to 2.0 M. When the concentration of the lithium salt is within the above range, the electrolyte has an appropriate conductivity and viscosity, so that it can exhibit excellent electrolyte performance and the lithium ion can effectively move.
  • the electrolyte may contain, for example, a haloalkylene carbonate-based compound such as difluoroethylene carbonate or the like, pyridine, triethanolamine, or the like for the purpose of improving lifetime characteristics of the battery, Ethyl phosphite, triethanol amine, cyclic ether, ethylenediamine, glyme, hexametriamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, At least one additive such as benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, benzyl alcohol, The additive may be included in an amount of 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate, it can be used in portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles hybrid electric vehicle (HEV)).
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles hybrid electric vehicle (HEV)).
  • HEV hybrid electric vehicles hybrid electric vehicle
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same.
  • the battery module or the battery pack may include a power tool; An electric vehicle including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); Or a power storage system, as shown in FIG.
  • a power tool including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); Or a power storage system, as shown in FIG.
  • EV electric vehicle
  • PHEV plug-in hybrid electric vehicle
  • PVDF polyvinylidene fluoride
  • Example 2 Was prepared in the same manner as in Example 1, except that Al 4 C 3 was used instead of B 4 C as a carbide.
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • LiNi 0.6 Co 0.2 Mn 0.2 O 2 in which no coating layer was formed was prepared.
  • LiNi 0 . 6 Co 0 . 2 Mn 0 . 2 O 2 and H 3 BO 3 100 a mixture in a weight ratio of 0.1 and heat-treated for about 3 hours in an oxygen atmosphere to 400 °C the LiNi 0. 6 Co 0 . 2 Mn 0 . 2 O 2 Of the particle surface.
  • LiNi 0 . 6 Co 0 . 2 Mn 0 . 2 O 2 , polyvinylidene fluoride (PVDF) and carbon black were mixed at a weight ratio of 100: 2: 0.1 and heat-treated at 400 ° C for about 3 hours in an oxygen atmosphere to form the particle surface of LiNi 0.6 Co 0.2 Mn 0.2 O 2 To form a coating layer.
  • PVDF polyvinylidene fluoride
  • the thickness was very uneven, and no carbon black was detected in the coating layer. It is thought that carbon black was decomposed and removed into CO 2 or CO during the heat treatment process.
  • LiNi 0 . 6 Co 0 . 2 Mn 0 . 2 O 2 and B 4 C 100 a mixture in a weight ratio of 0.1 and heat-treated for about 3 hours in an oxygen atmosphere to 400 °C the LiNi 0. 6 Co 0 . 2 Mn 0 . 2 O 2 Of the particle surface.
  • PVDF polyvinylidene fluoride
  • FIG. 1 and FIG. 2 (Example 1) and FIGS. 3 and 4 (Comparative Example 2) are photographs of a cathode active material produced according to Example 1 and Comparative Example 2, which are observed by a scanning electron microscope (SEM) .
  • SEM scanning electron microscope
  • Example 1 prepared by coating with a coating polymer and a hybrid coating of carbide shows that a film-like coating layer surrounding the active material particle surface is formed to a thickness of 1,000 nm on average I could confirm.
  • Comparative Example 2 coated with H 3 BO 3 which is a conventional coating material, it can be confirmed that an island-shaped coating portion is formed on the surface of the active material particle.
  • carbon black and PVDF binder were mixed in a N-methylpyrrolidone solvent in a weight ratio of 96: 2: 2, was coated on one side of the aluminum current collector, dried at 130 ⁇ , and rolled to prepare a positive electrode.
  • a negative electrode active material natural graphite, a carbon black conductive material and a PVdF binder were mixed in a N-methylpyrrolidone solvent in a weight ratio of 85: 10: 5 to prepare a composition for forming an anode, To prepare a negative electrode.
  • a lithium secondary battery was prepared by preparing an electrode assembly between a positive electrode and a negative electrode manufactured as described above through a separator of porous polyethylene, positioning the electrode assembly inside a case, and then injecting an electrolyte into the case.
  • Each of the prepared lithium secondary battery cells was charged at a rate of 0.7 C and 4.4 V in a CCCV mode at 25 ° C and 45 ° C, cut off at 0.55C, The capacity retention (%) was measured while discharging to 3.0 V and performing charge / discharge 100 times. The results are shown in Table 1.
  • Examples 1 to 4 which were prepared by coating a coating polymer and a hybrid coating of carbide, were compared with Comparative Example 1 which was not coated or coated with H 3 BO 3 which is a conventional coating material (25 ° C.) and high temperature (45 ° C.) under high voltage compared to Example 2.
  • the cycle characteristics of Examples 1 to 4 were remarkably superior to those of Comparative Example 3 in which a polymer and carbon (carbon black) were coated as a coating material.
  • Comparative Example 4 in which B 4 C was coated as a single coating material, the cyclotoxicity at room temperature (25 ° C) and high temperature (45 ° C) was lower than those in Examples 1 to 4 and was similar to that in Comparative Example 2 . Also, in Comparative Example 5 in which PVDF was coated as a single coating material, cycle characteristics at room temperature (25 ° C) and high temperature (45 ° C) were significantly lower than those of Examples 1 to 4.
  • Each of the prepared lithium secondary battery cells was charged at a rate of 0.7 C and 4.4 V in a CCCV mode at 25 ° C and 45 ° C, cut off at 0.55C, And the resistance increase rate (DCIR [%]) was measured while charging / discharging was performed 100 times. The results are shown in Table 2.
  • Examples 1 to 4 prepared by coating with a coating polymer and a hybrid coating of carbide were compared with Comparative Example 1 which was not coated or coated with H 3 BO 3 which is a conventional coating material
  • the resistance increase rate at room temperature and high temperature (45 ° C) under a high voltage was remarkably reduced compared to Example 2.
  • the resistance characteristics of Examples 1 to 4 were remarkably superior to those of Comparative Example 3 in which a polymer and carbon (carbon black) were coated as a coating material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une méthode de préparation d'un matériau actif de cathode pour une batterie secondaire, comprenant les étapes consistant à : préparer un oxyde de métal de transition de lithium ; former un mélange par mélange de l'oxyde de métal de transition de lithium, d'un polymère de revêtement et d'un carbure ; et chauffer le mélange de manière à former, sur la surface des particules d'oxyde de métal de transition de lithium, une couche de revêtement comprenant un polymère de revêtement carboné et le carbure.
PCT/KR2018/011579 2017-09-29 2018-09-28 Méthode de préparation de matériau actif de cathode pour batterie secondaire, matériau actif de cathode ainsi préparé, et batterie secondaire au lithium le contenant WO2019066585A1 (fr)

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JP2020506194A JP6890874B2 (ja) 2017-09-29 2018-09-28 二次電池用正極活物質の製造方法、このように製造された正極活物質及びこれを含むリチウム二次電池
CN201880008691.6A CN110225887B (zh) 2017-09-29 2018-09-28 制备二次电池用正极活性材料的方法、由此制备的正极活性材料和包含其的锂二次电池
US16/481,718 US11189827B2 (en) 2017-09-29 2018-09-28 Method for preparing positive electrode active material for secondary battery, positive electrode active material thus prepared and lithium secondary battery including the same
US17/459,344 US11888153B2 (en) 2017-09-29 2021-08-27 Method for preparing positive electrode active material for secondary battery, positive electrode active material thus prepared and lithium secondary battery including the same

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KR20170127757 2017-09-29
KR10-2017-0127757 2017-09-29
KR1020180115214A KR102143101B1 (ko) 2017-09-29 2018-09-27 이차전지용 양극 활물질의 제조방법, 이와 같이 제조된 양극 활물질 및 이를 포함하는 리튬 이차전지
KR10-2018-0115214 2018-09-27

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US17/459,344 Division US11888153B2 (en) 2017-09-29 2021-08-27 Method for preparing positive electrode active material for secondary battery, positive electrode active material thus prepared and lithium secondary battery including the same

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CN110783537A (zh) * 2019-09-19 2020-02-11 安徽清泉新能源科技集团有限责任公司 一种聚吡咯锂硫电池材料

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