WO2019045443A1 - Procédé de fabrication de matériau actif positif, et matériau actif positif et batterie secondaire au lithium le comprenant - Google Patents
Procédé de fabrication de matériau actif positif, et matériau actif positif et batterie secondaire au lithium le comprenant Download PDFInfo
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- WO2019045443A1 WO2019045443A1 PCT/KR2018/009978 KR2018009978W WO2019045443A1 WO 2019045443 A1 WO2019045443 A1 WO 2019045443A1 KR 2018009978 W KR2018009978 W KR 2018009978W WO 2019045443 A1 WO2019045443 A1 WO 2019045443A1
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for producing a positive electrode active material, a positive electrode active material using the same, and a lithium secondary battery.
- lithium secondary batteries having advantages such as high energy density, discharge voltage, and output stability are attracting attention.
- a lithium secondary battery when used as a medium or large power source such as an electric vehicle or an energy storage system (ESS), it requires high stability, long life, high energy density and high output characteristics.
- ESS energy storage system
- the capacity of the lithium secondary battery varies depending on the kind of the electrode active material, and the capacity can not be secured by the theoretical capacity at the time of actual operation, and the lifetime characteristics are rapidly lowered due to side reactions under high temperature or high voltage.
- Li a M b X c (M: transition metal, X: anion) has the form of transition, while the transition metal causes oxidation reaction to increase the dislocation while discharging.
- Various types of anions such as O 2- , PO 4 3- , SO 4 2- , and SiO 4 4 - can participate in the composition and there are many characteristic differences depending on the kind.
- Lithium cobalt oxide (LiCoO 2 ) having a layered crystal structure is mainly used as the cathode active material, and lithium manganese oxide such as layered crystal structure LiMnO 2 and spinel crystal structure such as LiMn 2 O 4 and lithium nickel oxide (LiNiO 2 ) Etc. have been considered.
- lithium cobalt oxide represented by LiCoO 2 has a layered crystal structure and the theoretical capacity is as large as 270 to 280 mAh / g.
- the capacity of the lithium secondary battery due to dissolution, structural change and decomposition of electrolyte in the high voltage region of 4.3V or more is rapidly decreased, and the cost competitiveness is limited due to the resource limit of cobalt There is a limit in using a large amount as a power source such as an electric vehicle.
- the lithium nickel oxide cathode active material exhibits a relatively low cost and high discharge capacity, but exhibits a rapid phase transition of the crystal structure in accordance with the volume change accompanying the charging / discharging cycle. When exposed to air and moisture, .
- lithium manganese oxides such as LiMnO 2 have a spinel crystal structure, and the movement of lithium ions occurs three-dimensionally. Therefore, a variety of passages of lithium ions are suitable for high output energy sources such as electric vehicles. It is inexpensive and has the advantage of being environmentally friendly because it does not use harmful heavy metal materials such as cobalt.
- the lithium manganese oxide has a disadvantage that the capacity is small and the cycle characteristics are poor, and the decomposition reaction of the electrolyte is caused by the elution of manganese ions at high temperature, so that the lifetime of the lithium manganese oxide is rapidly lowered at a high temperature.
- Korean Patent Laid-Open Publication No. 2006-0121272 discloses that the deterioration of a cathode active material can be prevented by forming a cover layer of a lithium compound on the surface of a cathode active material core composed of an oxide containing lithium and nickel through vapor deposition have.
- Korean Patent No. 10-1588652 discloses a technique for coating a surface of lithium cobalt oxide with a nano-sized Zr oxide and a nano-sized Si oxide, and suppresses deterioration of capacity in a high-voltage and high-temperature environment by the coating It is possible.
- the present inventors have found that a coating composition containing a precursor of a metal-phosphorus-oxynitride in a solution phase is prepared, and a metal-phosphorus- Layer is formed, it is easy to form the protective layer and the coating property is excellent, so that the stability and lifespan characteristics of the cathode active material are improved.
- the present invention has been completed.
- an object of the present invention is to provide a method for producing a positive electrode active material, which is capable of producing a metal-phosphorus-nitride oxide protective layer having excellent characteristics on a positive electrode active material by a simpler process than a conventional method.
- Another object of the present invention is to provide a cathode active material produced by the above production method and a lithium secondary battery including the same.
- the precursor of the metal-phosphorus-oxynitride may be one produced by the reaction of a compound containing a phosphorus-nitrogen bond and a metal salt compound.
- the phosphorus-nitrogen bond-containing compound may include at least one compound represented by the following general formulas (1) to (3)
- the metal salt compound may include at least one selected from the group consisting of lithium, sodium, magnesium, calcium, zinc, and aluminum.
- the coating composition may comprise a compound comprising a phosphorus-nitrogen bond, a metal salt compound and an organic solvent.
- the coating composition may comprise from 0.002 to 27% by weight of a compound containing phosphorus-nitrogen bonds, from 0.0005 to 12% by weight of a metal salt compound and from 70 to 99.99% by weight of an organic solvent, based on 100% by weight of the total composition.
- the coating composition may further comprise a chalcogen compound.
- the cathode active material may include a lithium transition metal oxide.
- the cathode active material may be spherical, elliptical, spindle-shaped, scaly, plate-shaped, fibrous, rod-shaped, core-shell or irregular.
- step (b) at least one of spray coating, spin coating, dip coating, inkjet printing, offset printing, reverse offset printing, gravure printing and roll printing may be used.
- the heat treatment may be performed at a temperature ranging from 150 ° C to less than 500 ° C.
- the present invention provides a cathode active material produced by the above production method.
- the present invention provides a lithium secondary battery comprising the cathode active material.
- the method for producing a cathode active material according to the present invention is a method for producing a cathode active material comprising a metal-phosphorus-oxide nitride and / or a derivative thereof on a cathode active material through a solution process using a liquid coating composition comprising a precursor of metal-
- the protective layer can be easily formed through a simple reaction under mild conditions.
- the manufacturing method of the present invention can be applied to commercial use because it can minimize the manufacturing cost and shorten the manufacturing time.
- the cathode active material having the protective layer prepared according to the production method of the present invention can provide a cathode active material which is excellent in reaction stability with an electrolyte solution and exhibits ionic conductivity to enable high capacity and long life, The capacity and life characteristics of the secondary battery can be improved.
- Example 1 is a scanning electron microscope image of the cathode active material prepared in Example 1 of the present invention.
- lithium secondary batteries Recently, the application field of lithium secondary batteries has been expanded from electric appliances such as mobile phones to electric vehicles, and development of lithium secondary batteries having high performance, long life and high reliability has been required.
- cathode active materials In response to these demands, various materials are being used and developed as cathode active materials. However, in actual operation, not only the theoretical capacity and the energy density are all realized, but cycle efficiency and stability are insufficient, so that it is difficult to secure sufficient life characteristics. As described above, when the impurities exist on the surface of the cathode active material in addition to the limitations of the cathode active material itself, it not only affects the stability over time of the anode manufactured, but also reacts with the electrolyte during operation of the battery, ) Phenomenon.
- the electrolyte contains a fluorine-based material such as LiPF 6
- the fluorine-based material reacts with moisture or impurities to generate hydrofluoric acid, thereby causing corrosion and the like, thereby deteriorating the electrode cycle.
- the composition of the cathode active material or the method of introducing the coating layer to the surface of the cathode active material has been suggested, but the stability and lifetime characteristics of the cathode active material have not been effectively improved.
- step (a) produces a coating composition comprising a precursor of a metal phosphorus oxynitride.
- the coating composition may comprise a compound comprising a phosphorus (P) - nitrogen (N) bond, a metal salt compound and an organic solvent.
- the phosphorus-nitrogen bond-containing compound of the present invention is a kind of skeleton compound containing a phosphorus-nitrogen bond.
- the phosphorus-nitrogen-oxygen skeleton is a lattice structure of metal-phosphorus-oxynitride finally formed by the heat treatment described later It serves to provide.
- the phosphorus-nitrogen bond may be a single bond or a double bond.
- the phosphorus-nitrogen bond-containing compound may be at least one compound represented by the following general formulas (1) to (3)
- X 1 are the same or different and are each independently OR 1 , F, Cl, Br or I, wherein R 1 is an alkyl group having 1 to 5 carbon atoms.
- R 2 and R 3 are the same or different and are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.
- X 2 are the same or different from each other and each independently R 4 , OR 5 , NR 6 R 7 , F, Cl, Br or I, wherein R 4 to R 7 are the same or different, Or an aryl group having 6 to 20 carbon atoms,
- n is an integer of 100 to 100,000).
- " alkyl group " used in the present invention may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.
- " aryl group " used in the present invention means a single or multiple aromatic carbon-based ring having 6 to 20 carbon atoms.
- the aryl group includes, but is not limited to, a phenyl group, a biphenyl group, and a fluorene group.
- the phosphorus-nitrogen bond-containing compound may be a monomolecular compound represented by Formula 1 or 2, a polymer compound represented by Formula 3, or a mixture thereof.
- the phosphorus-nitrogen bond containing compound may be selected from the group consisting of Hexachlorophosphazene, Hexafluorophosphazene, Hexabromophosphazene, Hexaiodophosphazene, (Diphenyl phosphoramidate), poly (dichlorophosphazene), poly (diphenyl phosphoramidate), poly (dichlorophosphazene), and poly (vinylidene fluoride) (Poly (bis (ethoxy) phosphazene) and poly (bis (phenoxy) phosphazene) (poly (bis (phenoxy) phosphazene) . And preferably at least one selected from the group consisting of hexachlorophosphazene, diphenyl phosphoramidite and poly (dichlorophosphazene).
- the phosphorus-nitrogen bond-containing compound may be contained in an amount of 0.002 to 27% by weight based on 100% by weight of the entire coating composition.
- the phosphorus-nitrogen bond-containing compound may be contained in an amount of 20 to 90% by weight, preferably 50 to 80% by weight based on 100% by weight of the solid content of the coating composition. If the amount of the phosphorus-nitrogen bond-containing compound contained in the coating composition is less than the above range, the formation of the final product, metal-phosphorus-oxynitride may be difficult to occur uniformly.
- the optimal optimum amount of the phosphorus-nitrogen bond-containing compound may be set differently depending on the other characteristics of the positive electrode active material to be provided and the battery having the negative electrode active material, and the use environment thereof. It does not mean anything.
- the metal salt compound of the present invention is not particularly limited as long as it is capable of dissociating into a cation and an anion in an organic solvent to provide a metal cation, and any of those generally used in the art can be used without limitation.
- the metal salt compound may be a monovalent metal such as lithium (Li) or sodium (Na); Divalent metals such as magnesium (Mg), calcium (Ca) and zinc (Zn); And aluminum (Al), and may have various forms such as halides, hydroxides, acetates, alkoxides and the like.
- the metal salt compound may be a lithium salt containing a lithium ion (Li + ) as a monovalent metal cation, wherein the lithium salt is CH 3 COOLi, LiX (wherein X represents F, Cl, Br or I ), LiNO 3, LiOH, LiOR (wherein, R may be such represents an alkyl group having 1 to 5 carbon atoms).
- the metal salt compound is a magnesium salt containing a magnesium ion (Mg 2+ ) as a divalent metal cation
- the magnesium salt is (CH 3 COO) 2 Mg, MgX 2 wherein X is F, Cl, Br Or I), and the like.
- the metal salt compound may be contained in an amount of 0.005 to 12 wt% based on 100 wt% of the entire coating composition.
- the metal salt compound may be contained in an amount of 5 to 40% by weight, preferably 10 to 30% by weight.
- the content of the metal salt compound is less than the above range, it is difficult to secure the ion conductivity of the protective layer of the present invention. On the contrary, when the content exceeds the above range, formation of an inhomogeneous film and resistance increase, The surface side reaction can not be suppressed or the performance of the battery may be deteriorated.
- the organic solvent of the present invention ionizes the aforementioned metal salt compound to provide metal cations.
- the organic solvent may be a protonic solvent or an aprotic polar solvent.
- organic solvent examples include dimethylsulfoxide (DMSO), N, N-dimethylformamide, N-methyl formamide, methanol, ethanol Ethanol, isopropanol, 2-methoxyethanol, water and the like. These may be used alone or in combination of two or more.
- DMSO dimethylsulfoxide
- N N-dimethylformamide
- N-methyl formamide N-methyl formamide
- methanol ethanol Ethanol
- isopropanol 2-methoxyethanol
- the organic solvent may be contained in an amount of 70 to 99.99% by weight, preferably 80 to 99.9% by weight based on 100% by weight of the entire coating composition. If the content of the organic solvent is less than the above range, the metal salt compound may not be sufficiently dissolved, the performance of the cathode active material may be deteriorated due to side reactions, and it may be difficult to form a uniform thickness layer. The excess energy is consumed in the process of removing the protective layer, so that the economical efficiency and the productivity are lowered, and it is difficult to obtain the desired protective layer function.
- the coating compositions comprising the foregoing components are uniformly mixed on an organic solvent to form a precursor of the metal-phosphorus-oxynitride for metal-phosphorus-oxynitride formation.
- the precursor of the metal-phosphorus-oxynitride is produced by the reaction of a compound containing a phosphorus-nitrogen bond and a metal salt compound.
- the coating composition may be heated at a predetermined temperature in a state in which the above-mentioned components are mixed.
- the coating composition may be heated at a temperature of from 40 to 150 DEG C before being used in a subsequent solution process.
- Such a heating process is for a type of pretreatment, and the components forming the coating composition may react to form a precursor that partially replicates the lattice structure of the metal-phosphorus-oxynitride.
- the coating composition may comprise a chalcogenide.
- the chalcogen compound is excellent in electrical conductivity, when a chalcogen compound is further contained in the coating composition, the chalcogen element in the lattice structure of the finally formed metal-phosphorus-oxynitride is included, thereby further improving the conductivity.
- the chalcogen compound may be selected from the group consisting of TiS 2 , VS 2 , FeS 2 , MoS 2 , CoS 3 , TiSe 2 , VSe 2 , NbSe 3 , SeO 2 , TiTe 2 , VTe 2 , LiTiS 2 and LiVS 2 And may include at least one kind selected.
- step (b) forms the precursor layer on the cathode active material by a solution process of the coating composition prepared in step (a) described above.
- the coating composition is coated on the cathode active material by a solution process to form a precursor layer.
- a deposition process such as sputtering or vapor deposition is used to form a protective layer that protects the surface of the cathode active material Respectively.
- a protective layer is formed by such a deposition process, it is excellent in terms of quality but it is difficult to apply the material when the object is a particle, and since it needs to work in a vacuum state and requires a separate device, .
- the present invention is characterized in that it is suitable for a solution process by preparing the coating composition in the liquid phase in the step (a), and can be applied to various shapes unlike the conventional deposition process.
- the uniformity of the coating of the protective layer is excellent by using the solution process, and the process can be simplified, and the process time and cost can be greatly reduced.
- the solution process may be at least one of spray coating, spin coating, dip coating, inkjet printing, offset printing, reverse offset printing, gravure printing, and roll printing.
- the cathode active material to be coated is used in a lithium secondary battery, and all the cathode active materials known in the art can be used.
- the cathode active material may include a conventional cathode active material that can be used for a cathode of a conventional lithium secondary battery, for example, an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a Group 15 element, a transition metal, a rare earth element, A lithium-containing metal oxide can be used. Chalcogenide-based compounds are also applicable.
- LiMn 2 O 4 lithium-manganese composite oxide such as, LiNiO 2 , Lithium cobalt oxide such as LiCoO 2 , vanadium oxide containing lithium, or a chalcogen compound or the like in which a part of manganese, nickel, or cobalt of these oxides is replaced with another common transition metal or the like) have.
- the cathode active material may be spherical, elliptical, spindle-shaped, scaly, plate-shaped, fibrous, rod-shaped, core-shell or irregular.
- a precursor layer may be coated on the surface of the cathode active material by adding a particle type cathode active material to the coating composition and stirring the mixture.
- the solution process may be performed in an inert atmosphere such as nitrogen or argon or a dry air condition of 5% or less relative humidity.
- an organic solvent removing process may be performed before the heat treatment process for forming the metal-phosphorus-oxide nitride protective layer.
- the organic solvent removal process may be a heat treatment process performed at a lower temperature than the heat treatment process for forming the protective layer.
- the temperature of the organic solvent removal process may vary depending on the type of the organic solvent included in the coating composition.
- the organic solvent removal step may be performed at a temperature close to the boiling point of the organic solvent, for example, 40 to 150 ° C. By performing the organic solvent removing step, it is possible to reduce the mechanical stress of the protective layer due to the volume reduction after the heat treatment step for forming the protective layer described later. Accordingly, a protective layer uniformly coated on the cathode active material can be formed.
- the organic solvent removal step may also be performed in an inert atmosphere such as nitrogen or argon, or in dry air at a relative humidity of 5% or less.
- step (c) the cathode active material having the precursor layer formed in the step (b) described above is heat-treated to form a metal-phosphorus-oxynitride protective layer on the cathode active material.
- a heating polymerization reaction of the components constituting the precursor layer occurs through a heat treatment process to form a metal-phosphorus-oxynitride or a derivative thereof, and a protective layer including the metal-phosphorus- In the heat polymerization reaction, a ring-opening reaction, a condensation reaction and a polymerization reaction of the components contained in the precursor layer occur, and a metal-phosphorus-oxynitride in which phosphorus and nitrogen are mixed is formed. In this case, one nitrogen forms a phosphorous-nitrogen-oxygen skeleton which bonds with two or three atoms.
- a heating polymerization reaction takes place and unnecessary impurities can be removed by heat.
- the impurities may be carbon, hydrogen, chlorine, etc. contained in the coating composition.
- the metal-phosphorus-oxynitride included in the protective layer includes chemical structures represented by Chemical Formulas 4 and 5, which include amorphous phases of metal-phosphorus-oxynitride.
- M n + in each of the following formulas (4) and (5) represents a monovalent, divalent or trivalent metal cation. That is, M represents a kind of metal, n represents any integer of 1 to 3, and M n + may represent Li + , Mg 2 + , Al 3 +, or the like.
- the chemical structure of Formula 4 is a partial chemical structure that contains a single combination of phosphorus and nitrogen, in the case of the monovalent cation M + [PO 2 O 1/ 2 N 1/3] - a 2 in the case of the cation M 2 + 2 [PO 2 O 1/2 N 1/3] - may be represented by -, the three cases of the cation M 3+ 3 [PO 2 O 1 /2 N 1/3].
- the chemical structure represented by Chemical Formula 4 may be connected to phosphorus of M 1 / n PO 3 to form two phosphorus-nitrogen bonds, thereby forming a phosphorus-nitrogen-phosphorus bond.
- O < - > may be combined with M < n + >, and O < 1/2 > may be combined with another phosphorus to form phosphorous-oxygen-phosphorous bonds.
- O - can be bonded to M n +
- O 1/2 can be bonded to another phosphorus to form a phosphorus-oxygen-phosphorus bond.
- the heat treatment process may be performed in an inert atmosphere such as nitrogen or argon, or dry air having a relative humidity of 5% or less.
- the temperature of the heat treatment process may be performed at 150 ° C or higher and lower than 500 ° C.
- the precursor layer may be formed through a solution process in the step (b) of the present invention, as compared with a case where the precursor layer is formed at a temperature higher than 500 ° C.
- the heat treatment process is preferably performed for at least 5 minutes or more, and the heat treatment process may be performed for 5 minutes to 1 hour, for example.
- the metal-phosphorus-oxynitride protective layer formed from the step (c) may be formed on at least a part of the above-mentioned cathode active material.
- the protective layer may be formed over a part or the entire surface of the cathode active material .
- the protective layer may be formed to have a surface area of 50% or more, preferably 70% or more of the total surface area of the cathode active material.
- the protective layer may include 0.01 to 5% by weight, preferably 0.05 to 3% by weight based on 100% by weight of the total amount of the cathode active material. It is preferable that the protective layer is formed in the above-described range because it can improve not only the stability of the active material but also the ion conductivity.
- the thickness of the protective layer may be 1 to 1000 nm, preferably 1 to 100 nm.
- one protective layer can be formed.
- (B) and (c) may be performed again after the protective layer is formed, that is, the protective layer is already formed on the positive electrode active material, so that the protective layer can be formed secondarily.
- the protective layer may be laminated by repeating the steps (b) and (c) to form a multi-layered protective layer. That is, the thickness of the protective layer and the laminated structure can be easily controlled by repeating the process.
- the above-described method for producing a cathode active material can easily produce a protective layer including a metal-phosphorus-oxynitride or a derivative thereof in a uniform quality through a metal-phosphorus-nitride precursor solution process.
- the protective layer prepared from the above method is excellent in uniformity and coating property, so that in the case of the cathode active material prepared according to the present invention, the stability of reaction with the electrolyte is improved, and the ionic conductivity of the protective layer is constant, . Accordingly, the cycle characteristics, stability, and life characteristics of the lithium secondary battery including the cathode active material of the present invention can be improved.
- the present invention also provides a lithium secondary battery comprising the cathode active material.
- the secondary battery includes a positive electrode; cathode; And a separator interposed between the anode and the cathode, and an electrolyte, wherein the anode comprises the cathode active material produced according to the present invention.
- the positive electrode and the negative electrode can be manufactured by a conventional method known in the art.
- the electrode slurry is prepared by mixing each of the positive electrode active material and the negative electrode active material with a binder, a conductive material, etc., , Rolling and drying. At this time, a small amount of conductive material and / or binder may be selectively added.
- the positive electrode may include a positive electrode collector and a positive electrode active material coated on one or both surfaces of the positive electrode collector.
- the positive electrode collector is for supporting the positive electrode active material and is not particularly limited as long as it has excellent conductivity and is electrochemically stable in the voltage range of the lithium secondary battery.
- the positive electrode collector may be any metal selected from the group consisting of copper, aluminum, stainless steel, titanium, silver, palladium, nickel, alloys thereof, and combinations thereof, , Nickel, titanium or silver.
- the alloy may be an aluminum-cadmium alloy.
- a non-conductive polymer surface-treated with a conductive material such as sintered carbon, a conductive polymer, or the like may be used have.
- the cathode current collector may have fine irregularities on the surface thereof to enhance the bonding force with the cathode active material, and various forms such as a film, a sheet, a foil, a mesh, a net, a porous body, a foam, and a nonwoven fabric may be used.
- the cathode active material may include a cathode active material and optionally a conductive material and a binder.
- the cathode active material follows the above description.
- the conductive material serves as a path for electrically connecting the cathode active material and the electrolyte to move the electrons from the current collector to the active material, and can be used without limitation as long as it does not cause chemical change in a cell having porous and conductive properties .
- carbon-based materials having porosity can be used.
- the carbon-based materials include carbon black, graphite, graphene, activated carbon, carbon fiber, and the like; metallic fibers such as metal mesh; Metallic powder such as copper, silver, nickel, and aluminum; Or an organic conductive material such as a polyphenylene derivative.
- the conductive materials may be used alone or in combination.
- Commercially available conductive materials include acetylene black series (Chevron Chemical Company or Gulf Oil Company products), Ketjen Black EC series (Armak Company Vulcan XC-72 (Cabot Company) and Super P (MMM Co., Ltd.).
- the binder is a material which is contained in the current collector to hold the slurry composition forming the anode and which is well dissolved in a solvent and can stably form a conductive network with the above-mentioned active material and conductive material. All binders known in the art can be used unless otherwise specified.
- the binder may include a fluororesin binder including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE); Rubber-based binders including styrene butadiene rubber (SBR), acrylonitrile-butadiene rubber, and styrene-isoprene rubber; Cellulose-based binders including carboxyl methyl cellulose (CMC), starch, hydroxypropylcellulose, and regenerated cellulose; Polyalcohol-based binders; Polyolefin binders including polyethylene and polypropylene; Polyimide-based binders; Polyester binders; And a silane-based binder; and mixtures or copolymers of two or more thereof.
- PVdF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- Rubber-based binders including styrene butadiene rubber (SBR), acrylonitrile-butadiene
- the negative electrode may include a negative electrode active material, a conductive material, and a binder in the same manner as the positive electrode, and the conductive material and the binder are as described above.
- the negative electrode active material is a material capable of reversibly intercalating or deintercalating lithium ions (Li + ), a material capable of reversibly reacting with lithium ions to form a lithium-containing compound, and includes a lithium metal, a lithium alloy , A transition metal complex oxide, a silicon-based material, a tin-based material, and a carbon-based material.
- the negative electrode active material may be selected from the group consisting of crystalline artificial graphite, crystalline natural graphite, amorphous hard carbon, low crystalline soft carbon, carbon black, acetylene black, Ketjenblack, Super-P, graphene, One or more carbon-based materials selected; Silicone-based materials, 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 ': a transition metal complex oxide such as Al, B, P, Si, Group 1, Group 2 or Group 3 elements of the periodic table, Halogen; 0? X? 1; 1? Y?
- Lithium metal Lithium alloy; Silicon based alloys; Tin alloy; 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, Bi 2 O 5 and the like; Conductive polymers such as polyacetylene; Li-Co-Ni-based materials; Titanium oxide; Lithium titanium oxide, and the like, but the present invention is not limited thereto.
- the separation membrane is used for physically separating both electrodes in the lithium secondary battery of the present invention and can be used without any particular limitation as long as it is used as a separation membrane in a lithium secondary battery. It is preferable that the wetting ability is excellent.
- the separator may be formed of a porous substrate.
- the porous substrate may be any porous substrate commonly used in an electrochemical device.
- the porous substrate may be a polyolefin porous film or a nonwoven fabric. .
- polyolefin-based porous film examples include polyolefin-based polymers such as polyethylene, polypropylene, polybutylene, and polypentene, such as high-density polyethylene, linear low density polyethylene, low density polyethylene and ultra high molecular weight polyethylene, One membrane can be mentioned.
- the nonwoven fabric may include, in addition to the polyolefin nonwoven fabric, for example, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polycarbonate ), Polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide, polyphenylenesulfide, and polyethylene naphthalate, which are used alone or in combination, Or a nonwoven fabric formed of a polymer mixed with these.
- the structure of the nonwoven fabric may be a spun bond nonwoven fabric or a melt blown nonwoven fabric composed of long fibers.
- the thickness of the porous substrate is not particularly limited, but may be 1 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
- the size and porosity of the pores present in the porous substrate are also not particularly limited, but may be 0.001 to 50 ⁇ and 10 to 95%, respectively.
- the electrolyte includes lithium ions and is used for causing an electrochemical oxidation or reduction reaction between the positive electrode and the negative electrode through the electrolyte.
- the electrolyte may be a non-aqueous electrolyte or a solid electrolyte which does not react with lithium metal, but is preferably a nonaqueous electrolyte, and includes an electrolyte salt and an organic solvent.
- the electrolyte salt contained in the non-aqueous electrolyte is a lithium salt.
- the lithium salt can be used without limitation as long as it is commonly used in an electrolyte for a lithium secondary battery.
- 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, LiN (SO 2 F) 2 , chloroborane lithium, lower aliphatic carboxylate lithium, lithium 4-phenylborate, lithium imide and the like can be used.
- organic solvent included in the non-aqueous electrolyte examples include those commonly used in electrolytes for lithium secondary batteries, such as ether, ester, amide, linear carbonate, cyclic carbonate, etc., Can be used. Among them, an ether compound may be typically included.
- the ether compound may be selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether, dimethoxy ethane, methoxyethoxyethane, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetra At least one selected from the group consisting of ethylene glycol methyl ethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, and polyethylene glycol methyl ethyl ether may be used, but is not limited thereto.
- ester in the organic solvent examples include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate,? -Butyrolactone,? -Valerolactone,? -Caprolactone, Valerolactone, and epsilon -caprolactone, or a mixture of two or more thereof, but the present invention is not limited thereto.
- linear carbonate compound examples include any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate and ethyl propyl carbonate A mixture of two or more of them may be used as typical examples, but the present invention is not limited thereto.
- cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate , 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and halides thereof, or a mixture of two or more thereof.
- halides include, but are not limited to, fluoroethylene carbonate (FEC) and the like.
- the electrolyte may include at least one selected from the group consisting of a liquid electrolyte, a gel polymer electrolyte, and a solid polymer electrolyte. And may be an electrolyte in a liquid state.
- the injection of the nonaqueous electrolyte solution can be performed at an appropriate stage of the manufacturing process of the electrochemical device according to the manufacturing process and required properties of the final product. That is, it can be applied before assembling the electrochemical device or in the final stage of assembling the electrochemical device.
- the lithium secondary battery according to the present invention can be laminated, stacked, and folded in addition to winding, which is a general process.
- the shape of the secondary battery is not particularly limited and may be various shapes such as a cylindrical shape, a laminate shape, and a coin shape.
- 0.0034 M hexachlorophosphazene and 0.0204 M lithium hydroxide hydrate were mixed with water and a 2-methoxyethanol mixture (1:19 (by volume)) for the preparation of a coating composition comprising a precursor with a lithium and phosphorus atomic ratio of 2: 20 < 0 > C for 40 minutes at 70 [deg.] C to prepare a coating composition.
- the cathode active material was heat-treated at 500 ⁇ under an inert nitrogen atmosphere to prepare a cathode active material having a protective layer having a thickness of 5 nm.
- a cathode active material was prepared in the same manner as in Example 1, except that a protective layer having a thickness of 2 nm was formed using a coating composition comprising a precursor having an atomic ratio of lithium and phosphorus of 2: 1.
- a cathode active material was prepared in the same manner as in Example 1, except that a protective layer having a thickness of 1 nm was formed using a coating composition containing a precursor having an atomic ratio of lithium and phosphorus of 2: 1.
- Example 1 The cathode active materials prepared in Example 1 and Comparative Example 1 were observed using a scanning electron microscope (SEM) (Model: S-4800, HITACHI). The results obtained at this time are shown in Figs. 1 and 2.
- SEM scanning electron microscope
- FIG. 1 shows that the surface of the positive electrode active material of Comparative Example 1 is exposed.
- the positive electrode was prepared using the positive electrode active material prepared in the above Examples and Comparative Examples.
- a cathode active material prepared in Examples and Comparative Examples 0.45 g of the cathode active material prepared in Examples and Comparative Examples, 0.025 g of a binder (KF1100) and 0.025 g of a conductive material (denka black) were mixed with 0.7 g of N-methylpyrrolidone (NMP) to prepare a cathode slurry .
- the positive electrode slurry was coated on an aluminum current collector having a thickness of 20 ⁇ m to a thickness of 200 ⁇ m, followed by drying.
- the battery manufactured by the above method was evaluated for lifetime and capacity characteristics using a constant current-constant voltage method. The results obtained at this time are shown in FIG. 3 and FIG.
- FIG. 3 shows that the discharge capacities of Examples 1 to 3 in which a protective layer is formed are higher than those of Comparative Example 1 in which no protective layer is formed.
- FIG. 4 shows that the capacity retention rate of the battery including the cathode active material of the embodiment is excellent, and in particular, in the case of Example 1, the capacity stably maintains 90% or more even after 150 cycles .
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Abstract
La présente invention concerne un procédé de fabrication d'un matériau actif positif, ainsi qu'un matériau actif positif et une batterie secondaire au lithium l'utilisant et, plus spécifiquement, un procédé de fabrication d'un matériau actif positif, comprenant les étapes suivantes : (a) préparation d'une composition de revêtement comprenant un précurseur d'oxynitrure de phosphore métallique ; (b) formation d'une couche de précurseur sur un matériau actif positif au moyen d'un traitement en solution de la composition de revêtement ; et (c) formation d'une couche de protection d'oxynitrure de phosphore métallique sur le matériau actif positif par traitement thermique du matériau actif positif sur lequel est formée la couche de précurseur. Le procédé de fabrication d'un matériau actif positif selon la présente invention non seulement est avantageux en termes de simplification de processus global et de réduction de coût par utilisation d'un traitement en solution, mais aussi permet une capacité élevée, une stabilité élevée et une longue durée de vie étant donné qu'il comprend la couche de protection formée ayant d'excellentes propriétés.
Priority Applications (4)
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JP2019531203A JP7062150B2 (ja) | 2017-09-01 | 2018-08-29 | 正極活物質の製造方法及びこれを用いた正極活物質及びリチウム二次電池 |
EP18850580.4A EP3546429B8 (fr) | 2017-09-01 | 2018-08-29 | Procédé de fabrication de matériau actif positif, et matériau actif positif et batterie secondaire au lithium le comprenant |
CN201880008690.1A CN110225885B (zh) | 2017-09-01 | 2018-08-29 | 正极活性材料的制备方法以及使用所述方法制备的正极活性材料和锂二次电池 |
US16/470,149 US11444275B2 (en) | 2017-09-01 | 2018-08-29 | Method for manufacturing positive active material, and positive active material and lithium secondary battery using same |
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KR1020180101231A KR102148512B1 (ko) | 2017-09-01 | 2018-08-28 | 양극 활물질의 제조방법 및 이를 이용한 양극 활물질 및 리튬 이차전지 |
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