WO2019045408A1 - Procédé de fabrication de matériau actif négatif, matériau actif négatif et batterie secondaire au lithium le comprenant - Google Patents

Procédé de fabrication de matériau actif négatif, matériau actif négatif et batterie secondaire au lithium le comprenant Download PDF

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WO2019045408A1
WO2019045408A1 PCT/KR2018/009906 KR2018009906W WO2019045408A1 WO 2019045408 A1 WO2019045408 A1 WO 2019045408A1 KR 2018009906 W KR2018009906 W KR 2018009906W WO 2019045408 A1 WO2019045408 A1 WO 2019045408A1
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active material
phosphorus
negative electrode
metal
electrode active
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PCT/KR2018/009906
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English (en)
Korean (ko)
Inventor
성다영
김명길
장민철
황혜원
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주식회사 엘지화학
중앙대학교 산학협력단
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Priority claimed from KR1020180099369A external-priority patent/KR102148511B1/ko
Application filed by 주식회사 엘지화학, 중앙대학교 산학협력단 filed Critical 주식회사 엘지화학
Priority to US16/469,328 priority Critical patent/US10971754B2/en
Priority to EP18849998.2A priority patent/EP3546428B8/fr
Priority to JP2019532788A priority patent/JP7062151B2/ja
Priority to CN201880008708.8A priority patent/CN110234605A/zh
Publication of WO2019045408A1 publication Critical patent/WO2019045408A1/fr

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • 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
    • H01M4/36—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
    • 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 manufacturing an anode active material, an anode active material using the anode active material, and a lithium secondary battery.
  • lithium secondary batteries having advantages such as high energy density, discharge voltage, and output stability are attracting attention.
  • the lithium secondary battery has a structure in which an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode is laminated or wound, and the electrode assembly is embedded in a battery case and a non-aqueous electrolyte is injected into the electrode assembly .
  • the capacity of the lithium secondary battery differs depending on the type of the electrode active material, and a sufficient capacity can not be secured by the theoretical capacity at the time of actual operation, so that the lithium secondary battery has not been commercialized.
  • the anode active material of the lithium secondary battery may be a crystalline carbon such as natural graphite or artificial graphite, a pseudo-graphite structure obtained by carbonizing a hydrocarbon or a polymer at a temperature of 1000 to 1500 ° C, A carbon-based material such as low crystalline carbon having a turbostratic structure is used.
  • This carbon-based material has a standard redox potential of about -3 V against the standard hydrogen electrode (SHE) potential, and has a layered structure, which is very useful for insertion and desorption of lithium ions And is excellent in charge / discharge reversibility.
  • SHE standard hydrogen electrode
  • the theoretical capacity of graphite is limited to 372 mAh / g, which limits the capacity to high capacity.
  • a metallic material having a large theoretical capacity such as lithium (3,860 mAh / g), silicon (4,200 mAh / g) and tin (990 mAh / g) is used as a negative electrode active material.
  • a metal such as lithium, silicon, or tin
  • the volume expands to about 4 times as much as the lithium-alloyed charging process, and shrinks during discharge.
  • the active material gradually becomes undifferentiated due to a large change in the volume of the electrode repeatedly generated during charging and discharging, and the capacitance is rapidly reduced due to dropping from the electrode. As a result, stability and reliability can not be secured.
  • a negative electrode active material and an electrolyte react with each other to form a solid electrolyte interphase (SEI) on the surface, thereby causing irreversible capacity reduction.
  • SEI solid electrolyte interphase
  • the formed passivation layer causes a difference in current density on a localized portion to form dendritic lithium dendrites on the surface of the negative electrode active material.
  • Lithium dendrites not only shorten the lifetime of lithium secondary batteries but also cause internal short circuit and dead lithium, which adversely affects the physical and chemical instability of lithium secondary batteries, adversely affecting capacity, cycle characteristics and lifetime of the battery .
  • the passive layer is thermally unstable and can be gradually disintegrated by the increased electrochemical energy and thermal energy during the charge and discharge processes of the cell, especially during high temperature storage in a fully charged state. Due to the collapse of the passivation layer, the exposed surface of the negative electrode active material reacts directly with the electrolyte, and the electrolyte decomposes continuously. As a result, the resistance of the negative electrode increases and the charge / discharge efficiency of the battery decreases.
  • Korean Patent Laid-Open Publication No. 2015-0077053 discloses a method for manufacturing a negative electrode active material and a secondary battery including the same by forming a ceramic coating layer containing aluminum oxide, zirconium oxide, or the like on the surface of a negative electrode active material core Life and performance can be improved.
  • Korean Patent Laid-Open Publication No. 2016-0034183 discloses a positive electrode active layer containing a lithium metal or a lithium alloy and a polymer matrix capable of protecting the negative electrode and accumulating an electrolyte solution to form a protective layer to prevent electrolyte loss and dendrite formation And the like.
  • Korean Patent Publication No. 2015-0077053 (2015.07.07), an anode active material, a method for manufacturing a secondary battery and an anode active material containing the same
  • Korean Patent Publication No. 2016-0034183 (Mar. 29, 2016), a cathode for a lithium secondary battery and a lithium secondary battery comprising the same
  • 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, the protective layer is easily formed and the coating property is improved, so that the lifetime characteristics of the negative electrode active material are improved.
  • the present invention has been completed.
  • an object of the present invention is to provide a method of manufacturing a negative electrode active material, which can manufacture a metal-phosphorus-nitride oxide protective layer having excellent characteristics on a negative electrode active material by a simple process as compared with the prior art.
  • Another object of the present invention is to provide a negative active material and a lithium secondary battery including the negative active material according to the above production method.
  • 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 negative electrode active material may include at least one selected from the group consisting of lithium metal, a lithium alloy, a transition metal oxide, a silicon-based material, a tin-based material, and a carbon-based material.
  • the negative electrode active material may be in the form of a sphere, an ellipse, a spiral, an scaly, a plate, a fiber, a rod, a core-shell or an irregular shape.
  • 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 the negative electrode active material produced by the above production method.
  • the present invention provides a lithium secondary battery comprising the negative active material.
  • the method for preparing the negative electrode active material according to the present invention is a method for producing a negative active material comprising a metal-phosphorus-oxynitride precursor and a metal-phosphorus-oxynitride precursor,
  • the protective layer can be easily formed.
  • the anode active material can be manufactured through mild reaction under mild conditions, as well as minimizing the manufacturing cost and shortening the manufacturing time, so that it can be applied commercially.
  • the negative electrode active material having the protective layer prepared according to the production method of the present invention can provide an anode active material which is excellent in the reaction stability with the electrolyte solution and has ion conductivity and can provide high capacity and long life, The capacity and life characteristics of the battery can be improved.
  • Example 2 is a scanning electron microscope image of the negative electrode active material prepared in Example 1 of the present invention.
  • Example 3 is an image showing an EDS elemental analysis result of the negative electrode active material prepared in Example 1 of the present invention.
  • Example 4 is a graph showing an EDS elemental analysis result of the negative electrode active material prepared in Example 1 of the present invention.
  • lithium secondary batteries have been expanded from cell phones and wireless electronic devices to electric vehicles, and it is required to develop a lithium secondary battery capable of miniaturization, light weight, thinness, and portability and having high performance, long life and high reliability have.
  • a negative electrode active material for forming a negative electrode active material layer in order to uniformly form a protective layer containing a specific compound on the surface of the negative electrode active material through a simple process, and to secure the performance and life-span improvement effect of the lithium secondary battery including the positive electrode active material, A negative electrode active material for forming a negative electrode active material layer.
  • 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 specific optimum amount of the phosphorus-nitrogen-containing compound may be varied depending on other properties of the negative 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-methylformamide, methanol, ethanol Ethanol, isopropanol, 2-methoxyethanol, water and the like. These may be used alone or in combination of two or more.
  • 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 sufficiently dissolve, the performance of the negative electrode 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 a precursor layer on the anode active material by a solution process of the coating composition prepared in step (a) described above.
  • the coating composition is coated on the anode active material to form a precursor layer.
  • a deposition process such as sputtering or vapor deposition is used to form a protective layer on the anode active material.
  • 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 anode active material to be coated is used in a lithium secondary battery, and all the anode active materials known in the related art can be used.
  • 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 negative electrode active material may be in the form of a sphere, an ellipse, a spiral, an scaly, a plate, a fiber, a rod, a core-shell or an irregular shape.
  • the precursor layer may be coated on the surface of the negative electrode active material by injecting and stirring the particle-shaped negative active material into the coating composition.
  • 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 step may be performed before the heat treatment step for forming the metal-phosphorus-oxynitride 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.
  • a protective layer that is uniformly coated on the entire surface of the anode 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 precursor layer formed in step (b) is annealed to form a metal-phosphorus-oxynitride protective layer on the anode 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 < - &gt 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 negative electrode active material described above. Specifically, the protective layer may be formed over a part or the entire surface of the negative electrode active material . For example, the protective layer may be formed to be 50% or more, preferably 70% or more of the total surface area of the negative electrode 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 entire negative electrode 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 negative 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 method of manufacturing the negative electrode active material according to the present invention can easily produce a protective layer containing 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 has excellent uniformity and coating property, the negative electrode active material prepared according to the present invention improves the reaction stability with the electrolyte and has a certain level of ionic conductivity by the protective layer, . Accordingly, the cycle characteristics, stability, and lifetime characteristics of the lithium secondary battery including the negative electrode active material of the present invention can be improved
  • the present invention also provides a lithium secondary battery comprising the negative electrode active material.
  • the secondary battery includes a positive electrode; cathode; And a separator interposed between the positive electrode and the negative electrode, and an electrolyte, wherein the negative electrode includes the negative electrode active material prepared 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 may be a layered compound such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals; Lithium manganese oxides such as Li 1 + x Mn 2-x O 4 (0 ? X?
  • 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.
  • the conductive material may be any material that does not cause chemical change in a porous and conductive battery. have.
  • 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 for holding the slurry composition forming the anode and is well dissolved in a solvent and is capable of stably forming the 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 follows the above description.
  • 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 an electrolyte for a lithium secondary battery, such as an ether, an ester, an amide, a linear carbonate, and a cyclic carbonate, 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.
  • graphite having an average particle diameter of 15 ⁇ m was added to the coating composition so that the ratio of the active material to the coating composition was 0.5% by weight, stirred at 50 ° C. for 1 hour, and vacuum dried to remove the organic solvent.
  • An anode active material was prepared in the same manner as in Example 1, except that the ratio of the active material to the coating composition containing the precursor having an atomic ratio of lithium and phosphorus of 2: 1 was 0.1% by weight.
  • An anode active material was prepared in the same manner as in Example 1, except that the ratio of the active material to the coating composition containing the precursor having an atomic ratio of lithium and phosphorus of 2: 1 was 0.05 wt%.
  • Graphite having an average particle size of 15 mu m without forming a protective layer was used as the negative electrode active material.
  • Example 1 The negative electrode active materials prepared in Example 1 and Comparative Example 1 were subjected to a scanning electron microscope (SEM) (model: S-4800, HITACHI) and an energy dispersive spectroscopy (EDS) M, Bruker). The results obtained at this time are shown in Figs. 1 to 4.
  • SEM scanning electron microscope
  • HITACHI HITACHI
  • EDS energy dispersive spectroscopy
  • the surface of the negative electrode active material of Comparative Example 1 is directly exposed, whereas the negative active material of Example 1 shows that the protective layer is uniformly formed on the surface.
  • the phosphorus (P) element originating from the precursor of the metal-phosphorus-oxynitride is uniformly coated on the entire surface of the anode active material.
  • FIG. 4 shows that the phosphorus (P) element content is about 0.3 wt% .
  • the negative electrode was prepared using the negative active material prepared in the above Examples and Comparative Examples.
  • a lithium metal foil having a thickness of 150 ⁇ m was used as the counter electrode.
  • the prepared negative electrode and the counter electrode were placed face to face with a polyethylene separator interposed therebetween. Thereafter, ethylene carbonate, diethyl carbonate and dimethyl carbonate (25: 50: 25 (volume ratio)) dissolved in 1 M LiPF 6 as an electrolyte A half cell was fabricated by injecting mixed solvent.
  • Example 1 st Efficiency (%) Example 1 93.45
  • Example 2 92.9
  • Example 3 91.69 Comparative Example 1 91.43

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  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne un procédé de fabrication d'un matériau actif négatif, ainsi qu'un matériau actif négatif et une batterie secondaire au lithium l'utilisant et, plus spécifiquement, un procédé de fabrication d'un matériau actif négatif, 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 négatif 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 négatif par traitement thermique du matériau actif négatif sur lequel est formée la couche de précurseur. Le procédé de fabrication d'un matériau actif négatif selon la présente invention non seulement est avantageux en termes de simplification de processus global et de réduction de coût en utilisant un traitement en solution, aussi mais 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.
PCT/KR2018/009906 2017-09-01 2018-08-28 Procédé de fabrication de matériau actif négatif, matériau actif négatif et batterie secondaire au lithium le comprenant WO2019045408A1 (fr)

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US16/469,328 US10971754B2 (en) 2017-09-01 2018-08-28 Method for manufacturing negative active material, and negative active material and lithium secondary battery using same
EP18849998.2A EP3546428B8 (fr) 2017-09-01 2018-08-28 Procédé de fabrication de matériau actif négatif, matériau actif négatif et batterie secondaire au lithium le comprenant
JP2019532788A JP7062151B2 (ja) 2017-09-01 2018-08-28 負極活物質の製造方法及びこれを用いた負極活物質及びリチウム二次電池
CN201880008708.8A CN110234605A (zh) 2017-09-01 2018-08-28 负极活性材料的制备方法以及使用所述方法得到的负极活性材料和锂二次电池

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