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WO2021033852A1 - Matériau actif positif, son procédé de préparation, et batterie rechargeable au lithium à électrode positive le comprenant - Google Patents

Matériau actif positif, son procédé de préparation, et batterie rechargeable au lithium à électrode positive le comprenant Download PDF

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WO2021033852A1
WO2021033852A1 PCT/KR2019/018554 KR2019018554W WO2021033852A1 WO 2021033852 A1 WO2021033852 A1 WO 2021033852A1 KR 2019018554 W KR2019018554 W KR 2019018554W WO 2021033852 A1 WO2021033852 A1 WO 2021033852A1
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active material
positive electrode
electrode active
formula
transition metal
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Korean (ko)
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서민호
김지영
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SM Lab Co Ltd
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SM Lab Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

  • It relates to a positive electrode active material having a novel composition, and a lithium secondary battery including a positive electrode including the same.
  • the present invention was made with the funding of the Ministry of Trade, Industry and Energy under the title of "Development of High Strength/Long Life/High Stability Ni-rich NCA (> 210mAh/g, @4.3V) Cathode Material for Medium and Large Size Lithium Secondary Battery” .
  • NCM and NCA with a molar ratio of Ni of 50 mol% or more are attracting attention in terms of high capacity.
  • such a Ni-based positive electrode active material is prepared by mixing a transition metal compound precursor synthesized by a coprecipitation method with a lithium source and then synthesizing it in a solid state.
  • the Ni-based cathode material synthesized in this way exists in the form of secondary particles in which small primary particles are agglomerated, and there is a problem that micro-crack occurs inside the secondary particles during a long-term charging/discharging process.
  • the microcracks cause a side reaction between the new interface of the positive electrode active material and the electrolyte, and as a result, deterioration of battery performance such as degradation of stability due to gas generation and degradation of battery performance due to depletion of the electrolyte is caused.
  • an increase in electrode density (>3.3g/cc) is required to realize a high energy density, which causes the collapse of secondary particles, causing electrolyte depletion due to side reactions with the electrolyte, causing a sharp decline in initial lifespan. Consequently, it means that the Ni-based cathode active material in the form of secondary particles synthesized by the conventional co-precipitation method cannot realize high energy density.
  • the single crystal type Ni-based positive electrode active material does not cause particle collapse when the electrode density is increased (> 3.3g/cc) to realize high energy density, so it can realize excellent electrochemical performance.
  • a single crystal type Ni-based positive electrode active material has a problem in that battery stability is deteriorated due to structural and/or thermal instability due to unstable Ni 3+ and Ni 4+ ions during electrochemical evaluation. Therefore, in order to develop a high-energy lithium secondary battery, there is still a need for a technology for stabilizing unstable Ni ions in a single crystal Ni-based positive electrode active material.
  • a positive electrode active material with improved high energy density and long life characteristics is provided.
  • a core comprising a lithium transition metal oxide including W and B; And a phosphorus-containing coating layer disposed on the surface of the core.
  • a Li-containing compound, W-containing compound, B-containing compound, A-containing compound, M-containing compound, T-containing compound, and phosphorus-containing compound to obtain a lithium transition metal oxide precursor
  • A is one or more elements selected from the group consisting of Na, K, Rb and Cs,
  • T is one or more elements selected from the group consisting of S, F and P,
  • M includes at least one element selected from the group consisting of Ni, Co, Mn, Al, Mg, V, Ti and Ca,
  • a positive electrode including the positive electrode active material; cathode; And there is provided a lithium secondary battery comprising an electrolyte.
  • the cathode active material according to an aspect of the present invention is doped with a heterogeneous element in single crystal and single particle lithium transition metal oxide particles, and the heterogeneous element is introduced into the hollow lattice in the single crystal and single particle, thereby unstable present in the high-Ni-based cathode active material.
  • Ni ions were stabilized, and as a result, the capacity per unit volume and life stability were improved.
  • the P-containing coating layer on the surface of the lithium transition metal oxide particles the effect of suppressing side reactions with the electrolyte and reducing residual lithium was achieved.
  • Example 1 is a SEM photograph of the cathode active material of Example 1 and Comparative Example 1.
  • Example 2 is a graph showing the particle size distribution of positive electrode active materials of Example 1 and Comparative Example 1.
  • Example 3 is an XRD graph of the positive electrode active material of Example 1 and Comparative Example 1.
  • FIG. 4 is a graph of life retention rates for the half cells of Example 4 and Comparative Example 7.
  • FIG. 4 is a graph of life retention rates for the half cells of Example 4 and Comparative Example 7.
  • Example 5 is a graph showing the life retention rate for the half cells of Example 4 and Comparative Examples 8 to 9;
  • Example 6 is a graph of life retention rates for the half cells of Example 4 and Comparative Examples 10 to 11.
  • Example 7 is a graph of life retention rates for the half cells of Example 4 and Comparative Example 12;
  • Example 8 is a graph of life retention rates for the half cells of Example 5 and Comparative Example 13.
  • Example 9 is a graph of life retention rates for the half cells of Example 6 and Comparative Example 14;
  • FIG. 10 is a schematic diagram of a lithium battery according to an exemplary embodiment.
  • lithium battery 2 negative electrode
  • the positive electrode active material includes a core including a lithium transition metal oxide including W and B; And a phosphorus-containing coating layer including a phosphorus-containing compound disposed on the surface of the core.
  • B and W elements are introduced into the lithium transition metal oxide, thereby improving structural stability due to an increase in the ordering of Ni ions contained in the transition metal oxide, and increasing the bonding strength between the transition metal and oxygen.
  • oxygen emission can be suppressed during charging and discharging of the lithium battery, and side reactions with the electrolyte can be suppressed to prevent depletion of the electrolyte.
  • the phosphorus-containing compound reacts preferentially with HF derived from the binder and the electrolyte to transfer lithium
  • the phosphorus-containing compound may preferentially react with moisture present in the electrolyte to suppress side reactions with lithium transition metal oxides.
  • the lithium transition metal oxide may be represented by the following Formula 1:
  • A is one or more elements selected from the group consisting of Na, K, Rb and Cs,
  • T is one or more elements selected from the group consisting of S, F and P,
  • M includes at least one element selected from the group consisting of Ni, Co, Mn, Al, Mg, V, Ti and Ca,
  • the lithium transition metal oxide includes W and B, as represented by Formula 1, when a part of Li in the lithium transition metal oxide is replaced with a small amount of alkali metal, when charging a lithium battery, Li Structural stability of the lithium transition metal oxide is improved by suppressing structural deformation caused by ion desorption.
  • A may be Na, and T may be S.
  • M includes M1, M2 and M3, and M1 is Ni, and M2 and M3 are independently of each other from Co, Mn, Al, Mg, V, Ti, and Ca. It is a selected element, and the molar ratio of Ni in M may be 75 mol% or more.
  • M is selected from M1, M2 and M3, M1 is Ni, M2 is Co, and M3 is selected from Mn, Al, Mg, V, Ti and Ca. Element, and the molar ratio of Ni in M may be 75 mol% or more.
  • M includes M1 and M2, M1 is Ni, M2 is Co, and the molar ratio of Ni in M may be 75 mol% or more.
  • the lithium transition metal oxide may be represented by any one of the following Formulas 2 to 4:
  • the lithium transition metal oxide may be a single particle.
  • a single particle is a concept that is distinguished from secondary particles formed by agglomeration of a plurality of particles or particles formed by agglomeration of a plurality of particles and coating around an aggregate. Since the lithium transition metal oxide has a single particle shape, it is possible to prevent the particles from being broken even at a high electrode density. Accordingly, it is possible to realize a high energy density of the positive electrode active material. In addition, compared to the secondary particles in which a plurality of single particles are agglomerated, breakage is suppressed during rolling, thereby enabling high energy density to be realized, and life deterioration due to breakage of particles can be prevented.
  • the lithium transition metal oxide may have a single crystal.
  • Single crystals have a concept that is distinct from single grains.
  • a single particle refers to a particle formed of one particle regardless of the type and number of crystals therein, and a single crystal means having only one crystal in the particle. Since the core has a single crystal, structural stability is very high, and lithium ion conduction is easier than that of polycrystal, and high-speed charging characteristics are superior to that of a polycrystalline active material.
  • the positive electrode active material is a single crystal and a single particle.
  • structurally stable and high-density electrodes can be implemented, and a lithium secondary battery including the same can have improved lifespan characteristics and high energy density at the same time.
  • the positive electrode active material represented by Formulas 2 to 4 has a single crystal and a single particle, and a part of Li in the lithium transition metal oxide is substituted with Na, some of the transition metal is substituted with W and B, and a part of O is substituted with S. As it is substituted, structural stability can be remarkably improved to exhibit long life characteristics.
  • a positive electrode active material having a high capacity and long life that is structurally stable in a single crystal was obtained. Furthermore, in order to suppress the side reaction between the lithium transition metal oxide and the electrolyte or moisture, a phosphorus-containing compound, for example, Li 3 PO 4 , on the surface of the lithium transition metal oxide was introduced into a phosphorus-containing coating layer. This phosphorus-containing compound prevents side reactions with HF derived from the electrolyte or moisture present in the electrolyte, thereby ensuring high stability and long life characteristics.
  • a phosphorus-containing compound for example, Li 3 PO 4
  • the core including the lithium transition metal compound may have a uniform composition over the entire range. Accordingly, it is possible to maintain a structurally stable structure even during charging and discharging, and since it does not interfere with the movement of lithium, it has high rate characteristics.
  • the phosphorus-containing compound may be crystalline, amorphous, or a combination thereof.
  • the phosphorus-containing compound may include a crystalline Li 3 PO 4 or an amorphous phosphorus-containing compound including lithium, phosphorus and oxygen atoms.
  • the molar ratio of the phosphorus (P) element in the positive electrode active material may be 0.2 mol% or less of the total elements included in the positive electrode active material.
  • the phosphorus-containing compound may include a compound represented by the following formula (5):
  • the coating layer may have a continuous coating layer on the core surface or an island-shaped coating layer partially present on the core surface.
  • the coating layer may have an island-shaped coating layer on the core surface.
  • the coating layer may have a thickness of several nanometers.
  • the coating layer may be 1 nm to 10 nm.
  • a peak at 2 ⁇ 20° to 25° in the X-ray diffraction spectrum indicates the presence of Li 3 PO 4.
  • this peak is observed in the coating layer of the positive electrode active material, it can be seen that the positive electrode active material does not contain the P element in the core.
  • the coating layer containing the phosphorus-containing compound for example Li 3 PO 4
  • the coating layer containing the phosphorus-containing compound is a residual lithium compound generated during the synthesis of a Ni-based positive electrode active material, for example, Li 2 CO 3 , a reaction product of LiOH and a phosphorus-containing compound, Accordingly, generation of gas due to a side reaction between the residual lithium compound and the electrolyte is suppressed, thereby improving the stability of the battery.
  • the coating layer including Li 3 PO 4 has a high ionic conductivity and can promote the diffusion of lithium ions.
  • the average particle diameter (D 50 ) of the positive electrode active material may be 0.1 ⁇ m to 20 ⁇ m.
  • the average particle diameter (D 50 ) is 0.1 ⁇ m to 15 ⁇ m, 0.1 ⁇ m to 10 ⁇ m, 1 ⁇ m to 20 ⁇ m, 5 ⁇ m to 20 ⁇ m, 1 ⁇ m to 15 ⁇ m, 1 ⁇ m to 10 ⁇ m, 5 ⁇ m To 15 ⁇ m, or 5 ⁇ m to 10 ⁇ m.
  • a desired energy density per volume may be achieved.
  • the average particle diameter of the positive electrode active material exceeds 20 ⁇ m, the charge/discharge capacity rapidly decreases, and when it is less than 0.1 ⁇ m, it is difficult to obtain a desired energy density per volume.
  • the method for preparing a cathode active material is a lithium transition by mixing a Li element-containing compound, W element-containing compound, B element-containing compound, A element-containing compound, M element-containing compound, T element-containing compound, and P element-containing compound. Obtaining a metal oxide precursor; And heat-treating the precursor to obtain a positive electrode active material comprising a lithium transition metal oxide represented by the following Formula 1; including, wherein the lithium transition metal oxide includes a phosphorus-containing coating layer on the surface:
  • A is one or more elements selected from the group consisting of Na, K, Rb and Cs,
  • T is one or more elements selected from the group consisting of S, F and P,
  • M includes at least one element selected from the group consisting of Ni, Co, Mn, Al, Mg, V, Ti and Ca,
  • the mixing step includes mechanical mixing the specific element-containing compounds.
  • the mechanical mixing is carried out dry.
  • the mechanical mixing is to form a uniform mixture by pulverizing and mixing substances to be mixed by applying a mechanical force.
  • Mechanical mixing is a mixing device such as a ball mill, a planetary mill, a stirred ball mill, a vibrating mill, etc. using chemically inert beads. It can be done using At this time, in order to maximize the mixing effect, alcohol such as ethanol and higher fatty acids such as stearic acid may be selectively added in small amounts.
  • the mechanical mixing is carried out in an oxidizing atmosphere, which is to prevent reduction of the transition metal in a transition metal source (eg, Ni compound), thereby realizing structural stability of the active material.
  • a transition metal source eg, Ni compound
  • the lithium element-containing compound may include lithium hydroxide, oxide, nitride, carbonate, or a combination thereof, but is not limited thereto.
  • the lithium precursor may be LiOH or Li 2 CO 3 .
  • the compound containing element A may include a hydroxide, oxide, nitride, carbonate, or a combination of at least one element selected from the group consisting of Na, K, Rb, and Cs, but is not limited thereto.
  • it may be NaOH, Na 2 CO 3 , KOH, K 2 CO 3 , RbOH, Rb 2 CO 3 , CsOH or Cs 2 CO 3 .
  • the W precursor may include a hydroxide, oxide, nitride, carbonate, or a combination thereof of W, but is not limited thereto.
  • it may be W(OH) 6 , WO 3 or a combination thereof.
  • the B element-containing compound may include a hydroxide, oxide, nitride, carbonate, or a combination thereof of B, but is not limited thereto.
  • it may be B(OH) 3 , B 2 O 3 , or a combination thereof.
  • the M element-containing compound may include, but is not limited to, hydroxides, oxides, nitrides, carbonates, or combinations thereof of at least one element among Ni, Co, Mn, Al, Mg, V, Ti, and Ca.
  • the T element-containing compound may include, but is not limited to, a hydroxide, oxide, nitride, carbonate, ammonium, or a combination of one or more elements of S, F, and P.
  • it may be (NH 4 ) 2 S.
  • the P element-containing compound includes all compounds capable of providing the P element. For example, it may be (NH 4 ) 2 HPO 4.
  • the mixing step may include a step of heat treatment.
  • the heat treatment step may include a first heat treatment step and a second heat treatment step.
  • the first heat treatment step and the second heat treatment step may be performed continuously or may have a rest period after the first heat treatment step.
  • the first heat treatment step and the second heat treatment step may be performed in the same chamber or may be performed in different chambers.
  • the heat treatment temperature in the first heat treatment step may be higher than the heat treatment temperature in the second heat treatment step.
  • the first heat treatment step may be performed at a heat treatment temperature of 800°C to 1200°C.
  • the heat treatment temperature may be, for example, 850°C to 1200°C, 860°C to 1200°C, 870°C to 1200°C, 880°C to 1200°C, 890°C to 1200°C, or 900°C to 1200°C, but limited thereto It does not, and includes all the ranges configured by selecting any two points within the range.
  • the heat treatment temperature may be performed at 700°C to 800°C.
  • the heat treatment temperature is 710 °C to 800 °C, 720 °C to 800 °C, 730 °C to 800 °C, 740 °C to 800 °C, 750 °C to 800 °C, 700 °C to 780 °C, 700 °C to 760 °C, 700 °C to 750 °C, or 700 °C to 730 °C may be, but is not limited thereto, and includes all ranges configured by selecting any two points within the above range.
  • the heat treatment time in the first heat treatment step may be shorter than the heat treatment time in the second heat treatment step.
  • the heat treatment time in the first heat treatment step may be 3 hours to 5 hours, 4 hours to 5 hours, or 3 hours to 4 hours, but is not limited thereto, and any two points within the above range are selected. It includes all the ranges constructed by this.
  • the heat treatment time in the second heat treatment step may be 10 hours to 20 hours, 10 hours to 15 hours, but is not limited thereto, and includes all ranges configured by selecting any two points within the range. .
  • the first heat treatment step may include performing heat treatment at a heat treatment temperature of 800°C to 1200°C for 3 to 5 hours.
  • the second heat treatment step may include performing heat treatment at a heat treatment temperature of 700°C to 800°C for 10 to 20 hours.
  • the lithium transition metal oxide forms the positive electrode active material having a layered structure and at the same time causes the growth of particles, thereby forming a single crystal shape.
  • the primary particles in the lithium transition metal oxide in the form of secondary particles rapidly grow and are fused to each other while revealing the inside of the primary particles as they cannot withstand the stress between the particles, so that the single crystal positive active material for secondary batteries is It is thought to be formed.
  • the second heat treatment step increases the crystallinity of the layered structure generated in the first heat treatment step by performing heat treatment at a lower temperature for a long time in the first heat treatment step. Through the first and second heat treatment steps, a single phase, single crystal, and single particle nickel-based positive electrode active material may be obtained.
  • the lithium transition metal oxide manufactured by the above manufacturing method is a single crystal or a single particle, and the single crystal may have a layered structure.
  • the average particle diameter of the lithium transition metal oxide may be 0.1 ⁇ m to 20 ⁇ m.
  • the positive electrode active material prepared by the method for preparing the positive electrode active material W and B elements are substituted for Ni in the structure, and T element, for example, S element is substituted for O.
  • T element for example, S element is substituted for O.
  • a element is substituted at the position of Li, the oxidation of Ni 2+ is suppressed, and reduction of the existing unstable Ni 3+ ions to Ni 2+ ions is induced.
  • the reduced Ni 2+ ions and Li + ions have similar ionic radii, which promotes Li/Ni disordering, partially changing the oxygen lattice structure within the core.
  • the P element occupies a tetrahedral position in the structure, so that the PO 4 structure cannot be formed, so that the P element cannot penetrate into the tetrahedral position in the core, and a phosphorus-containing compound on the surface of the positive electrode active material It exists in the form of Li 3 PO 4.
  • the positive electrode active material prepared by the above method includes a coating layer including a phosphorus-containing compound on the surface, thereby obtaining a positive electrode active material in which the amount of residual lithium and the amount of unstable Ni ions are simultaneously reduced, and lithium employing such a positive electrode active material
  • the secondary battery has a high energy density and long life.
  • a positive electrode including the positive electrode active material described above is provided.
  • the positive electrode and a lithium secondary battery including the same may be manufactured by the following method.
  • the anode is prepared.
  • a cathode active material composition in which the above-described cathode active material, conductive material, binder, and solvent are mixed is prepared.
  • the positive electrode active material composition is directly coated on a metal current collector to prepare a positive electrode plate.
  • the positive electrode active material composition may be cast on a separate support, and then a film peeled from the support may be laminated on a metal current collector to prepare a positive electrode plate.
  • the anode is not limited to the shapes listed above, but may be in a shape other than the above shape.
  • Examples of the conductive material include graphite such as natural graphite and artificial graphite; Carbon black; Conductive tubes such as carbon nanotubes; Conductive whiskers such as fluorocarbon, zinc oxide, and potassium titanate; Conductive metal oxides such as titanium oxide; And the like may be used, but are not limited thereto, and any material that can be used as a conductive material in the art may be used.
  • binder vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene, mixtures thereof, metal salts, or styrene butadiene Rubber-based polymers and the like may be used, but are not limited thereto, and any one that can be used as a binder in the art may be used.
  • VDF polyvinylidene fluoride
  • polyacrylonitrile polymethyl methacrylate
  • polytetrafluoroethylene mixtures thereof
  • metal salts metal salts
  • styrene butadiene Rubber-based polymers and the like may be used, but are not limited thereto, and any one that can be used as a binder in the art may be used.
  • lithium salt, sodium salt, calcium salt, or Na salt of the above-described polymer may be used.
  • N-methylpyrrolidone N-methylpyrrolidone, acetone, or water
  • any solvent that can be used in the art may be used.
  • the contents of the positive electrode active material, the conductive material, the binder, and the solvent are the levels commonly used in lithium batteries.
  • One or more of the conductive material, the binder, and the solvent may be omitted depending on the use and configuration of the lithium battery.
  • an anode active material composition is prepared by mixing an anode active material, a conductive material, a binder, and a solvent.
  • the negative electrode active material composition is directly coated and dried on a metal current collector having a thickness of 3 ⁇ m to 500 ⁇ m to prepare a negative electrode plate.
  • a film peeled from the support may be laminated on a metal current collector to prepare a negative electrode plate.
  • the negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes to the battery, and for example, copper, nickel, or copper surface-treated with carbon may be used.
  • the anode active material may be any material that can be used as an anode active material for lithium batteries in the art.
  • it may include at least one selected from the group consisting of lithium metal, a metal alloyable with lithium, a transition metal oxide, a non-transition metal oxide, and a carbon-based material.
  • the metal alloyable with lithium is Si, Sn, Al, Ge, Pb, Bi, Sb Si-Y alloy (wherein Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth Element or a combination element thereof, not Si), Sn-Y alloy (the Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth element, or a combination element thereof, but not Sn ), etc.
  • the element Y is Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, It may be Se, or Te.
  • the transition metal oxide may be lithium titanium oxide, vanadium oxide, lithium vanadium oxide, or the like.
  • the non-transition metal oxide may be SnO 2 , SiO x (0 ⁇ x ⁇ 2), or the like.
  • the carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof.
  • the crystalline carbon may be graphite such as amorphous, plate-shaped, flake, spherical or fibrous natural graphite or artificial graphite, and the amorphous carbon is soft carbon (low temperature calcined carbon) or hard carbon (hard carbon). carbon), mesophase pitch carbide, calcined coke, or the like.
  • the conductive material, the binder, and the solvent may be the same as those of the positive electrode active material composition.
  • the contents of the negative electrode active material, the conductive material, the binder, and the solvent are generally used in lithium batteries.
  • One or more of the conductive material, the binder, and the solvent may be omitted depending on the use and configuration of the lithium battery.
  • the separator may be a single film or a multilayer film, for example, as selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), or a combination thereof. , It may be in the form of a non-woven fabric or a woven fabric.
  • a mixed multilayer film such as a polyethylene/polypropylene two-layer separator, a polyethylene/polypropylene/polyethylene three-layer separator, a polypropylene/polyethylene/polypropylene three-layer separator, and the like may be used.
  • a woundable separator such as polyethylene or polypropylene may be used for a lithium ion battery, and a separator having excellent organic electrolyte impregnation ability may be used for a lithium ion polymer battery.
  • the separator may be manufactured according to the following method.
  • a polymer resin, a filler, and a solvent are mixed to prepare a separator composition.
  • the separator composition may be directly coated and dried on an electrode to form a separator.
  • a separator film peeled off from the support may be laminated on an electrode to form a separator.
  • the polymer resin used for manufacturing the separator is not particularly limited, and all materials used for the bonding material of the electrode plate may be used.
  • vinylidene fluoride/hexafluoropropylene copolymer polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, or mixtures thereof may be used.
  • PVDF polyvinylidene fluoride
  • the electrolyte may be an organic electrolyte.
  • the electrolyte may be a solid.
  • boron oxide, lithium oxynitride, etc. may be used, but the present invention is not limited thereto, and any solid electrolyte may be used as long as it can be used as a solid electrolyte in the art.
  • the solid electrolyte may be formed on the negative electrode by a method such as sputtering.
  • the organic electrolyte may be prepared by dissolving a lithium salt in an organic solvent.
  • the organic solvent may be used as long as it can be used as an organic solvent in the art.
  • cyclic carbonates such as propylene carbonate, ethylene carbonate, fluoroethylene carbonate, butylene carbonate, and vinylene carbonate
  • Chain carbonates such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate and dibutyl carbonate
  • Esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and ⁇ -butyrolactone
  • Ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, and 2-methyltetrahydrofuran
  • Nitriles such as acetonitrile
  • the lithium salt may also be used as long as it can be used as a lithium salt in the art.
  • the positive electrode active material according to an embodiment of the present invention may have excellent stability even when a fluorine-containing electrolyte is used due to the presence of a coating layer including a phosphorus-containing compound.
  • the lithium battery 1 includes a positive electrode 3, a negative electrode 2, and a separator 4.
  • the positive electrode 3, the negative electrode 2 and the separator 4 described above are wound or folded to be accommodated in the battery case 5.
  • an organic electrolyte is injected into the battery case 5 and sealed with a cap assembly 6 to complete the lithium battery 1.
  • the battery case 5 may be a cylindrical shape, a square shape, a pouch type, a coin type, or a thin film type.
  • the lithium battery 1 may be a thin film type battery.
  • the lithium battery 1 may be a lithium ion battery.
  • a separator may be disposed between the positive electrode and the negative electrode to form a battery structure. After the battery structure is stacked in a bi-cell structure, it is impregnated with an organic electrolyte, and the resulting product is accommodated in a pouch and sealed to complete a lithium ion polymer battery.
  • a plurality of battery structures are stacked to form a battery pack, and the battery pack can be used in all devices requiring high capacity and high output.
  • the battery pack can be used for laptop computers, smart phones, electric vehicles, and the like.
  • the lithium battery since the lithium battery has excellent life characteristics and high rate characteristics, it can be used in an electric vehicle (EV). For example, it can be used in hybrid vehicles such as plug-in hybrid electric vehicles (PHEVs). In addition, it can be used in a field requiring a large amount of power storage. For example, it can be used for electric bicycles, power tools, power storage systems, and the like.
  • EV electric vehicle
  • PHEVs plug-in hybrid electric vehicles
  • PHEVs plug-in hybrid electric vehicles
  • PHEVs plug-in hybrid electric vehicles
  • it can be used in a field requiring a large amount of power storage. For example, it can be used for electric bicycles, power tools, power storage systems, and the like.
  • the cathode active material obtained in Example 1 the conductive material: the binder was mixed in a weight ratio of 94:3:3 to prepare a slurry.
  • carbon black was used as the conductive material
  • PVdF polyvinylidene fluoride
  • the slurry was uniformly coated on an Al current collector and dried at 110° C. for 2 hours to prepare a positive electrode.
  • the loading level of the electrode plate was 11.0 mg/cm 2 and the electrode density was 3.6 g/cc.
  • a lithium foil used as a counter electrode Using the positive electrode thus prepared as a working electrode, a lithium foil used as a counter electrode, and the EC / EMC / DEC as a lithium salt in a mixed solvent in a volume ratio of 3/4/3 to the concentration of 1.3M LiPF 6
  • a CR2032 half cell was fabricated according to a commonly known process using a liquid electrolyte added as possible.
  • a half cell was manufactured in the same manner as in Example 4, except that the positive electrode active materials obtained in Examples 2 to 3 were used, respectively, instead of the positive electrode active material obtained in Example 1.
  • Example 1 In place of the positive electrode active material obtained in Example 1, a half cell was manufactured in the same manner as in Example 4, except that the positive electrode active materials obtained in Comparative Examples 9 to 16 were respectively used.
  • Evaluation Example 1 Evaluation of the composition of the positive electrode active material
  • Example 1 The positive electrode active material synthesized in Example 1 and Comparative Example 1 was subjected to inductively coupled plasma (ICP) analysis using a 700-ES (Varian) equipment, and the results are shown in Table 1 below.
  • ICP inductively coupled plasma
  • the positive electrode active material of Example 1 contains 0.2 mol of P, which does not affect the stoichiometric value of the transition metal or Li. This suggests that element P is included in the coating layer.
  • Example 1 The appearance of the positive electrode active material synthesized in Example 1 and Comparative Example 1 was obtained using a Verios 460 (FEI) equipment, and SEM images were obtained and shown in FIG. 1. In addition, the particle size distribution was measured using a Cilas 1090 (scinco) equipment, and is shown in Table 2 and FIG. 2 below.
  • FEI Verios 460
  • Cilas 1090 Tinco
  • the coating layer was introduced in the positive electrode active material of Example 1, but there was no change in the particle diameter. Referring to FIG. 1, no significant difference was observed on the positive electrode active material surfaces of Example 1 and Comparative Example 1. Considering that there is no, it can be seen that the coating layer present only on the surface of the positive electrode active material of Example 1 exists in a nanometer size.
  • the residual lithium content was measured as follows.
  • DIW deionized water
  • Example 3 As shown in Table 3, in the positive electrode active material of Example 1 including a coating layer containing a phosphorus-containing compound, it can be seen that the amount of residual lithium is significantly reduced.
  • the half-cells prepared in Examples 4 to 6 and Comparative Examples 9 to 16 were paused for 10 hours, and then charged in CC mode to 4.3V at 0.1C, and then charged in CV mode to a current corresponding to 0.05C . Then, discharged in CC mode to 3.0V at 0.1C to complete the formation process.
  • Example 4 shows a life retention rate of about 22% higher after 100 cycles compared to Comparative Example 9. This is because the introduction of Na into the structure suppresses structural deformation due to the desorption of Li, and the introduction of the B and W elements increases the ordering of Ni ions in the structure, thereby improving structural stability, and improving the structural stability. It is thought that stability and life characteristics are improved by suppressing side reactions with the electrolyte by suppressing the release of oxygen in the structure by increasing the bonding strength between transition metal and oxygen.
  • Li 3 PO 4 present on the surface of the positive electrode active material core reacts preferentially with HF of a strong acid generated by decomposition of the binder and electrolyte salt, and reacts with moisture in the electrolyte solution, thereby causing a side reaction between the positive electrode active material and HF or electrolyte. It is considered to have a long life because it suppresses deterioration of the positive electrode active material.
  • Example 10 not introducing W and B
  • Comparative Example 11 not introducing Na and S. Contrast life stability is greatly improved. As a result of the room temperature life evaluation, the lifespan of Example 4 was improved by about 10% compared to Comparative Example 10 and about 9% compared to Comparative Example 11.
  • Example 4 improved the room temperature life retention rate by about 4% compared to Comparative Example 12 and about 3% compared to Comparative Example 13.
  • Example 4 including a phosphorus-containing compound has improved lifespan. That is, as a result of the room temperature lifetime evaluation, Example 4 improved the room temperature lifetime maintenance rate of about 6% compared to Comparative Example 14. Without being bound by theory, it is believed that this is due to securing the anode/electrolyte interface stability through suppression of side reactions with the electrolyte.
  • Comparative Example 15 employing a positive electrode active material containing lithium nickel-cobalt-aluminum oxide
  • Comparative Example 16 employing a positive electrode active material containing lithium nickel-cobalt oxide.
  • Na, W, B, S through the introduction and addition of the phosphorus-containing coating layer was confirmed to improve the life retention rate of about 25% to 35%.

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

Abstract

La présente invention porte sur un matériau actif positif comportant : un noyau comprenant un oxyde de métal de transition de lithium contenant W et B ; et une couche de revêtement contenant du phosphore disposée sur la surface du noyau, sur une batterie rechargeable au lithium le comprenant et sur son procédé de préparation.
PCT/KR2019/018554 2019-08-16 2019-12-27 Matériau actif positif, son procédé de préparation, et batterie rechargeable au lithium à électrode positive le comprenant Ceased WO2021033852A1 (fr)

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KR102816259B1 (ko) * 2023-03-10 2025-06-05 주식회사 엘지화학 양극 활물질 제조방법, 양극 활물질 및 이를 포함하는 리튬이차전지

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