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WO2018008952A1 - Méthode de fabrication de matériau actif d'électrode positive pour batterie secondaire et matériau actif d'électrode positive pour batterie secondaire fabriqué grâce à celle-ci - Google Patents

Méthode de fabrication de matériau actif d'électrode positive pour batterie secondaire et matériau actif d'électrode positive pour batterie secondaire fabriqué grâce à celle-ci Download PDF

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Publication number
WO2018008952A1
WO2018008952A1 PCT/KR2017/007114 KR2017007114W WO2018008952A1 WO 2018008952 A1 WO2018008952 A1 WO 2018008952A1 KR 2017007114 W KR2017007114 W KR 2017007114W WO 2018008952 A1 WO2018008952 A1 WO 2018008952A1
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Prior art keywords
active material
positive electrode
electrode active
precursor
secondary battery
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English (en)
Korean (ko)
Inventor
이혁
조승범
손산수
주진욱
최상순
김종필
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020170084337A external-priority patent/KR102026918B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP17824508.0A priority Critical patent/EP3388394B1/fr
Priority to US16/069,710 priority patent/US10637056B2/en
Priority to CN201780010065.6A priority patent/CN108602689B/zh
Priority to JP2018558102A priority patent/JP6968428B2/ja
Publication of WO2018008952A1 publication Critical patent/WO2018008952A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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 and a positive electrode active material produced according to the present invention can be doped to uniformly doped without fear of damage on the surface of the active material and exhibit excellent structural stability.
  • Lithium secondary batteries have been widely used as power sources for portable devices since they emerged in 1991 as small, light and large capacity batteries. Recently, with the rapid development of electronics, telecommunications, and computer industry, camcorders, mobile phones, notebook PCs, etc. have emerged, and they are developing remarkably. Doing.
  • Lithium secondary batteries have a problem in that their lifespan drops rapidly as they are repeatedly charged and discharged. In particular, this problem is more serious under high temperature or high voltage. This is due to a phenomenon in which the electrolyte is decomposed or the active material is deteriorated due to moisture or other effects in the battery, and the internal resistance of the battery is increased.
  • LiCoO 2 having a layered structure. LiCoO 2 is most commonly used due to its excellent lifespan characteristics and charge and discharge efficiency. However, LiCoO 2 has a low structural stability and thus is not applicable to high capacity technology of batteries.
  • LiNiO 2 LiMnO 2 , LiMn 2 O 4 , LiFePO 4 or Li (Ni x CoyMnz) O 2
  • LiNiO 2 has the advantage of exhibiting battery characteristics of high discharge capacity, but the synthesis is difficult by a simple solid phase reaction, there is a problem of low thermal stability and low cycle characteristics.
  • lithium manganese oxides such as LiMnO 2 or LiMn 2 O 4 have advantages in that they are excellent in thermal safety and inexpensive, but have a small capacity and low temperature characteristics.
  • LiMn 2 O 4 but a part merchandising products to low cost, since the Mn + 3 structure modification (Jahn-Teller distortion) due to the not good life property.
  • LiFePO 4 has a low price and excellent safety and is currently being studied for a hybrid electric vehicle (HEV), but due to low conductivity it is difficult to apply to other fields.
  • Li (NixCoyMnz) O 2 is the most recently attracting attention as an alternative cathode active material for LiCoO 2 .
  • X, y, and z are atomic fractions of independent oxide composition elements, respectively, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, and 0 ⁇ x + y + z ⁇ 1.
  • This material is cheaper than LiCoO 2 and has advantages in that it can be used for high capacity and high voltage, but has a disadvantage in that the rate capability and the service life at high temperature are poor.
  • the positive electrode active material may be doped with Al, Ti, Sn, Ag, or Zn inside the positive electrode active material, or by dry or wet coating a conductive metal on the surface of the positive electrode active material.
  • the structural stability of the positive electrode active material is improved, but there is a problem that the capacity is lowered.
  • the uniform distribution of the doped material in the positive electrode active material is difficult, there is a problem of deterioration of the active material properties due to the non-uniform distribution of the doped material.
  • the first technical problem to be solved by the present invention is to improve the structural stability by uniformly doping with a doping element without fear of damage on the surface of the active material and deterioration of characteristics by using acoustic resonance, thereby improving capacity It is to provide a method for producing a positive electrode active material that can improve battery characteristics such as minimization and improved cycle characteristics.
  • the second technical problem to be solved by the present invention is to be prepared by the manufacturing method, having an improved structural stability, thereby providing a cathode active material that can improve the capacity, rate (rate) and cycle characteristics of the battery will be.
  • the third technical problem to be solved by the present invention is to provide a positive electrode and a lithium secondary battery including the positive electrode active material.
  • preparing a precursor doped with the doping element by mixing the metal precursor for the positive electrode active material and the raw material including the doping element using an acoustic resonance; And mixing the doped precursor with a lithium raw material, followed by heat treatment, wherein the raw material including the metal precursor and the doping element for the positive electrode active material has an average particle size ratio of 2000 to 5: 1. It provides a method of manufacturing.
  • a cathode active material for a secondary battery comprising the lithium composite metal oxide of Formula 2 prepared by the manufacturing method, doped with a metal element:
  • M comprises any one or two or more elements selected from the group consisting of Mn and Al,
  • M ' is any one selected from the group consisting of Y, Zr, La, Sr, Ga, Mg, Sc, Gd, Sm, Ca, Ce, Fe, Al, Ti, Ta, Nb, W, Mo, and Cr or Contains two or more elements, and
  • a cathode and a lithium secondary battery including the cathode active material are provided.
  • the lithium composite metal oxide is used as a doping element without fear of damage on the surface of the active material and deterioration of properties.
  • the lithium composite metal oxide is used as a doping element without fear of damage on the surface of the active material and deterioration of properties.
  • Example 1 is a photograph of the doping precursor prepared in Example 1-1 using a scanning electron microscope (SEM).
  • Figure 2 is a photograph of the doping precursor prepared in Comparative Example 1-1 using the SEM.
  • Figure 3 is a photograph of the doping precursor prepared in Comparative Example 1-2 using the SEM.
  • FIG. 4 is a SEM photograph of the metal precursor (a)), the doped precursor (b), and the cathode active material (c) in the preparation of the cathode active material according to Example 1-1.
  • FIG. 5 is a SEM photograph of a metal precursor (a)), a doped precursor (b)) and a cathode active material (c) in the preparation of the cathode active material according to Comparative Example 1-1.
  • FIG. 6 is an SEM observation photograph of a doping precursor obtained after an acoustic resonance treatment of a mixture of a metal precursor and a doping element-containing raw material in Example 1-2.
  • FIG. 6 is an SEM observation photograph of a doping precursor obtained after an acoustic resonance treatment of a mixture of a metal precursor and a doping element-containing raw material in Example 1-2.
  • FIG. 7 is an SEM observation photograph of a doping precursor obtained after an acoustic resonance treatment of a mixture of a metal precursor and a doping element-containing raw material in Example 1-3.
  • FIG. 7 is an SEM observation photograph of a doping precursor obtained after an acoustic resonance treatment of a mixture of a metal precursor and a doping element-containing raw material in Example 1-3.
  • FIG. 8 is an SEM observation photograph of a doping precursor obtained after an acoustic resonance treatment of a mixture of a metal precursor and a doping element-containing raw material in Comparative Example 1-3.
  • FIG. 8 is an SEM observation photograph of a doping precursor obtained after an acoustic resonance treatment of a mixture of a metal precursor and a doping element-containing raw material in Comparative Example 1-3.
  • FIG. 9 is an SEM observation photograph of a doping precursor obtained after an acoustic resonance treatment of a mixture of a metal precursor and a doping element-containing raw material in Comparative Example 1-4.
  • FIG. 9 is an SEM observation photograph of a doping precursor obtained after an acoustic resonance treatment of a mixture of a metal precursor and a doping element-containing raw material in Comparative Example 1-4.
  • FIG. 10 is an SEM observation photograph of the result obtained after mixing the doped precursor and the lithium raw material during the preparation of the cathode active material according to Example 1-4.
  • FIG. 10 is an SEM observation photograph of the result obtained after mixing the doped precursor and the lithium raw material during the preparation of the cathode active material according to Example 1-4.
  • FIG. 11 is an SEM observation photograph of a result obtained after mixing a doped precursor and a lithium raw material during a process of preparing a cathode active material according to Comparative Example 1-1.
  • FIG. 12 is a graph illustrating discharge characteristics of the half-coin cell including the positive electrode active material prepared in Examples 1-4 and Comparative Examples 1-5.
  • Example 13 is a SEM photograph of the surface of the positive electrode active material prepared in Example 1-6.
  • the production of the conventionally doped cathode active material has been carried out by heat treatment after dry mixing or wet mixing of the cathode active material or its precursor and the dopant-containing raw material.
  • dry mixing the process is simple, but there is a problem that uniform dispersion or doping material is agglomerated easily, and dust is generated when fine powder is used.
  • wet mixing uniform dispersion and doping are possible as compared to dry, but there are disadvantages in that the process is complex.
  • both dry and wet methods had problems of dead zone generation due to agitation deviation during mixing and the possibility of mixing by a continuous process.
  • the metal precursor for the cathode active material and the doping element-containing raw material are mixed by using acoustic resonance, and the particles of the metal precursor and the doping element-containing raw material according to the acoustic resonance conditions are used.
  • the metal precursor can be uniformly doped with a doping element without fear of damage on the surface of the active material and deterioration of properties, and the dead zone due to the stirring variation can be minimized.
  • the structural stability of the positive electrode active material is significantly increased, thereby further improving the capacity, rate characteristics, and cycle characteristics of the battery.
  • Step 1 Preparing a precursor doped with the doping element by mixing the metal precursor for the positive electrode active material and the raw material including the doping element by using acoustic resonance (step 1); And
  • the raw material including the metal precursor and the doping element for the positive electrode active material is to have an average particle size ratio of 2000 to 5: 1.
  • step 1 is a step of preparing a doped precursor.
  • step 1 may be performed by mixing the metal precursor for the positive electrode active material and the raw material including the doping element by using acoustic resonance.
  • the mixing by acoustic resonance may be larger because the frequency of acoustic energy is several hundred times lower than that of ultrasonic mixing.
  • uniform mixing is possible because mixing occurs frequently in small scale mixing throughout the mixing system.
  • a doping element including a doping element such as yttria stabilized zirconia which is used for doping the metal precursor for the positive electrode active material, does not have uniform doping because of very low miscibility and reactivity to the precursor.
  • a doping element including a doping element such as yttria stabilized zirconia, which is used for doping the metal precursor for the positive electrode active material, does not have uniform doping because of very low miscibility and reactivity to the precursor.
  • by performing the mixing by acoustic resonance it is possible to increase the dispersibility of the raw material including the doping element, and to increase the reactivity to the precursor to uniformly doping the precursor surface.
  • Mixing by the acoustic resonance may be performed using a conventional acoustic resonance apparatus, and specifically, may be performed using an acoustic mixer.
  • the mixing process by acoustic resonance may have different mixing conditions depending on the particle size ratio of the metal precursor for the positive electrode active material and the raw material including the doping element, and furthermore, the damage and loss to the surface of the metal precursor and the active material. It may be desirable to optimize the particle size of the metal precursor and the doping element-containing raw material in order to obtain doping efficiency with a uniform and excellent efficiency while minimizing, and even more preferably to optimize each type together.
  • the average particle size ratio of the metal precursor for the cathode active material and the raw material including the doping element may be 2000 to 5: 1, more specifically 1000 to 5: 1 or 300 to 5: 1, and more specifically 7.5 To 5: 1.
  • the doping element-containing raw material may be uniformly dispersed with superior efficiency without damaging or losing the precursor particles.
  • the average particle diameter (D 50 ) of the doping element-containing raw material is 4 nm to 5 ⁇ m, or 10 nm to 5 ⁇ m, and more specifically 50 nm to 3 ⁇ m, and the average particle diameter of the metal precursor for the positive electrode active material ( Under the condition that D 50 ) is 10 ⁇ m to 20 ⁇ m, the metal precursor for the positive electrode active material and the raw material including the doping element may have an average particle size of 2000 to 5: 1, more specifically, 1000 to 5: 1, or 300 to 5: 1, and more specifically 7.5 to 5: 1.
  • mixing by acoustic resonance with respect to the metal precursor for the positive electrode active material and the doping element-containing raw material satisfying the particle size condition may be performed by applying acoustic energy of 50 g to 90 g, more specifically 50 g to 90 g of acoustic energy may be performed by applying 1 to 5 minutes.
  • the mixing mode of the doping material and the metal precursor may vary according to the structure of the metal precursor for the positive electrode active material.
  • the metal precursor for the positive electrode active material may be secondary particles in which a plurality of primary particles are aggregated, and the primary particles may have a plate-like shape.
  • the densities of the metal precursors on the secondary particles vary according to the plate thickness of the primary particles, and as a result, the doping aspect of the doping element for the metal precursor may vary. Therefore, more uniform and efficient doping is applied by optimizing the conditions at the time of the acoustic resonance according to the plate thickness of the primary particles.
  • the primary particles forming the metal precursor for the positive electrode active material have a plate-like shape, and the average thickness of the plate. May be 150 nm or less, and more specifically, 80 nm to 130 nm.
  • gap is formed between plate-shaped primary particles, and the metal precursor of secondary particle shape may have a large specific surface area.
  • the amount of the doping element to be doped may be small or the voids remain empty, and the doping by the doping element may be caused by the secondary particle metal. It can occur mainly at the precursor surface.
  • the mixing by the acoustic resonance is performed by applying a force of 50g to 90g for 1 to 4 minutes, the doping element is uniformly introduced into the pores between the primary particles on the plate can exhibit excellent doping efficiency, as a result As a result, the structural stability of the active material can be improved.
  • the 'plate shape' or 'plate shape' refers to an aggregate structure in which two surfaces corresponding or facing each other are flat, and the size in the horizontal direction is larger than the size in the vertical direction, Flakes, scales, and the like, which are similar in shape to a plate, may also be included.
  • grains is an average value of the plate
  • the primary particles forming the metal precursor for the positive electrode active material have a plate-like shape, and the average thickness of the plate
  • the metal precursor may be a secondary particle having a dense structure with less pore-shaped primary interparticle pores.
  • the doping element is more likely to be introduced into the pores between the primary particles of the doping element than the metal precursor including the thin plate-shaped primary particles.
  • the doping element It is mainly located on the surface, where local agglomeration of the doping element may occur locally on the secondary particulate surface.
  • a layer of the coating element on which the doping element is uniformly applied is formed on the precursor surface of the secondary particles.
  • the content of the doped lithium composite metal oxide on the surface of the active material increases, and as a result, the stability of the surface of the active material can be improved.
  • the doping element is specifically Y, Zr, La, Sr, Ga, Mg, Sc, Gd, Sm, Ca, Ce, Fe, Al, Ti, Ta, Nb, W, Mo, Cr or the like, and may include any one or two or more of these.
  • the doping element may be an element corresponding to group 6 (VIB group) of the periodic table that can improve the structural stability of the active material by inhibiting particle growth during the firing process during the production of the active material particles. More specifically, the doping element may be any one or two or more elements selected from the group consisting of W, Mo and Cr, more specifically any one or two or more elements selected from the group consisting of W and Cr. Can be.
  • the doping element may be more specifically an element corresponding to Group 13 (Group IIIA) of the periodic table, and more specifically may be any one or two or more elements selected from the group consisting of B, Al, Ga and In. have.
  • the doping element may be any one or two or more elements selected from the group consisting of Group III (Group IIIB) and Group IV (Group IV) elements, more specifically, Ti, Sc, Y, Zr And La may be any one or two or more elements selected from the group consisting of.
  • the doping element may be an element corresponding to Group 5 (Group V) elements more specifically, and may be more specifically any one or two or more elements selected from the group consisting of V, Nb, and Ta. .
  • the doping element-containing raw material may be an oxide, hydroxide, or oxyhydroxide such as Al 2 O 3 including the doping element, and any one or a mixture of two or more thereof may be used.
  • the dopant-containing raw material may be a ceramic-based ion conductor that not only has excellent lithium ion conductivity in itself, but also may further improve the structure stability of the active material with a better doping effect when doping with a metal element derived therefrom.
  • the ceramic ion conductor may specifically include at least one of an ion conductive ceramic and a metal ceramic.
  • the ion conductive ceramics specifically include Y, Ca, Ni, such as yttria stabilized zirconia (YSZ ) , calcia stabilized zirconia (CSZ), scandia-stabilized zirconia (SSZ), and the like.
  • YSZ yttria stabilized zirconia
  • CSZ calcia stabilized zirconia
  • SSZ scandia-stabilized zirconia
  • ZrO 2 zirconia
  • GDC gadolinia doped ceria
  • SDC samarium doped ceria
  • YDC yttria-doped ceria
  • LSGM Lanthanum strontium gallate magnesite
  • LSM lanthanum strontium manganite
  • LSCF lanthanum strontium cobalt ferrite
  • the YSZ is a ceramic material made of zirconium oxide (zirconia) added with yttrium oxide (yttria) to be stable at room temperature.
  • the YSZ may be part of the yttria is added by being Zr 4 + ions to be substituted for the zirconia are Y 3+. This is replaced by three O 2 ions instead of four O 2 ions, resulting in oxygen vacancy.
  • the generated oxygen deficiency YSZ is O 2- ion have jeondoseongreul and the higher the temperature, the better the conductivity.
  • YSZ is Zr (1-x) Y x O 2 -x / 2 , where 0.01 ⁇ x ⁇ 0.30, and more specifically 0.08 ⁇ x ⁇ 0.10.
  • normal temperature means the temperature range in 23 +/- 5 degreeC unless it is specifically defined.
  • the YSZ is Zr (1-x) Y x O 2 -x / 2 (where, 0.01 ⁇ x ⁇ 0.30, and more specifically 0.08 ⁇ x ⁇ 0.10).
  • the metal ceramic is produced by mixing and sintering the ceramic and the metal powder, and has both the characteristics of a ceramic having high heat resistance and hardness, and a metal having plastic deformation or electrical conductivity.
  • the ceramic may be the ion conductive ceramic described above, and the metal may be nickel, molybdenum, cobalt, or the like. More specifically, the metal ceramic may be a cermet such as nickel-yttria stabilized zirconia cermet (Ni-YSZ cermet).
  • the average particle diameter (D 50 ) of the doping element containing the raw material may be 4nm to 5 ⁇ m.
  • the average particle diameter (D 50 ) of the doping element-containing raw material may be 10nm to 5 ⁇ m, even more specifically 50nm to 3 ⁇ m.
  • the average particle diameter (D 50 ) of the doping element containing the raw material may be defined as the particle size at 50% of the particle size distribution.
  • the average particle diameter (D 50 ) of the doping element-containing raw material may be measured by using a laser diffraction method, and specifically, introduced into a laser diffraction particle size measuring device (for example, Microtrac MT 3000) to about 28 after examining the kHz ultrasound of 60 W in output, it can be used to calculate the average particle diameter (D 50) of from 50% based on the particle size distribution of the measuring device.
  • a laser diffraction particle size measuring device for example, Microtrac MT 3000
  • the doping element-containing raw material is the content of the metal element derived from the doping element-containing raw material doped in the lithium composite metal oxide in the positive electrode active material to be produced finally Therefore, the amount of usage can be appropriately selected.
  • the doping element-containing raw material may be used in an amount of 500 ppm to 20,000 ppm, more specifically 1,000 ppm to 8,000 ppm with respect to the total content of the metal precursor for the positive electrode active material and the doping element-containing raw material. .
  • the metal precursor for the cathode active material is a material capable of forming a lithium composite metal oxide capable of reversible intercalation and deintercalation of lithium.
  • the metal-containing oxide, hydroxide, oxyhydroxide or phosphate for the positive electrode active material may be used, and any one or a mixture of two or more thereof may be used.
  • the metal for the positive electrode active material may specifically include one or two or more metal elements selected from the group consisting of nickel, cobalt manganese and aluminum.
  • the metal precursor for the positive electrode active material may be prepared by a conventional manufacturing method.
  • it when prepared by the coprecipitation method, it can be prepared by adding the ammonium cation-containing complex former and the basic compound to the aqueous solution of the metal-containing raw material for the positive electrode active material by coprecipitation reaction.
  • the metal-containing raw material for the positive electrode active material may be determined according to the composition of the lithium composite metal oxide constituting the target active material. Specifically, hydroxides, oxyhydroxides, nitrates, halides, carbonates, acetates, oxalates, citrates or sulfates containing metals constituting the lithium composite metal oxide may be used.
  • the cathode active material metal may be any one or two or more mixed metals selected from the group consisting of Fe, Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Mo, Ti, Zn, Al, Ga and Mg. In more detail, it may be any one or two or more mixed metals selected from the group consisting of Ni, Co, Mn, and Al.
  • the cathode active material contains a lithium-nickel-cobalt-manganese compound as a lithium composite metal compound, as a precursor
  • nickel (Ni) is contained as a raw material for producing a metal-containing hydroxide for the cathode active material.
  • Raw materials, cobalt (Co) containing raw materials and manganese (Mn) containing raw materials may be used.
  • Each of the metal element-containing raw materials may be used without particular limitation as long as they are usually used in the production of the positive electrode active material.
  • the Co-containing raw material may be specifically Co (OH) 2 , CoO, CoOOH, Co (OCOCH 3 ) 2 ⁇ 4H 2 O, Co (NO 3 ) 2 ⁇ 6H 2 O or Co (SO 4 ) 2 7H 2 O and the like, any one or a mixture of two or more of the above compounds may be used.
  • the metal-containing raw material for the positive electrode active material is preferably used in an appropriate content ratio in consideration of the content of metals in the lithium composite metal oxide in the final positive electrode active material.
  • the metal-containing raw material for the positive electrode active material is water; Or it can be used as an aqueous solution by dissolving in the mixture of the organic solvent (specifically alcohol etc.) and water which can be mixed uniformly with water.
  • the organic solvent specifically alcohol etc.
  • ammonium cation-containing complex forming agent that can be used to prepare the metal-containing hydroxide for the positive electrode active material is specifically NH 4 OH, (NH 4 ) 2 SO 4 , NH 4 NO 3 , NH 4 Cl, CH 3 COONH 4 , or NH 4 CO 3 and the like, any one or a mixture of two or more thereof may be used.
  • the ammonium cation-containing complex forming agent may be used in the form of an aqueous solution, wherein the solvent is water; Alternatively, a mixture of water and an organic solvent (specifically alcohol or the like) that can be mixed with water uniformly can be used.
  • the basic compound usable for the preparation of the metal-containing hydroxide for the positive electrode active material may be a hydroxide of an alkali metal or alkaline earth metal such as NaOH, KOH, or Ca (OH) 2 , or a hydrate thereof, any one or two of them Mixtures of the above may be used.
  • the basic compound may also be used in the form of an aqueous solution, and as the solvent, a mixture of water or an organic solvent (specifically, alcohol, etc.) that can be mixed uniformly with water may be used.
  • the coprecipitation reaction for forming the particles of the metal-containing hydroxide for the positive electrode active material may be carried out under the condition that the pH of the aqueous solution of the metal-containing raw material is 8 to 14.
  • the pH value means a pH value at the temperature of the liquid 25 °C.
  • the coprecipitation reaction may be carried out in an inert atmosphere at a temperature of 30 °C to 60 °C.
  • the metal precursor for the positive electrode active material prepared by the manufacturing method as described above may be secondary particles in which a plurality of primary particles are aggregated.
  • the primary particles may have a plate shape. At this time, the plate thickness of the primary particles can be adjusted by controlling the reaction rate in the manufacturing process.
  • the metal precursor for the positive electrode active material may be secondary particles in which a plurality of primary particles having an average thickness of 150 nm or less, more specifically, 80 nm to 130 nm, are aggregated, or an average thickness of a plate is greater than 150 nm, Specifically, the secondary particles may be agglomerated secondary particles of 200 nm to 250 nm.
  • the average particle diameter (D 50 ) of the metal precursor for the positive electrode active material may be 4 ⁇ m to 30 ⁇ m, and more specifically 10 ⁇ m to 20 ⁇ m. When the average particle diameter of the precursor is in the above range, more efficient application is possible. In the present invention, the average particle diameter (D 50 ) of the metal precursor for the positive electrode active material may be defined as the particle size at 50% of the particle size distribution.
  • the average particle diameter (D 50 ) of the metal precursor for the positive electrode active material may be measured by using a laser diffraction method, and specifically, introduced into a laser diffraction particle size measuring apparatus (for example, Microtrac MT 3000) to about 28 after examining the kHz ultrasound of 60 W in output, it can be used to calculate the average particle diameter (D 50) of from 50% based on the particle size distribution of the measuring device.
  • a laser diffraction particle size measuring apparatus for example, Microtrac MT 3000
  • the doped metal element may be uniformly distributed in the precursor depending on the position preference of the metal element and the crystal structure of the precursor material, or may have a concentration gradient that increases or decreases the content distribution from the particle center of the precursor to the surface. Or on the surface side of the precursor.
  • step 2 is a step of preparing a cathode active material by mixing the doping precursor prepared in step 1 with a lithium raw material and heat treatment.
  • the lithium raw material examples include hydroxides, oxyhydroxides, nitrates, halides, carbonates, acetates, oxalates or citrates including lithium, and any one or a mixture of two or more thereof may be used.
  • the lithium raw material is Li 2 CO 3 , LiNO 3 , LiNO 2 , LiOH, LiOHH 2 O, LiH, LiF, LiCl, LiBr, LiI, CH 3 COOLi, Li 2 O, Li 2 SO 4 , CH 3 COOLi and Li 3 C 6 H 5 O 7 It may include any one or two or more compounds selected from the group consisting of.
  • the lithium raw material may be used in accordance with the lithium content in the final lithium composite metal oxide to be produced.
  • Mixing of the doped precursor and the lithium raw material may be performed by a conventional mixing method using a ball mill, a bead mill, a high pressure homogenizer, a high speed homogenizer, an ultrasonic dispersing apparatus, or the like. It may also be performed by acoustic resonance as shown.
  • the average particle size ratio of the doped precursor and the lithium raw material may be controlled to increase the mixing efficiency when mixing by the acoustic resonance. Specifically, the average particle size ratio of the doped precursor and the lithium raw material is 10: 1. To 3: 1.
  • the first heat treatment of the mixture of the doped precursor and the lithium raw material may be performed at a temperature of 700 ° C. to 950 ° C. If the temperature is less than 700 °C during the first heat treatment, there may be a decrease in discharge capacity per unit weight, cycle characteristics, and a decrease in operating voltage due to residual unreacted raw materials. There is a fear of lowering the discharge capacity per unit weight, lowering of cycle characteristics and lowering of operating voltage.
  • the primary heat treatment may be performed in the air or under an oxygen atmosphere, and may be performed for 5 hours to 30 hours.
  • the diffusion reaction between the particles of the mixture can be sufficiently made.
  • a cathode active material containing lithium composite metal oxide particles, wherein the lithium composite metal oxide present on the surface side of the particles is doped with a metal element derived from the doping element-containing raw material is prepared.
  • the method of manufacturing a cathode active material according to an embodiment of the present invention may further include a washing process for the resultant obtained after the first heat treatment in step 2.
  • the washing process may be performed using a conventional washing method such as mixing with water. More specifically, the washing process may be performed by mixing the resultant product with water by mixing by acoustic resonance.
  • the conventional water washing method has a water washing restriction due to the capillary phenomenon between the aggregated particles, and there is a problem in that the characteristics of the positive electrode active material are lowered when overwashing.
  • water dispersion can be easily performed, so that water washing can be performed with excellent efficiency without limitation of water washing, and the water washing time can be adjusted to prevent deterioration of the characteristics of the cathode active material. .
  • the acoustic resonance at the time of washing may be performed by applying 20g to 90g of acoustic energy for 10 seconds to 30 minutes.
  • the method of manufacturing a cathode active material according to an embodiment of the present invention may further include a surface treatment process for the resultant obtained after the heat treatment in the step 2 or after the washing process.
  • the surface treatment process may be carried out according to a conventional method, specifically, the resultant obtained after the heat treatment and the surface treatment agent may be performed by mixing using an acoustic resonance and then further heat treatment (hereinafter referred to as secondary heat treatment). .
  • the surface treatment agent is heat treated after mixing with Me raw material (Me is any one or two or more elements selected from the group consisting of Al, Y, B, W, Hf, Nb, Ta, Mo, Si, Sn and Zr)
  • Me raw material Me is any one or two or more elements selected from the group consisting of Al, Y, B, W, Hf, Nb, Ta, Mo, Si, Sn and Zr
  • Me-containing acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide may be used as Me raw material.
  • Me is B
  • boric acid, lithium tetraborate, boron oxide, ammonium borate, and the like may be used, and any one or a mixture of two or more thereof may be used.
  • Me is tungsten, tungsten oxide (VI) etc. are mentioned.
  • the acoustic resonance treatment for forming the surface treatment layer may be performed by applying 30 g to 100 g of acoustic energy for 1 to 30 minutes.
  • the secondary heat treatment for forming the surface treatment layer may be performed at 300 °C to 900 °C.
  • the melting point of the Me raw material may be differently applied depending on the reaction temperature. If the secondary heat treatment temperature is less than 300 ° C., the surface treatment layer may not be sufficiently formed.
  • the atmosphere during the heat treatment is not particularly limited, and may be performed in a vacuum, inert or air atmosphere.
  • a surface treatment layer including the compound of formula 1 may be formed on the surface of the active material by the surface treatment process as described above:
  • Me is any one or two or more elements selected from the group consisting of Al, Y, B, W, Hf, Nb, Ta, Mo, Si, Sn and Zr, 2 ⁇ m ⁇ 10, n is the oxidation number of Me)
  • the doping element is uniformly dispersed and doped as compared to the doping by the conventional dry mixing method or wet mixing method, thereby greatly improving the structural safety, as a result of battery application Dose reduction can be minimized. At the same time, the output characteristics, rate characteristics and cycle characteristics can be further improved.
  • a cathode active material prepared by the above-described manufacturing method is provided.
  • the cathode active material includes a lithium composite metal oxide doped with the doping element. More specifically, the lithium composite metal oxide doped with the doping element may be uniformly distributed in the precursor, or may have a concentration gradient that increases or decreases in content distribution from the particle center of the precursor to the surface, or May exist only on the surface side.
  • the 'surface side' of the lithium composite metal oxide particles means a region close to the surface except for the center of the particles, specifically, the distance from the surface of the lithium composite metal oxide particles to the center, that is, the lithium composite metal oxide Means a region corresponding to a distance of 0% or more and less than 100% from the particle surface, more specifically 0% to 50% from the particle surface, and more specifically 0% to 30% from the particle surface with respect to the semi-diameter of .
  • the lithium composite metal oxide doped by the metal element of the ceramic ion conductor may be a compound of Formula 2 below:
  • M is at least one metal element selected from the group consisting of Mn and Al,
  • M ' is a metal element derived from a dopant-containing raw material, specifically, Y, Zr, La, Sr, Ga, Mg, Sc, Gd, Sm, Ca, Ce, Fe, Al, Ti, Ta, Nb, It may be any one selected from the group consisting of W, Mo, and Cr or a mixed element of two or more thereof, more specifically in the group consisting of Y, Zr, La, Sr, Ga, Sc, Gd, Sm and Ce It may be any one or two or more mixed elements selected, and more specifically at least one element selected from the group consisting of Y and Zr, provided that M and M 'may be different elements.
  • 0 ⁇ A ⁇ 1, 0 ⁇ a ⁇ 0.33, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, and 0 ⁇ s ⁇ 0.2, but b and c are not 0.5 at the same time. More specifically, 0 ⁇ a ⁇ 0.09 under conditions satisfying A, b, c, and s, and more specifically 0.9 ⁇ A ⁇ 1, a under conditions satisfying b, c, and s. It may be zero.
  • the effect of doping the raw material including the doping element on the lithium composite metal particles is not more than about 10% of the difference in life characteristic effect compared to the case of doping the metal element by a conventional doping method. You may not.
  • the effect of doping the raw material including the doping element on the lithium composite metal oxide particles is 30% longer than the case of doping the metal element by the conventional doping method. Up to 70%.
  • M ' may be distributed in a concentration gradient gradually decreasing from the particle surface to the center in the particles of the lithium composite metal oxide.
  • concentration of the doped metal is gradually changed according to the position of the particles of the positive electrode active material, so that there is no abrupt phase boundary region in the active material, so that the crystal structure is stabilized and thermal stability is increased.
  • the doping element is distributed at a high concentration on the surface side of the active material particles and includes a concentration gradient in which the concentration decreases toward the particle center, it is possible to prevent a decrease in capacity while exhibiting thermal stability.
  • the concentration of the doping element M ' indicates a concentration gradient, based on the total atomic weight of the doping element M' included in the positive electrode active material, 10% by volume from the center of the particle
  • the difference between the concentrations of M 'in the region within (hereinafter referred to simply as' Rc 10 region') and the region within 10% by volume (hereinafter referred to simply as' Rs 10 region ') is 10 to 90 atoms. %
  • the concentration difference of M ′′ may be from 10 atomic% to 90 atomic%.
  • the concentration gradient structure and the concentration of the doping element in the positive electrode active material particles are determined by the Electron Microbe (Electron Probe Micro Analyzer, EPMA), Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-). AES) or Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and more specifically, using EPMA to move from the center of the cathode active material to the surface. While measuring the atomic ratio of each metal (atomic ratio) can be measured.
  • the cathode active material according to an embodiment of the present invention may further include a surface treatment layer made of the lithium composite metal oxide of Chemical Formula 2 when using a metal precursor made of primary particles having a plate thickness of more than 150 nm.
  • the surface treatment layer may be formed in a thickness ratio of 0.001 to 0.1 with respect to the semi-diameter of the lithium composite metal oxide particles on the surface of the lithium composite metal oxide particles, more specifically, may be formed in a thickness range of 1nm to 1000nm. .
  • the cathode active material according to an embodiment of the present invention may be primary particles of a lithium composite metal oxide or secondary particles formed by assembling the primary particles.
  • the cathode active material is a primary particle of a lithium composite metal oxide
  • generation of surface impurities such as Li 2 CO 3 , LiOH, and the like caused by reaction with moisture or CO 2 in the air is reduced, thereby reducing battery capacity and gas generation.
  • excellent high temperature stability can be exhibited.
  • the cathode active material is secondary particles in which primary particles are assembled, output characteristics may be more excellent.
  • the primary average particle size (D 50) of the particles may be 10nm to 200nm.
  • the form of such active material particles may be appropriately determined according to the composition of the lithium composite metal oxide constituting the active material.
  • a positive electrode including the positive electrode active material prepared by the above-described manufacturing method.
  • the positive electrode may be manufactured by a conventional positive electrode manufacturing method known in the art, except for using the positive electrode active material described above.
  • a positive electrode is prepared by mixing and stirring a solvent, a binder, a conductive material, or a dispersant in a positive electrode active material, if necessary, and then coating (coating) and drying the positive electrode current collector to form a positive electrode active material layer. can do.
  • the positive electrode current collector is a metal having high conductivity, and may be any metal as long as it is a metal that the slurry of the positive electrode active material can easily adhere to.
  • Non-limiting examples of the positive electrode current collector include a foil made of aluminum, nickel, or a combination thereof.
  • the solvent for forming the positive electrode includes an organic solvent such as NMP (N-methyl pyrrolidone), DMF (dimethyl formamide), acetone, dimethyl acetamide or water, and these solvents are used alone or 2 It can mix and use species.
  • the amount of the solvent used is sufficient to dissolve and disperse the positive electrode active material, the binder, and the conductive material in consideration of the coating thickness of the slurry and the production yield.
  • the binder may be vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethylmethacrylate, poly Vinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), liquor
  • Various types of binder polymers can be used, such as fonned EPDM, styrene butadiene rubber (SBR), fluorine rubber, poly acrylic acid and polymers in which hydrogen thereof is replaced with Li, Na or Ca, or various copolymers. have.
  • the binder may be included in an amount of 1 to 30% by weight based on the total weight of the positive electrode active material layer.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • Examples of the conductive material include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, farnes black, lamp black, thermal black, carbon nanotubes or carbon fibers; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskers such as fluorocarbon, zinc oxide or potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, and any one or a mixture of two or more thereof may be used.
  • the conductive material may be included in an amount of 1 to 30 wt% based on the total weight of the cathode active material layer.
  • a lithium secondary battery including the cathode active material manufactured by the above-described manufacturing method.
  • the lithium secondary battery specifically includes a separator interposed between the positive electrode, the negative electrode, the positive electrode and the negative electrode.
  • a carbon material lithium metal, silicon, tin, or the like, in which lithium ions may be occluded and released, may be used.
  • a carbon material may be used, and as the carbon material, both low crystalline carbon and high crystalline carbon may be used.
  • Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is natural graphite, Kish graphite, pyrolytic carbon, liquid crystal pitch carbon fiber.
  • High temperature calcined carbon such as (mesophase pitch based carbon fiber), meso-carbon microbeads, Mesophase pitches and petroleum or coal tar pitch derived cokes.
  • the negative electrode current collector is generally made of a thickness of 3 ⁇ m to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy, and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the binder and the conductive material used for the negative electrode may be used as can be commonly used in the art as the positive electrode.
  • the negative electrode may prepare a negative electrode by mixing and stirring the negative electrode active material and the additives to prepare a negative electrode active material slurry, and then applying the same to a current collector and compressing the negative electrode.
  • porous polymer films conventionally used as separators for example, polyolefins such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer, etc.
  • the porous polymer film made of the polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used. It is not.
  • Examples of the electrolyte used in the present invention include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery. no.
  • the lithium salt which can be included as an electrolyte used in the present invention can be used without limitation, those which are commonly used in a lithium secondary battery electrolyte, such as the lithium salt, the anion is F -, Cl -, Br -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 - may be any one
  • the lithium secondary battery having the above configuration may be manufactured by manufacturing an electrode assembly through a separator between a positive electrode and a negative electrode, placing the electrode assembly inside a case, and then injecting an electrolyte solution into the case.
  • the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate, portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles It is useful in the field of electric vehicles.
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same are provided.
  • the battery module or the battery pack is a power tool (Power Tool); Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
  • Power Tool Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
  • YSZ yttria-stabilized zirconia
  • the acoustic energy of 60g was applied for 2 minutes using an acoustic mixer (LabRAM II) to obtain a precursor doped with ceramic elements (Y and Zr) derived from the raw material including the YSZ doping element.
  • LiOH was added at a molar ratio of 1.02 to the doped precursor and mixed for 10 minutes at 15000 rpm using a blending mixer, followed by heat treatment at 800 ° C. in an oxygen atmosphere to prepare a positive electrode active material of a lithium composite metal oxide doped with Y and Zr. It was.
  • LiOH was added to the mixed precursor at a molar ratio of 1.02, and the mixture was mixed at 15000 rpm for 10 minutes using a blending mixer, followed by secondary heat treatment at 800 ° C. in an oxygen atmosphere to prepare a cathode active material.
  • LiOH was added to the resultant reactant at a molar ratio of 1.02, and the mixture was mixed at 15000 rpm for 10 minutes using a blending mixer, and then calcined at 800 ° C. in an oxygen atmosphere to prepare a cathode active material.
  • Example 1-1 In preparing the cathode active materials according to Example 1-1 and Comparative Examples 1-1 and 1-2, the doped precursor was observed under a scanning electron microscope. The results are shown in FIGS. 1 to 3, respectively.
  • a positive electrode active material was prepared in the same manner as in Example 1, except that the particle size of the precursor particles and the doping element-containing raw material were variously changed as shown in Table 1 below.
  • Example 1-2 Example 1-3 Comparative Example 1-3 Comparative Example 1-4 Average Plate Thickness of Primary Particles in Metal Precursors (nm) 100 230 100 230 Metal precursor average particle diameter (D 50 ) ( ⁇ m) 15 15 15 15 15 Average particle size of raw material including doping element (D 50 ) ( ⁇ m) 2 3 3.5 4
  • the average plate thickness of the primary particles in the prepared metal precursor was observed and measured using a scanning electron microscope, and the average particle diameter of the metal precursor on the secondary particles and the average particle diameter of the raw material including the doping element were A metal precursor and a doping element-containing raw material were respectively introduced into a laser diffraction particle size measuring device (e.g., Microtrac MT 3000) and irradiated with an ultrasonic wave of about 28 kHz at an output of 60 W.
  • the average particle diameter (D 50 ) of was calculated.
  • Examples 1-2 and 1-3 where a metal precursor having a D 50 of 15 ⁇ m and a raw material including a doping element having a D 50 of 2 ⁇ m or 3 ⁇ m was mixed, the precursors were homogeneous by uniform mixing.
  • the doping element-containing raw material was partially aggregated and distributed on the precursor surface on the precursor surface, and the doping material was partially aggregated and present.
  • YSZ yttria-stabilized zirconia
  • LiOH was added to the doped precursor at a molar ratio of 1.02, and 80 g of acoustic energy was mixed for 2 minutes using an acoustic mixer (LabRAM II), followed by heat treatment at 800 ° C. in an oxygen atmosphere, and Y, Zr, and Al were doped.
  • a cathode active material of the lithium composite metal oxide was prepared.
  • YSZ yttria-stabilized zirconia
  • LiOH was added at a molar ratio of 1.02 to the doped precursor and mixed for 10 minutes at 15000 rpm using a blending mixer, followed by secondary heat treatment at 800 ° C. in an oxygen atmosphere to form a positive electrode of a lithium composite metal oxide doped with Y, Zr, and Al.
  • An active material was prepared.
  • Example 1-4 the doping precursor and the lithium raw material were uniform even though the acoustic mixing process time for the doped precursor and the lithium raw material was shorter than that of the blending mixing process in Comparative Example 1-1. After mixing, the lithium raw material was uniformly dispersed on the surface of the precursor particles. In addition, no damage to the doped precursor particle surface and bulk was observed. In addition to the manufacturing process of the doping precursor in the preparation of the doped cathode active material from this, it can be seen that it is possible to produce a cathode active material having better surface properties without surface damage by applying acoustic resonance when mixing with the lithium raw material after the doping.
  • the cathode active material prepared in Example 1-4, super P as a conductive material and PVDF as a binder were mixed at a polymerization ratio of 92.5: 2.5: 5 to prepare a composition for forming a cathode. After coating it on an aluminum foil, it was uniformly compressed using a roll press and vacuum dried for 12 hours at 130 ° C. in a vacuum oven to prepare a cathode for a lithium secondary battery. After the production of a half coin cell (half coin cell) of the 2032 standard using the positive electrode was evaluated the capacity characteristics. At this time, the half-coin cell was prepared using the cathode active material prepared in Comparative Example 1-5 for comparison.
  • the capacity characteristics of the lithium secondary battery is charged at 25 ° C. with a constant current (CC) of 0.2C until 4.25V, and then charged with a constant voltage (CV) of 4.25V until the charging current reaches 0.05mAh.
  • the first charge was performed. After standing for 20 minutes, the battery was discharged until it reached 2.5V with a constant current of 0.2C. Through this, the discharge capacity was evaluated and compared. The results are shown in Table 2 and FIG. 12.
  • the capacity characteristics of the battery are reduced, and additionally, particles which may act as impurities on the surface are generated due to the inhomogeneous doping or doping raw material remaining and agglomeration, thereby improving the battery characteristics. Can be reduced.
  • the battery containing the positive electrode active material of Example 1-4 showed a higher capacity characteristics than Comparative Example 1-5, from which the doping efficiency in the positive electrode active material prepared by the manufacturing method according to the present invention You can see that this is higher.
  • YSZ yttria-stabilized zirconia
  • LiOH was added to the doped precursor at a molar ratio of 1.03, and 80 g of acoustic energy was mixed for 2 minutes using an acoustic mixer (LabRAM II), followed by heat treatment at 780 ° C. in an oxygen atmosphere.
  • the resultant obtained after the heat treatment was dispersed in deionized water, and then washed with an acoustic mixer (LabRAM II) while applying 40g of acoustic energy for 5 minutes, filtered for 3 minutes or more, and then dried in a vacuum oven at 130 ° C. for 12 hours or more.
  • a cathode active material of a lithium composite metal oxide doped with Y, Zr, and Al was prepared.
  • Example 1-6 Of positive electrode active material Produce
  • LiOH was added to the mixed precursor at a molar ratio of 1.03, and 80 g of acoustic energy was applied for 2 minutes using an acoustic mixer (LabRAM II), followed by mixing, followed by heat treatment at 780 ° C. in an oxygen atmosphere.
  • the resultant after the heat treatment was dispersed in deionized water, washed with a mechanical stirrer (mechanical stirrer) for 5 minutes at 400rpm, filtered for 3 minutes, and then dried for 12 hours at 130 °C vacuum oven to prepare a cathode active material.
  • LiOH (% by weight) 100 ⁇ [(2 ⁇ EP-FP) ⁇ 0.1 ⁇ 0.001 ⁇ 23.94] / 5
  • Li 2 CO 3 (% by weight) 100 ⁇ [(FP-EP) ⁇ 0.1 ⁇ 0.001 ⁇ 73.89] / 5
  • Equations 1 and 2 EP is an evaluation point and FP is a fixed point.
  • the positive electrode active material of Example 1-5 using the acoustic mixer during the washing process showed a lower content of impurities and a pH value than those of Example 1-6.
  • a positive electrode active material of a lithium composite metal oxide doped with Al was prepared in the same manner as in Example 1-5, except that Al 2 O 3 was used instead of YSZ.
  • a positive electrode active material of a lithium composite metal oxide doped with ceramic elements (Sc and Zr) derived from a raw material including an SSZ doping element was prepared in the same manner as in Example 1-5 except that SSZ was used instead of YSZ. It was.
  • N-methyl-2 Positive electrode slurry was prepared by addition to pyrrolidone (NMP).
  • NMP pyrrolidone
  • the positive electrode slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 ⁇ m, dried to prepare a positive electrode, and then roll rolled to prepare a positive electrode.
  • LiPF 6 was added to a non-aqueous electrolyte solvent prepared by mixing ethylene carbonate and diethyl carbonate as a electrolyte in a volume ratio of 30:70 to prepare a 1 M LiPF 6 non-aqueous electrolyte.
  • a cell was prepared by injecting a lithium salt-containing electrolyte solution through a separator of porous polyethylene between the positive electrode and the negative electrode prepared above.
  • a lithium secondary battery was manufactured by the same method as in Example 2-1, except for using the cathode active materials prepared in Examples 1-2 to 1-8, respectively.
  • the positive electrode active material doped with a metal element containing a doping element using an acoustic resonance has improved structural stability, thereby minimizing capacity reduction in battery application. It was confirmed to exhibit excellent cycle characteristics.

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Abstract

La présente invention concerne un procédé de fabrication d'un matériau actif d'électrode positive pour une batterie secondaire, comprenant les étapes consistant à : mélanger un précurseur de métal pour un matériau actif d'électrode positive ayant un rapport de diamètre de particule moyen de 2000 à 5: 1 avec une matière première comprenant un élément de dopage en utilisant la résonance acoustique pour préparer un précurseur ayant été dopé par l'élément de dopage; et mélanger le précurseur dopé avec une matière première de lithium puis traiter thermiquement, de manière à ce que la batterie secondaire soit uniformément dopée par divers éléments de dopage sans risque d'endommagement de la surface du matériau actif et de la détérioration de ses propriétés. En outre, la présente invention porte sur un matériau actif d'électrode positive, qui est fabriqué par le procédé et ainsi a une stabilité structurale améliorée, et peut améliorer une propriété d'une batterie, sur lequel le procédé est appliqué, par exemple, elle peut minimiser la réduction de la capacité de la batterie et améliorer une propriété de cycle de celle-ci.
PCT/KR2017/007114 2016-07-04 2017-07-04 Méthode de fabrication de matériau actif d'électrode positive pour batterie secondaire et matériau actif d'électrode positive pour batterie secondaire fabriqué grâce à celle-ci Ceased WO2018008952A1 (fr)

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EP17824508.0A EP3388394B1 (fr) 2016-07-04 2017-07-04 Méthode de fabrication de matériau actif d'électrode positive pour batterie secondaire et matériau actif d'électrode positive pour batterie secondaire fabriqué grâce à celle-ci
US16/069,710 US10637056B2 (en) 2016-07-04 2017-07-04 Method of preparing positive electrode active material for secondary battery and positive electrode active material for secondary battery prepared thereby
CN201780010065.6A CN108602689B (zh) 2016-07-04 2017-07-04 制备二次电池用正极活性材料的方法和由此制备的二次电池用正极活性材料
JP2018558102A JP6968428B2 (ja) 2016-07-04 2017-07-04 二次電池用正極活物質の製造方法およびこれにより製造された二次電池用正極活物質

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3761415A4 (fr) * 2018-04-06 2021-06-02 Lg Chem, Ltd. Matériau actif de cathode pour batterie rechargeable au lithium, son procédé de fabrication, cathode comprenant celui-ci et destinée à une batterie rechargeable au lithium, et batterie rechargeable au lithium
EP3881373A1 (fr) * 2019-11-12 2021-09-22 Johnson Matthey Public Limited Company Processus destiné à produire un matériau d'oxyde de métal lithium-nickel particulaire modifié en surface

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