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WO2017095153A1 - Matériau actif de cathode pour accumulateur et accumulateur comprenant celui-ci - Google Patents

Matériau actif de cathode pour accumulateur et accumulateur comprenant celui-ci Download PDF

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Publication number
WO2017095153A1
WO2017095153A1 PCT/KR2016/014004 KR2016014004W WO2017095153A1 WO 2017095153 A1 WO2017095153 A1 WO 2017095153A1 KR 2016014004 W KR2016014004 W KR 2016014004W WO 2017095153 A1 WO2017095153 A1 WO 2017095153A1
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Prior art keywords
active material
positive electrode
secondary battery
raw material
metal
Prior art date
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PCT/KR2016/014004
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English (en)
Korean (ko)
Inventor
박병천
정왕모
강성훈
신주경
박상민
이상욱
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LG Chem Ltd
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LG Chem Ltd
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Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP16871049.9A priority Critical patent/EP3386015B1/fr
Priority to ES16871049T priority patent/ES3027649T3/es
Priority to PL16871049.9T priority patent/PL3386015T3/pl
Priority to CN201680057268.6A priority patent/CN108140829B/zh
Priority to US15/760,111 priority patent/US11081694B2/en
Priority to JP2018519459A priority patent/JP7114148B2/ja
Priority claimed from KR1020160161896A external-priority patent/KR101989399B1/ko
Publication of WO2017095153A1 publication Critical patent/WO2017095153A1/fr
Anticipated expiration legal-status Critical
Priority to US17/352,950 priority patent/US11581538B2/en
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/50—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
    • 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 cathode active material for a secondary battery and a secondary battery including the same, which have a stable monolithic structure and can improve high temperature stability and capacity characteristics of the battery.
  • lithium secondary batteries having high energy density and voltage, long cycle life, and low self discharge rate have been commercialized and widely used.
  • a lithium secondary battery has a problem in that its life is rapidly decreased as charging and discharging are repeated. In particular, this problem is more serious at high temperatures. This is a phenomenon caused by decomposition of the electrolyte or deterioration of the active material due to moisture or other influences inside the battery, and increase of internal resistance of the battery.
  • LiCoO 2 having a layered structure. LiCoO 2 is most frequently used because of its excellent lifespan and efficiency of charging and discharging. However, the structural stability is low, there is a limit to apply to high capacity technology of the battery.
  • LiNiO 2 LiMnO 2 , LiMn 2 O 4 , LiFePO 4 , Li (Ni x1 Co y1 Mn z1 ) O 2
  • LiNiO 2 has an advantage of exhibiting battery characteristics of high discharge capacity.
  • a simple solid phase reaction is difficult to synthesize, and has a problem of low thermal stability and low cycle characteristics.
  • lithium manganese oxides such as LiMnO 2 or LiMn 2 O 4 have the advantages of excellent thermal stability and low price.
  • the lithium manganese oxide has a problem of low 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 a lot of research is being made for hybrid electric vehicles (HEV), but it is difficult to apply to other fields due to low conductivity.
  • 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 is in the form of secondary particles in which small primary particles are aggregated.
  • the secondary particles of the cathode active material lithium ions move to the surface of the active material and react with moisture or CO 2 in the air to easily form surface impurities such as Li 2 CO 3 and LiOH.
  • the surface impurities thus formed cause a swelling phenomenon of the battery by reducing the battery capacity or decomposing in the battery to generate gas, thereby causing a serious problem in high temperature stability.
  • the first technical problem to be solved by the present invention is to provide a cathode active material for a secondary battery and a method for manufacturing the same, which has a stable monolithic structure and can improve high temperature stability and capacity characteristics of a battery.
  • a second technical problem to be solved by the present invention is to provide a secondary battery positive electrode, a lithium secondary battery, a battery module and a battery pack including the positive electrode active material.
  • M1 is at least one selected from the group consisting of Al and Mn
  • M2 is any one or two or more elements selected from the group consisting of Zr, Ti, Mg, Ta and Nb
  • M3 is Any one or two or more elements selected from the group consisting of W, Mo and Cr, 1.0 ⁇ a ⁇ 1.5, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0.002 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.04, 0 ⁇ x + y ⁇ 0.7)
  • the nickel raw material, cobalt raw material, and M1 raw material (wherein M1 is at least one element selected from the group consisting of Al and Mn) is mixed and then reacted Preparing a precursor;
  • a cathode for a secondary battery a lithium secondary battery, a battery module, and a battery pack including the cathode active material.
  • the cathode active material for a secondary battery according to the present invention has a monolithic structure and maintains a stable crystal structure even during charging and discharging, so that there is no concern about a sudden drop in capacity due to a change in crystal structure, and generation of surface impurities is minimized. Accordingly, when the battery is applied, it can exhibit excellent high temperature stability and capacity characteristics.
  • Figure 1 is a photograph of the cathode active material prepared in Example 1-1 observed with a scanning electron microscope.
  • a cathode active material for a secondary battery according to an embodiment of the present invention is a primary particle having a monolithic structure including a lithium composite metal oxide of Formula 1 below, and an average particle diameter (D 50 ) of 2 ⁇ m to 20 ⁇ m. and a BET specific surface area 0.15m 2 / g to 1.9m 2 / g.
  • M1 is at least one selected from the group consisting of Al and Mn
  • M2 is any one or two or more elements selected from the group consisting of Zr, Ti, Mg, Ta and Nb
  • M3 is Any one or two or more elements selected from the group consisting of W, Mo and Cr, 1.0 ⁇ a ⁇ 1.5, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0.002 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.04, 0 ⁇ x + y ⁇ 0.7)
  • composition of the lithium composite metal oxide of Chemical Formula 1 is an average composition of the entire active material.
  • the "monolith structure” refers to a structure in which particles exist in an independent phase in which particles do not aggregate with each other in a morphology phase.
  • Particle structures in contrast to these monolithic structures, include structures in which small-sized particles ('primary particles') are physically and / or chemically aggregated to form relatively large particle forms ('secondary particles'). Can be.
  • the cathode active material according to the present invention has a monolithic structure, and thus, a migration path from lithium ions to the surface of the cathode active material becomes long. Accordingly, lithium ions moved to the surface of the active material react with moisture or CO 2 in the air, thereby minimizing the formation of surface impurities formed by adsorption of Li 2 CO 3 or LiOH on the oxide surface. In addition, many problems that can occur due to surface impurities, such as reduced battery capacity, increased interfacial resistance due to disturbance of lithium ions, gas generation due to decomposition of impurities, and swelling of the battery And the like can be prevented. As a result, capacity characteristics, high temperature stability, and charge / discharge characteristics may be improved when the cathode active material is applied to a battery.
  • the positive electrode active material according to an embodiment of the present invention may have excellent structural stability by including the lithium composite metal oxide of Formula 1, thereby improving the life characteristics of the battery.
  • Li may be included in an amount corresponding to a, that is, 1.0 ⁇ a ⁇ 1.5. If a is less than 1.0, the capacity may be lowered. If a is more than 1.5, the particles may be sintered in the firing step, and thus the production of the active material may be difficult. Considering the remarkable effect of improving the capacity characteristics of the positive electrode active material according to the Li content control and the sinterability in the preparation of the active material, the Li may be more specifically included in a content of 1.0 ⁇ a ⁇ 1.15.
  • Ni may be included in an amount corresponding to 1-xy, that is, 1-xy, for example, 0.3 ⁇ 1-xy ⁇ 1. have. In consideration of the remarkable effect of improving the capacity characteristic according to the inclusion of Ni, Ni may be included in an amount of 0.3 ⁇ 1-x-y ⁇ 0.6 or 0.6 ⁇ 1-x-y ⁇ 1.
  • Co may be included in an amount corresponding to x, that is, 0 ⁇ x ⁇ 0.5. If x is 0, the capacity characteristic may be lowered, and if it is more than 0.5, there is a fear of an increase in cost. Considering the remarkable effect of improving the capacity characteristics according to the inclusion of Co, the Co may be included in more specifically 0.10 ⁇ x ⁇ 0.35.
  • M1 may be at least one selected from the group consisting of Al and Mn.
  • M1 is Al
  • Mn structural stability of the active material may be improved to improve battery safety.
  • M1 may be included in an amount corresponding to y, that is, 0 ⁇ y ⁇ 0.5. If it exceeds 0.5, there is a fear that the output characteristics and the capacity characteristics of the battery are deteriorated. In consideration of the remarkable effect of improving the battery characteristics according to the inclusion of the M1 element, M1 may be included in a content of 0.10 ⁇ y ⁇ 0.3 more specifically.
  • M3 is an element corresponding to Group 6 (VIB group) of the periodic table, and serves to suppress grain growth during firing of active material particles.
  • M3 may be present at a position where these elements should be present by substituting a part of Ni, Co, or M1, or may react with lithium to form lithium oxide. Accordingly, the size of the crystal grains can be controlled by controlling the content of M3 and the timing of feeding.
  • M3 may be any one or two or more elements selected from the group consisting of W, V, Nb, Nd, and Mo, and more specifically, may be at least one element of W and Nb. Among them, when M3 is W, the output characteristic improvement effect is excellent, and in the case of Nb, the high temperature durability improvement effect is more excellent.
  • Such M3 may be included in an amount corresponding to z in the lithium composite metal oxide of Formula 1, that is, 0.002 ⁇ z ⁇ 0.03.
  • z is less than 0.002
  • the improvement of output and life characteristics may be insignificant.
  • z exceeds 0.03, the crystal structure may be distorted or collapsed.
  • battery capacity can be reduced by disturbing the movement of lithium ions. More specifically, considering the embodied particle structure according to the content control of the M3 element and the remarkable effect of improving the battery characteristics, it may be 0.005 ⁇ z ⁇ 0.01.
  • the elements of Ni, Co, and M1 in the lithium composite metal oxide or the lithium composite metal oxide of Formula 1 may be replaced by another element, that is, M2, to improve battery characteristics by controlling distribution of metal elements in the active material. It may be partially substituted or doped.
  • M2 may be any one or two or more elements selected from the group consisting of Zr, Ti, Mg, Ta, and Nb, and more specifically, may be Ti or Mg.
  • the element of M2 may be included in an amount corresponding to w, that is, 0 ⁇ w ⁇ 0.04, specifically 0 ⁇ w ⁇ 0.02 within a range that does not lower the characteristics of the positive electrode active material.
  • At least one metal element of nickel, M1, and cobalt included in the lithium composite metal oxide of Formula 1 may exhibit a concentration gradient that increases or decreases in the active material.
  • the concentration gradient or the concentration profile of the metal element means that the content of the metal element according to the depth of the center portion at the particle surface is determined when the X axis represents the depth of the center portion at the particle surface and the Y axis represents the content of the metal element.
  • Meaning graph to represent For example, a positive mean slope of the concentration profile means that the metal element is located in the center portion of the particle relatively more than the surface portion of the particle, and a negative mean slope means that the metal element is located in the surface portion of the particle more than the center portion of the particle. It means that it is located relatively much.
  • the concentration gradient and concentration profile of the metal in the active material is X-ray photoelectron spectroscopy (also called XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis), electron beam micro analyzer (Electron Probe Micro) Analyzer, EPMA), Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-AES), or Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS)
  • XPS X-ray Photoelectron Spectroscopy
  • ESCA Electrodetec Spectroscopy for Chemical Analysis
  • electron beam micro analyzer Electro Probe Micro
  • ICP-AES Inductively Coupled Plasma-Atomic Emission Spectrometer
  • ToF-SIMS Time of Flight Secondary Ion Mass Spectrometry
  • the at least one metal element of nickel, cobalt, and M1 may have a concentration gradient in which the metal concentration continuously changes throughout the active material particles, and the gradient of the concentration of the metal element may exhibit one or more values. .
  • the gradient of the concentration gradient of the metal is constant, the effect of improving the structural stability may be further improved.
  • the concentration of each metal in the active material particles through the concentration gradient it is possible to easily utilize the properties of the metal to further improve the battery performance improvement effect of the positive electrode active material.
  • “showing a concentration gradient in which the metal concentration continuously changes” means that the metal concentration exists in a concentration distribution that gradually changes throughout the active material particles.
  • the concentration distribution is 0.1 atomic% to 30 atomic%, respectively, based on the total atomic weight of the corresponding metal included in the precursor, the change in the metal concentration per 1 ⁇ m, more specifically 0.1 ⁇ m in the particles, Specifically, there may be a difference of 0.1 atomic% to 20 atomic%, and more specifically 1 atomic% to 10 atomic%.
  • the concentration of nickel contained in the active material may decrease while having a continuous concentration gradient from the center of the active material particles toward the surface of the particles.
  • the gradient of the concentration gradient of nickel may be constant from the center of the active material particles to the surface.
  • the concentration of M1 contained in the active material may increase while having a continuous concentration gradient from the center of the active material particles toward the surface of the particles.
  • the concentration gradient slope of M1 may be constant from the center of the active material particles to the surface.
  • M1 may be Mn.
  • the concentration of cobalt contained in the active material may increase while having a continuous concentration gradient from the center of the active material particles toward the surface of the particles.
  • the concentration gradient slope of the cobalt may be constant from the center of the active material particles to the surface.
  • the nickel, M1 and cobalt each independently exhibits a varying concentration gradient throughout the active material particles, the concentration of nickel decreases with a continuous concentration gradient from the center of the active material to the surface direction, and the cobalt And the concentration of M1 can be increased each independently having a continuous concentration gradient from the center of the active material to the surface direction.
  • the concentration of nickel decreases toward the surface of the active material and the concentration of M1 and cobalt increases throughout the active material, thereby improving thermal stability while maintaining the capacity characteristics of the positive electrode active material. .
  • the positive electrode active material according to an embodiment of the present invention may have a polyhedral shape by controlling the content of M3 element and the timing of addition and heat treatment conditions in the manufacturing process.
  • the positive electrode active material can be easily inserted and detached from lithium ions, and lithium ions can be moved at a high speed even in the active material particles, thereby exhibiting improved output characteristics when the battery is applied.
  • the positive electrode active material may have a rectangular parallelepiped shape or a plate-like shape having a rectangular cross section including a long axis passing through the center of the particle.
  • the cathode active material according to an embodiment of the present invention having the structure and configuration as described above has an average particle diameter (D 50 ) of 2 ⁇ m to 20 ⁇ m, and a BET specific surface area of 0.15 m 2 / g to 1.9 m 2. / g.
  • the efficiency of the battery to the weight decreases, and a relatively small amount of the positive electrode active material is included compared to the same standard or the coating property of the active material particles
  • the battery capacity may be reduced, such as being lowered and omitted in the manufacturing process of the electrode.
  • the positive electrode active material according to an embodiment of the present invention can not only significantly reduce the adsorption of surface impurities by simultaneously meeting the above average particle diameter and BET specific surface conditions, but also excellent in spite of a small ion contact area. Output characteristics can be indicated. More specifically, the cathode active material may have an average particle diameter (D 50 ) of 2 ⁇ m to 8 ⁇ m and BET specific surface area of 0.15m 2 / g to 0.5m 2 / g.
  • the average particle diameter (D 50 ) of the active material may be defined as the particle size at 50% of the particle size distribution.
  • the average particle diameter (D 50 ) of the active material is, for example, electron microscope observation using a scanning electron microscopy (SEM) or a field emission scanning electron microscopy (FE-SEM) or the like. Alternatively, it can be measured using a laser diffraction method. When measured by the laser diffraction method, more specifically, the active material was dispersed in a dispersion medium, and then introduced into a commercially available laser diffraction particle size measuring apparatus (for example, Microtrac MT 3000) to irradiate an ultrasonic wave of about 28 kHz at an output of 60 W.
  • a commercially available laser diffraction particle size measuring apparatus for example, Microtrac MT 3000
  • the mean particle size (D 50) of from 50% based on the particle size distribution of the measuring device is measured by the Brunauer-Emmett-Teller (BET) method, specifically, under the liquid nitrogen temperature (77K) using BELSORP-mino II manufactured by BEL Japan. It can calculate from nitrogen gas adsorption amount.
  • BET Brunauer-Emmett-Teller
  • the cathode active material according to an embodiment of the present invention may have a particle size distribution value (Dcnt) defined by Equation 1 below 0.5 to 1.0, more specifically 0.55 to 0.9. If the particle size distribution value of the active material is less than 0.5, the high-density electrode manufacturing process may not be easy, and if it exceeds 1.0, there is a fear of lowering of rolling processability.
  • Dcnt particle size distribution value
  • Dn90 is the average particle diameter measured under 90% in the absorbing mode using a Microtrac particle size analyzer after leaving the active material in distilled water for 3 hours
  • Dn10 is the number measured under the 10% basis Average particle diameter
  • Dn50 is the number average particle diameter measured on a 50% basis
  • the positive electrode active material according to an embodiment of the present invention has an average particle diameter and specific surface area in the above range of 3.0g / cc or more, or 3.0g / cc to 4.5g / cc under a pressure of 2ton? F It can exhibit high rolling density.
  • the rolling density of a positive electrode active material can be measured using a normal rolling density measuring instrument, and can be measured using a powder resistance characteristic measuring instrument (HPRM-A1, Hantech Co., Ltd.) specifically.
  • the rolling density may be calculated through the density of pellets formed while filling the powder into the insulating mold and applying pressure in the vertical direction. Rolling density is influenced by the size of the grains and the degree of aggregation of the particles.
  • the positive electrode active material according to an embodiment of the present invention is a mixture of a nickel raw material, cobalt raw material, and M1 raw material (wherein M1 is at least one element selected from the group consisting of Al and Mn) Thereafter, reacting to prepare a precursor (step 1);
  • the cathode active material further comprises M2 (wherein M2 is any one or two or more elements selected from the group consisting of Zr, Ti, Mg, Ta and Nb), each of the metal elements in step 1 M2 raw materials may be added when mixing the raw materials, or M2 raw materials may be added when mixing with the lithium raw materials in step 2. Accordingly, according to another embodiment of the present invention, a method of manufacturing the cathode active material is provided.
  • step 1 in the manufacturing method for the production of the cathode active material is a step of preparing a precursor using a nickel raw material, cobalt raw material, M1 raw material, and optionally M2 raw material .
  • the precursor may be prepared by co-precipitation by adding an ammonium cation-containing complex forming agent and a basic compound to a metal-containing solution prepared by mixing nickel raw material, cobalt raw material, M1 raw material, and M2 raw material. have.
  • the mixing ratio of each raw material may be appropriately determined within a range to satisfy the content condition of each metal element in the final cathode active material.
  • the metal-containing solution may be formed of an organic solvent (specifically, alcohol, etc.) capable of uniformly mixing nickel raw material, cobalt raw material, M1 containing raw material and optionally M2 containing raw material with a solvent, specifically water, or water, respectively. It may be prepared by adding to a mixture of water, or may be used after mixing a solution containing each raw material, specifically, an aqueous solution.
  • an organic solvent specifically, alcohol, etc.
  • a raw material including the metal element acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide, or oxyhydroxide may be used, and the like, and it is not particularly limited as long as it can be dissolved in water.
  • the cobalt raw material may be Co (OH) 2 , CoOOH, Co (SO 4 ) 2 , Co (OCOCH 3 ) 2 .4H 2 O, Co (NO 3 ) 2 .6H 2 O, CoCl 2 or Co (SO 4 ) 2 .7H 2 O, and the like. Can be used.
  • nickel raw material in the Ni (OH) 2, NiO, NiOOH, NiCO 3 and 2Ni (OH) 2 and 4H 2 O, NiC 2 O 2 and 2H 2 O, NiCl 2, Ni (NO 3) 2 and 6H 2 O, NiSO 4 , NiSO 4 .6H 2 O, fatty acid nickel salts or nickel halides, and the like, and any one or a mixture of two or more thereof may be used.
  • manganese oxides such as Mn 2 O 3 , MnO 2 , and Mn 3 O 4 ;
  • Manganese salts such as MnCO 3 , MnCl 2 , Mn (NO 3 ) 2 , MnSO 4 , manganese acetate, manganese dicarboxylic acid, manganese citrate and fatty acid manganese; Oxy hydroxide, and manganese chloride, and the like, and any one or a mixture of two or more thereof may be used.
  • the aluminum raw material may be AlSO 4 , AlCl 3 , Al-isopropoxide (Al-isopropoxide) or AlNO 3 and the like, any one or a mixture of two or more thereof may be used.
  • M2 raw material acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide containing M2 element may be used.
  • M 2 is Ti
  • titanium oxide may be used.
  • ammonium cation-containing complexing agent may specifically be 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. Species alone or mixtures of two or more may be used.
  • the ammonium cation-containing complex forming agent may be used in the form of an aqueous solution, wherein a solvent may be a mixture of water or an organic solvent (specifically, alcohol, etc.) that can be mixed with water uniformly.
  • the ammonium cation-containing complex forming agent may be added in an amount such that the molar ratio of 0.5 to 1 per mole of the metal-containing solution.
  • the chelating agent reacts with the metal in a molar ratio of at least 1: 1 to form a complex, but the unreacted complex which does not react with the basic aqueous solution may be converted into an intermediate product, recovered as a chelating agent, and reused.
  • the chelating usage can be lowered than usual. As a result, the crystallinity of the positive electrode active material can be increased and stabilized.
  • the basic compound may be a hydroxide of an alkali metal or an alkaline earth metal such as NaOH, KOH, or Ca (OH) 2 , or a hydrate thereof, and one or more of these 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 uniformly mixed with water may be used.
  • the coprecipitation reaction for forming the precursor may be carried out under the condition that the pH is 11 to 13. If the pH is out of the above range, there is a fear to change the size of the precursor to be prepared or cause particle splitting.
  • metal ions may be eluted on the surface of the precursor to form various oxides by side reactions. More specifically, the pH of the mixed solution may be performed at 11 to 12 conditions.
  • the ammonium cation-containing complexing agent and the basic compound may be used in a molar ratio of 1:10 to 1: 2 to satisfy the above pH range.
  • the pH value means a pH value at the temperature of the liquid 25.
  • the coprecipitation reaction may be performed at a temperature of 40 ° C. to 70 ° C. under an inert atmosphere such as nitrogen.
  • the stirring process may be selectively performed to increase the reaction rate during the reaction, wherein the stirring speed may be 100 rpm to 2000 rpm.
  • a metal containing nickel, cobalt, M1 containing raw material and optionally M2 containing raw material at a different concentration from the above metal containing solution After preparing the containing solution (hereinafter simply referred to as the second metal containing solution), the mixing ratio of the metal containing solution and the second metal containing solution is gradually increased from 100% by volume to 0% by volume and 100% by volume.
  • the second metal-containing solution may be added to the metal-containing solution so as to be changed, and the reaction may be performed by adding an ammonium cation-containing complex former and a basic compound.
  • nickel, cobalt, and M1 are independently from the center of the particle to the surface in one coprecipitation reaction process.
  • Precursors with continuously varying concentration gradients can be prepared.
  • the concentration gradient of the metal in the precursor and its slope can be easily controlled by the composition and the mixed feed ratio of the metal-containing solution and the second metal-containing solution, and to make a high density state with a high concentration of a specific metal It is preferable to lengthen the reaction time and to lower the reaction rate, and to shorten the reaction time and increase the reaction rate in order to make a low density state having a low concentration of a specific metal.
  • the speed of the second metal-containing solution added to the metal-containing solution may be carried out continuously increasing in the range of 1 to 30% compared to the initial charging speed.
  • the input speed of the metal-containing solution may be 150ml / hr to 210ml / hr
  • the input speed of the second metal-containing solution may be 120ml / hr to 180ml / hr
  • the initial charge within the input speed range The dosing rate of the second metal containing solution in the range of 1% to 30% of the rate can be continuously increased.
  • the reaction may be carried out at 40 °C to 70 °C.
  • the size of the precursor particles may be adjusted by adjusting the supply amount and the reaction time of the second metal-containing solution to the metal-containing solution.
  • the precursor particles of a composite metal hydroxide are generated as a precursor and are precipitated in a reaction solution.
  • the precursor may include a compound of Formula 2 below.
  • the nickel raw material, cobalt raw material and M1 raw material may be a metal powder containing each metal element.
  • the precursor may be prepared by mixing a powdery raw material containing each metal element and then heat-treating at 200 ° C to 500 ° C.
  • step 2 by mixing the precursor particles prepared in step 1 with a lithium-containing raw material, M3 raw material, and optionally M2 raw material and then calcining the formula It is a step of forming a lithium composite metal oxide of 1.
  • M2 raw material is the same as described above.
  • lithium-containing carbonate for example, lithium carbonate
  • hydrate for example, lithium hydroxide I hydrate (LiOH, H 2 O), etc.
  • hydroxide for example, lithium hydroxide, etc.
  • Nitrates e.g., lithium nitrate (LiNO 3 ), etc.
  • chlorides e.g., lithium chloride (LiCl), etc.
  • M3 raw material acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide containing M3 element may be used.
  • M 3 is W
  • tungsten oxide may be used.
  • the M3 raw material may be used in a range to satisfy the content condition of the M3 element in the positive electrode active material to be manufactured finally.
  • a preliminary heat treatment at 250 ° C to 500 ° C may be optionally performed before the firing process. Through such a preliminary heat treatment process, it is possible to increase the firing rate during the firing process.
  • the preliminary heat treatment process may be performed in one step, or may be performed in multiple steps at different temperatures.
  • the firing process may be performed at 700 °C to 900 °C, or 750 °C to 850 °C.
  • the firing process By controlling the temperature during the firing process, it is possible to control the shape and size, aspect ratio and orientation of the primary particles, it is possible to manufacture the positive electrode active material having the above structure by performing in the above temperature range.
  • the firing process may be carried out in a multi-step of 2-3 steps.
  • the firing process may be performed in an air atmosphere or an oxygen atmosphere (for example, O 2 ), and more specifically, may be performed in an oxygen atmosphere having an oxygen partial pressure of 20% by volume or more. In addition, the firing process may be performed for 5 hours to 48 hours, or 10 hours to 20 hours under the above conditions.
  • O 2 oxygen atmosphere
  • the firing process may be performed for 5 hours to 48 hours, or 10 hours to 20 hours under the above conditions.
  • the firing process may be carried out in the presence of a firing additive.
  • the calcining additive can easily grow crystals at low temperatures and minimize the heterogeneous reaction during dry mixing.
  • the calcining additive may be boron-based compounds such as boric acid, lithium tetraborate, boron oxide, and ammonium borate, and any one or a mixture of two or more thereof may be used.
  • the calcining additive may be used in an amount of 0.2 to 2 parts by weight, more specifically 0.4 to 1.4 parts by weight based on 100 parts by weight of the precursor.
  • the moisture removing agent may be optionally further added during the firing process.
  • the water removing agent may include citric acid, tartaric acid, glycolic acid or maleic acid, and any one or a mixture of two or more thereof may be used.
  • the moisture remover may be used in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the precursor.
  • step 3 may be a washing step and a drying step for removing impurities present on the surface of the reactants obtained as a result of firing.
  • the drying process may be carried out according to a conventional drying method, specifically, may be carried out by a method such as heat treatment or hot air injection in the temperature range of 150 °C to 400 °C, more specifically described above It may be performed for 15 to 30 hours in the temperature range.
  • the positive electrode active material prepared by the above process has a monolithic structure, which can maintain a stable crystal structure even during charging and discharging, so that there is no fear of a sudden drop in capacity due to a change in crystal structure, and generation of surface impurities is minimized. It can exhibit excellent high temperature stability and capacity characteristics in battery applications.
  • a cathode and a lithium secondary battery including the cathode active material are provided.
  • the positive electrode is formed on the positive electrode current collector and the positive electrode current collector, and includes a positive electrode active material layer containing the positive electrode active material.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • carbon, nickel, titanium on the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface treated with silver, silver or the like can be used.
  • the positive electrode current collector may have a thickness of about 3 to 500 ⁇ m, and may form fine irregularities on the surface of the current collector to increase adhesion of the positive electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the cathode active material layer may include a conductive material and a binder together with the cathode active material described above.
  • the conductive material is used to impart conductivity to the electrode.
  • the conductive material may be used without particular limitation as long as it has electronic conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, and the like, or a mixture of two or more kinds thereof may be used.
  • the conductive material may typically be included in an amount of 1% to 30% by weight based on the total weight of the positive electrode active material layer.
  • the binder serves to improve adhesion between the cathode active material particles and adhesion between the cathode active material and the current collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC).
  • the binder may be included in an amount of 1% by weight to 30% by weight based on the total weight of the positive electrode active material layer.
  • the positive electrode may be manufactured according to a conventional positive electrode manufacturing method except for using the positive electrode active material described above.
  • the positive electrode active material and optionally, a composition for forming a positive electrode active material layer including a binder and a conductive material may be prepared by applying a positive electrode current collector, followed by drying and rolling.
  • the type and content of the cathode active material, the binder, and the conductive material are as described above.
  • the solvent may be a solvent generally used in the art, and may include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone or acetone. Water, and the like, one of these alone or a mixture of two or more thereof may be used.
  • the amount of the solvent is sufficient to dissolve or disperse the positive electrode active material, the conductive material, and the binder in consideration of the coating thickness of the slurry and the production yield, and to have a viscosity that can exhibit excellent thickness uniformity during application for the production of the positive electrode. Do.
  • the positive electrode may be prepared by casting the composition for forming the positive electrode active material layer on a separate support, and then laminating the film obtained by peeling from the support onto a positive electrode current collector.
  • an electrochemical device including the anode is provided.
  • the electrochemical device may be specifically a battery, a capacitor, or the like, and more specifically, a lithium secondary battery.
  • the lithium secondary battery specifically includes a positive electrode, a negative electrode positioned to face the positive electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode, and the positive electrode is as described above.
  • the lithium secondary battery may further include a battery container for accommodating the electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member for sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer positioned on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • the negative electrode current collector may be formed on a 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.
  • the negative electrode current collector may have a thickness of about 3 to 500 ⁇ m, and like the positive electrode current collector, fine concavities and convexities may be formed on the surface of the current collector to enhance the bonding force of the negative electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the negative electrode active material layer optionally includes a binder and a conductive material together with the negative electrode active material.
  • the negative electrode active material layer is coated with a negative electrode active material, and optionally a composition for forming a negative electrode including a binder and a conductive material on a negative electrode current collector and dried, or casting the negative electrode forming composition on a separate support It can also be produced by laminating a film obtained by peeling from this support onto a negative electrode current collector.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fibers, and amorphous carbon;
  • Metallic compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys;
  • Metal oxides capable of doping and undoping lithium such as SiO x (0 ⁇ x ⁇ 2), SnO 2 , vanadium oxide, lithium vanadium oxide;
  • a composite including the metallic compound and the carbonaceous material such as a Si-C composite or a Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the anode active material.
  • the carbon material both low crystalline carbon and high crystalline carbon can be used. Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is amorphous, plate, scaly, spherical or fibrous natural graphite or artificial graphite, Kish graphite (Kish) graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar pitch High-temperature calcined carbon such as derived cokes is typical.
  • the binder and the conductive material may be the same as described above in the positive electrode.
  • the separator is to separate the negative electrode and the positive electrode and to provide a passage for the movement of lithium ions, if it is usually used as a separator in a lithium secondary battery can be used without particular limitation, in particular to the ion movement of the electrolyte It is desirable to have a low resistance against the electrolyte and excellent electrolytic solution-moisture capability.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • a porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
  • examples of the electrolyte used in the present invention include an organic 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. It doesn't happen.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • the organic solvent may be an ester solvent such as methyl acetate, ethyl acetate, ⁇ -butyrolactone or ⁇ -caprolactone; Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethylcarbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate, Carbonate solvents such as PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles such as R-CN (R is a C2 to C20 linear, branched or cyclic hydrocarbon group, which may include a
  • carbonate-based solvents are preferable, and cyclic carbonates having high ionic conductivity and high dielectric constant (for example, ethylene carbonate or propylene carbonate) that can improve the charge and discharge performance of a battery, and low viscosity linear carbonate compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate and the like is more preferable.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 and the like can be used.
  • the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc. for the purpose of improving battery life characteristics, reducing battery capacity, and improving discharge capacity of the battery.
  • haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc.
  • Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be included. In this case, the additive may be included in 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles ( It is useful for electric vehicle fields such as hybrid electric vehicle (HEV).
  • HEV hybrid electric vehicle
  • 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, 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, 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.
  • nickel sulfate, cobalt sulfate and manganese sulfate were mixed in a molar ratio of 60:20:20 and then mixed in water to prepare a metal containing solution at a 2 M concentration.
  • the vessel containing the metal containing solution was connected to enter the reactor, and prepared with 4M NaOH solution and 7% aqueous NH 4 OH solution was connected to each reactor.
  • 3 liters of deionized water was added to the coprecipitation reactor (capacity 5L), and nitrogen gas was purged at the reactor at a rate of 2 liters / minute to remove dissolved oxygen in water and to form a non-oxidizing atmosphere in the reactor. Since 4M NaOH was added 100ml, it was maintained at pH 12.0 at a stirring speed of 1,200rpm at 60 °C.
  • the precursor and the lithium hydroxide as the lithium raw material and the tungsten oxide (WO 3 ) as the tungsten raw material were mixed so that the molar ratio of M (total of Ni, Mn and Co): Li: W was 0.995: 2.0: 0.005.
  • boron oxide (B 2 O 3 ) was added in an amount of 0.5 parts by weight based on 100 parts by weight of the precursor.
  • the lithium composite metal oxide was prepared by heat treatment at 820 ° C. for 10 hours under an oxygen atmosphere (oxygen partial pressure 20%).
  • the lithium composite metal oxide and distilled water were mixed at a ratio of 1: 1 and stirred at a speed of 1,000 rpm for 10 minutes to remove residual lithium on the surface, followed by drying in an oven at 150 ° C. for 12 hours to form a cathode active material having a single phase structure ( a Li 1.07 (Ni 0. 6 Mn 0. 2 Co 0. 2) 0.995 W 0. 005 O 2) was prepared.
  • nickel sulfate, cobalt sulfate, manganese sulfate and magnesium sulfate were mixed in water at a molar ratio of 60: 20: 20: 0.02 to prepare a metal containing solution at a concentration of 2M
  • Nickel sulphate, cobalt sulphate, manganese sulphate and magnesium sulphate were mixed in water at a molar ratio of 40: 30: 30: 0.02 to prepare a second metal containing solution at a concentration of 2M.
  • the vessel containing the metal containing solution was connected to enter the reactor, and the vessel containing the second metal containing solution was connected to enter the metal containing solution container.
  • 4M NaOH solution and 7% NH 4 OH aqueous solution were prepared and connected to the reactor, respectively.
  • the metal-containing solution 180 ml / hr of the metal-containing solution, 180 ml / hr of the NaOH aqueous solution, and NH 4 OH aqueous solution were added at a rate of 10 ml / hr, followed by reaction for 30 minutes to form a seed of the hydroxide of the first metal-containing solution.
  • the second metal-containing solution was introduced into the container of the first metal-containing solution at 150 ml / hr to induce the growth of the hydroxide particles and to induce a concentration gradient inside the particles. Since the reaction was maintained for 24 hours to grow nickel manganese cobalt-based composite metal hydroxide.
  • the resulting nickel manganese cobalt-based composite metal hydroxide particles were separated and washed with water and dried in an oven at 120 °C to prepare a precursor.
  • the resulting precursor and the lithium hydroxide as a lithium raw material and the tungsten oxide (WO 3 ) as the tungsten raw material were M (total of Ni, Mn and Co): Mg: Li: W and the molar ratio of 0.975: 0.02: 2.0: 0.005 Mix as much as possible.
  • a boron oxide (B 2 O 3) by baking additive with respect to the 100 parts by weight of the precursor was added in an amount of 0.5 wt.
  • a lithium composite metal oxide was prepared by heat treatment at 820 ° C. for 10 hours under an oxygen atmosphere (oxygen partial pressure 20%).
  • the lithium composite metal oxide and distilled water were mixed at a ratio of 1: 1 and stirred at a speed of 1,000 rpm for 10 minutes to remove residual lithium on the surface, followed by drying in an oven at 150 ° C. for 12 hours to form a cathode active material having a single phase structure ( a Li 1.07 (Ni 0. 6 Mn 0. 2 Co 0. 2) 0.975 Mg 0 .02 W 0. 005 O 2) was prepared.
  • a batch 5 L reactor set at 60 ° C nickel sulfate, cobalt sulfate and manganese sulfate were mixed in water at a molar ratio of 60:20:20 to prepare a metal containing solution at a concentration of 2M.
  • the vessel containing the metal containing solution was connected to enter the reactor, and prepared with 4M NaOH solution and 7% aqueous NH 4 OH solution was connected to each reactor.
  • 3 liters of deionized water was added to the coprecipitation reactor (capacity 5L), and nitrogen gas was purged at the reactor at a rate of 2 liters / minute to remove dissolved oxygen in water and to form a non-oxidizing atmosphere in the reactor.
  • the precursor is mixed with lithium hydroxide as a lithium raw material such that the molar ratio of Li: M (total of Ni, Mn and Co) is 1: 1.07, and then heat-treated at 820 ° C. for 10 hours under an oxygen atmosphere (20% oxygen partial pressure).
  • the positive electrode active material Li 1.07 (Ni 0. 6 Mn 0. 2 Co 0. 2) O 2) was prepared.
  • Example 1-1 the precursor, the lithium hydrate as a lithium raw material, and the tungsten oxide (WO 3 ) as a tungsten raw material, M (total of Ni, Mn, and Co): Li: W have a molar ratio of 0.95: 2.0: 0.05, and the positive electrode active material is carried in the same manner as in example 1-1 except for the use of such (Li 1.07 (Ni 0. 6 Mn 0. 2 Co 0. 2) 0.95 W 0. 05 O 2) a Prepared.
  • Example 1-1 except that the precursor, lithium hydroxide and tungsten oxide mixed after the heat treatment in the presence of boron oxide for 10 hours at 1,050 °C to perform the same method as in Example 1 A cathode active material (Li 1.07 (Ni 0.6 Mn 0.2 Co 0.2 ) 0.995 W 0.005 O 2 ) was prepared.
  • a lithium secondary battery was manufactured using the cathode active materials prepared in Examples 1-1 and 1-2 and Comparative Examples 1-1 to 1-3, respectively.
  • the positive electrode active material prepared in Examples 1-1, 1-2 and Comparative Examples 1-1 to 1-3 carbon black as a conductive material and PVDF as a binder, 95 in N-methylpyrrolidone as a solvent.
  • natural graphite as a negative electrode active material, carbon black as a conductive material, and PVDF as a binder were mixed in a weight ratio of 85: 10: 5 in N-methylpyrrolidone as a solvent to prepare a composition for forming a negative electrode, which was added to a copper current collector. It was applied to prepare a negative electrode.
  • An electrode assembly was manufactured between the positive electrode and the negative electrode prepared as described above through a separator of porous polyethylene, the electrode assembly was placed in a case, and an electrolyte solution was injected into the case to prepare a lithium secondary battery.
  • Example 1-1 The cathode active material prepared in Example 1-1 was observed with a scanning electron microscope, and the results are shown in FIG. 1.
  • the cathode active material prepared according to Example 1-1 is a primary particle having a hexahedral shape having a monolithic structure, and its size is uniform.
  • the active material was etched using HCl for various times, and the amount of element elution according to the etching time or dissolution time was analyzed. ICP analysis was performed. The results are shown in Table 1 below.
  • Scan in Table 1 The location of Scan in Table 1 is as shown in FIG.
  • the concentration of Ni decreases from the center of the active material particles to the surface, and the concentration of Co and Mn is included as an increasing concentration gradient.
  • Mg was also present in the concentration gradient decreasing from the surface of the particle toward the center.
  • the average particle diameter, specific surface area, and rolling density of the cathode active material prepared in Example 1-1 were measured, and the results are shown in Table 2 below.
  • Average particle diameter (D 50 ) 50% of the particle size distribution in the measuring device after being introduced into a laser diffraction particle size measuring device (for example, Microtrac MT 3000) and irradiating an ultrasonic wave of about 28 kHz at an output of 60 W.
  • the average particle diameter (D 50 ) at the reference was calculated.
  • Particle size distribution value (Dcnt): The number average particle diameter (Dn90) measured under 90% in absorption mode using a Microtrac particle size analyzer after leaving the cathode active material prepared in Example 1-1 in distilled water for 3 hours. , The number average particle diameter (Dn10) measured under a 10% standard, and the number average particle diameter (Dn50) measured under a 50% standard were respectively measured and then calculated according to Equation 1 below.
  • BET specific surface area The specific surface area of the positive electrode active material was measured by the BET method. Specifically, it was calculated from the amount of nitrogen gas adsorption under liquid nitrogen temperature (77K) using BELSORP-mino II manufactured by BEL Japan. .
  • Example 1-1 Example 1-2 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Particle structure Primary Particles in Single Phase Structure Primary Particles in Single Phase Structure Secondary particles Secondary particles Primary Particles in Single Phase Structure Average particle diameter (D 50 ) ( ⁇ m) 4.6 4.4 5.8 1) 5.3 1) 6.4 Particle Size Distribution (Dcnt) 0.65 0.59 0.32 0.44 0.95 BET specific surface area (m 2 / g) 0.15 0.21 1.45 1.84 0.12 Rolling Density (g / cc) 3.28 3.16 2.24 2.07 2.87
  • the positive electrode active materials of Example 1-1 and Example 1-2 were primary particles having a single phase structure, but the positive electrode active materials of Comparative Example 1-1 and Comparative Example 1-2 were secondary particles.
  • the cathode active materials of Examples 1-1 and 1-2 are not only higher than those of Comparative Examples 1-1 and Comparative Examples 1-2, which are in the form of secondary particles, It confirmed that it was higher than the positive electrode active material of the comparative examples 1-3 which are particle
  • Coin cells prepared using the positive electrode active materials prepared in Examples 1-1 and Comparative Examples 1-1 to 1-3, respectively, had a constant current (CC) of 4.25V at 25 ° C. After that, the battery was charged to a constant voltage (CV) of 4.25V and charged first until the charging current became 0.05 mAh. After standing for 20 minutes, the battery was discharged to a constant current of 0.1C until 3.0V, and the discharge capacity of the first cycle was measured. Then, the charge and discharge capacity, charge and discharge efficiency and rate characteristics were evaluated by varying the discharge conditions at 2C. The results are shown in Table 3 below.
  • Example 2-1 and Comparative Examples 2-1 to 2-3 each containing the positive electrode active material in Example 1-1, and Comparative Examples 1-1 to 1-3 as follows Battery characteristics were evaluated by the method.
  • the lithium secondary battery was charged / discharged 300 times at a temperature of 45 ° C. under a condition of 1C / 2C within a 2.8V to 4.15V driving voltage range.

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Abstract

La présente invention concerne un matériau actif de cathode comprenant des particules primaires à structure monolithique contenant un oxyde métallique composite de lithium exprimé par la formule chimique 1 ci-dessous et possédant un diamètre de particule moyen (D50) de 2-20 ㎛ et une surface spécifique BET de 0,15 à 1,9 m2/g, et un accumulateur comprenant le matériau actif de cathode [formule chimique 1] LiaNi1-x-yCoxM1yM3zM2wO2 (dans la formule chimique 1, M1 à M3, a, x, y, z et w sont tels que définis dans la description). Le matériau actif de cathode pour un accumulateur selon la présente invention maintient une structure cristalline stable, même à l'état chargé et déchargé en raison de la structure monolithique et élimine donc le problème d'une soudaine chute de capacité provoquée par des changements dans la structure cristalline et, lorsque l'accumulateur est en service, peut présenter d'excellentes stabilité et capacité à haute température en minimisant la génération d'impuretés de surface.
PCT/KR2016/014004 2015-11-30 2016-11-30 Matériau actif de cathode pour accumulateur et accumulateur comprenant celui-ci Ceased WO2017095153A1 (fr)

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EP16871049.9A EP3386015B1 (fr) 2015-11-30 2016-11-30 Matériau actif de cathode pour accumulateur et accumulateur comprenant celui-ci
ES16871049T ES3027649T3 (en) 2015-11-30 2016-11-30 Cathode active material for secondary battery, and secondary battery comprising same
PL16871049.9T PL3386015T3 (pl) 2015-11-30 2016-11-30 Materiał aktywny katody do akumulatora i zawierający go akumulator
CN201680057268.6A CN108140829B (zh) 2015-11-30 2016-11-30 二次电池用正极活性物质以及包含该物质的二次电池
US15/760,111 US11081694B2 (en) 2015-11-30 2016-11-30 Positive electrode active material for secondary battery, and secondary battery comprising the same
JP2018519459A JP7114148B2 (ja) 2015-11-30 2016-11-30 二次電池用正極活物質及びこれを含む二次電池
US17/352,950 US11581538B2 (en) 2015-11-30 2021-06-21 Positive electrode active material for secondary battery, and secondary battery comprising the same

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Cited By (6)

* Cited by examiner, † Cited by third party
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CN110277553A (zh) * 2018-03-14 2019-09-24 株式会社东芝 电极、二次电池、电池组及车辆
US10790498B2 (en) 2017-10-20 2020-09-29 Unist (Ulsan National Institute Of Science And Technology) Positive active material for rechargeable lithium battery, method of preparing the same, electrode including the same, and rechargeable lithium battery including the electrode
JP2021508410A (ja) * 2017-12-22 2021-03-04 ユミコア 充電式リチウムイオンバッテリー用の正極材料
CN113169329A (zh) * 2018-11-20 2021-07-23 株式会社Lg化学 锂二次电池用正极活性材料及其制备方法
US11522186B2 (en) 2017-12-22 2022-12-06 Umicore Positive electrode material for rechargeable lithium ion batteries
EP4227267A1 (fr) * 2022-01-26 2023-08-16 REPT BATTERO Energy Co., Ltd. Matériau d'électrode positive ternaire et son procédé de préparation, feuille d'électrode positive et batterie au lithium-ion

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US10790498B2 (en) 2017-10-20 2020-09-29 Unist (Ulsan National Institute Of Science And Technology) Positive active material for rechargeable lithium battery, method of preparing the same, electrode including the same, and rechargeable lithium battery including the electrode
JP2021508410A (ja) * 2017-12-22 2021-03-04 ユミコア 充電式リチウムイオンバッテリー用の正極材料
JP7052072B2 (ja) 2017-12-22 2022-04-11 ユミコア 充電式リチウムイオンバッテリー用の正極材料
US11522187B2 (en) 2017-12-22 2022-12-06 Umicore Positive electrode material for rechargeable lithium ion batteries
US11522186B2 (en) 2017-12-22 2022-12-06 Umicore Positive electrode material for rechargeable lithium ion batteries
CN115763701A (zh) * 2017-12-22 2023-03-07 尤米科尔公司 用于能够再充电锂离子蓄电池的正电极材料
CN110277553A (zh) * 2018-03-14 2019-09-24 株式会社东芝 电极、二次电池、电池组及车辆
CN110277553B (zh) * 2018-03-14 2022-05-17 株式会社东芝 电极、二次电池、电池组及车辆
CN113169329A (zh) * 2018-11-20 2021-07-23 株式会社Lg化学 锂二次电池用正极活性材料及其制备方法
US12206104B2 (en) 2018-11-20 2025-01-21 Lg Chem, Ltd. Positive electrode active material for lithium secondary battery and method of preparing the same
EP4227267A1 (fr) * 2022-01-26 2023-08-16 REPT BATTERO Energy Co., Ltd. Matériau d'électrode positive ternaire et son procédé de préparation, feuille d'électrode positive et batterie au lithium-ion

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