WO2017150893A1 - Matériau actif de cathode pour une batterie secondaire au lithium et son procédé de préparation - Google Patents

Matériau actif de cathode pour une batterie secondaire au lithium et son procédé de préparation Download PDF

Info

Publication number
WO2017150893A1
WO2017150893A1 PCT/KR2017/002212 KR2017002212W WO2017150893A1 WO 2017150893 A1 WO2017150893 A1 WO 2017150893A1 KR 2017002212 W KR2017002212 W KR 2017002212W WO 2017150893 A1 WO2017150893 A1 WO 2017150893A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
active material
secondary battery
oxalate
boron
Prior art date
Application number
PCT/KR2017/002212
Other languages
English (en)
Korean (ko)
Inventor
노준석
조승범
박현아
안준성
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170025656A external-priority patent/KR101980103B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780003476.2A priority Critical patent/CN108140820B/zh
Priority to EP17760297.6A priority patent/EP3333944B1/fr
Priority to US15/760,089 priority patent/US10665857B2/en
Publication of WO2017150893A1 publication Critical patent/WO2017150893A1/fr
Priority to US16/849,290 priority patent/US11189829B2/en

Links

Images

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 and a method for manufacturing the same, and more particularly, to a cathode active material for a lithium secondary battery including a coating layer capable of reducing a lithium compound content remaining on a surface and suppressing surface activity and a method of manufacturing the same.
  • lithium secondary batteries use carbon such as graphite as a negative electrode active material, use an oxide containing lithium as a positive electrode active material, and use a non-aqueous solvent as an electrolyte, and lithium which is used as a positive electrode active material has a high tendency to ionize. Since it is a metal, high voltage expression is possible and it can provide a battery with high energy density.
  • Lithium-containing cobalt oxide (LiCo 2 ) having a layered structure is mainly used as the oxide containing lithium, and lithium-containing manganese oxides such as LiMnO 2 having a layered crystal structure and LiMn 2 O 4 having a spinel crystal structure, and lithium
  • lithium-containing manganese oxides such as LiMnO 2 having a layered crystal structure and LiMn 2 O 4 having a spinel crystal structure
  • lithium The use of containing nickel oxide (LiNiO 2 ) is contemplated.
  • lithium-nickel-based high voltage cathode active materials capable of expressing high capacity at a high Ni content of 200mAh / g or more.
  • lithium-nickel cathode active material is calcined in an oxygen atmosphere, a large amount of lithium derivatives such as lithium carbonate (Li 2 CO 3 ) and lithium hydroxide (LiOH) remain on the surface of the prepared cathode active material. do.
  • the lithium-nickel cathode active material has a disadvantage in that long-term storage is difficult because water is easily adsorbed on the surface.
  • Lithium precursor and moisture remaining on the surface of the positive electrode active material not only causes a gelation phenomenon during the positive electrode manufacturing process, making the electrode difficult, but also accelerates the deterioration of the surface of the positive electrode active material during charge and discharge after the secondary battery is manufactured. It is a cause of deterioration of performance.
  • cathode active material manufacturing method capable of preventing battery deterioration and performance deterioration due to lithium and moisture remaining on the surface of the cathode active material is required.
  • the first technical problem of the present invention is to provide a cathode active material for a lithium secondary battery comprising a coating layer capable of reducing the content of lithium derivative remaining on the surface and suppressing surface activity.
  • a second technical problem of the present invention is to provide a method for producing a cathode active material including the coating layer.
  • the third technical problem of the present invention is to provide a positive electrode capable of preventing performance degradation by including the positive electrode active material.
  • a fourth technical problem of the present invention is to provide a lithium secondary battery including the positive electrode.
  • the coating layer provides a cathode active material for a lithium secondary battery including a metal oxalate compound.
  • the coating layer may further include boron.
  • a method of manufacturing the cathode active material for a lithium secondary battery is provided.
  • the oxalic acid or metal oxalate compound precursor may be in liquid or powder state.
  • the heat treatment step may be carried out in a temperature range of 150 °C to 300 °C.
  • the method may further include a boron precursor in the step of mixing the lithium-nickel-based transition metal oxide particles and the oxalic acid or metal oxalate compound precursor.
  • the first heat treatment step may be performed at a temperature range of 150 ° C to 450 ° C.
  • the secondary heat treatment step may be carried out in a temperature range of 150 °C to 300 °C.
  • the boron precursor, oxalic acid or metal oxalate compound precursor may be in liquid or powder state.
  • an embodiment of the present invention provides a positive electrode including the positive electrode active material for the lithium secondary battery.
  • an embodiment of the present invention provides a lithium secondary battery including a separator and an electrolyte interposed between the positive electrode and the negative electrode for the lithium secondary battery, the positive electrode and the negative electrode.
  • the present invention by forming a coating layer containing a metal oxalate compound on the surface of the lithium-nickel-based transition metal oxide, the content of lithium derivatives such as lithium carbonate and lithium hydroxide remaining on the surface can be reduced.
  • a positive electrode active material that can reduce the moisture adsorption amount during long-term storage. Therefore, it is possible to prevent the gelation phenomenon of the positive electrode active material generated due to the residual lithium derivative and water, and to suppress the generation of gas due to side reaction between these and the electrolyte solution.
  • the positive electrode including the positive electrode active material of the present invention and the secondary battery having the same may have excellent capacity characteristics and excellent life characteristics.
  • the present invention can be easily applied to an industry requiring the high capacity and long lifespan of an electric vehicle.
  • 3 and 4 are graphs showing the capacity test results of the lithium secondary battery according to Experimental Example 2 of the present invention.
  • 5 and 6 are graphs showing the cycle life characteristics of the lithium secondary battery according to Experimental Example 3 of the present invention.
  • the coating layer provides a cathode active material for a lithium secondary battery including a metal oxalate compound.
  • the lithium-nickel transition metal oxide may be represented by the following Chemical Formula 1.
  • M is at least one metal element selected from the group consisting of Al, Mg, Fe, Cu, Zn, Cr, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si, Ti and Zr , -0.1 ⁇ a ⁇ 0.2, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 0.2.
  • nickel of the lithium-nickel transition metal oxide may be included in 40 mol% or more, preferably 40 to 95 mol% based on the total moles of the transition metal except lithium in the lithium-nickel transition metal oxide.
  • the lithium-nickel-based transition metal oxide may be formed of secondary particles having an agglomerated structure composed of aggregates of fine particles.
  • the average particle diameter (D 50 ) of the lithium-nickel-based transition metal oxide may be 3 ⁇ m to 30 ⁇ m. If the average particle diameter of the lithium-nickel-based transition metal oxide is less than 3 ⁇ m, the energy density and adhesive strength may be reduced due to the excessive use of the binder for the small particles in electrode production. Is low, and particle cracking may occur due to rolling during electrode production.
  • the metal oxalate compound included in the coating layer may be Li, B, Mg, Ca, V, Sr, Ba, Y, Ti, Zr, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Zn, Al, Ga, In, Si, Ge, Sn, La, Ce, Na, K, Rb, Cs, Fr, Sc, Fe, Ni, Cu, Ru, It contains ions of one or more elements selected from the group consisting of Rh, Pd, Ag, Cd, Sb, Hf, Ta, Re, Os, Pt, Au, Tl, Pb, Bi and Po, and anion C 2 O 4 It may include two .
  • the coating layer may further include boron.
  • the coating layer of the present invention is a single layer structure containing a metal oxalate compound, or a single layer structure containing an oxalate compound including a metal and boron, or a first coating layer containing a boron compound and a metal and boron. It may be a multilayered structure composed of a second coating layer containing an oxalate compound.
  • the coating layer is a lithium oxalate compound, lithium-boron oxalate compound, magnesium oxalate compound, lithium-magnesium oxalate compound, magnesium-boron oxalate, lithium magnesium-boron oxalate, sodium oxalate compound, lithium- Sodium oxalate compound, sodium-boron oxalate, lithium sodium-boron oxalate, aluminum oxalate compound, lithium-aluminum oxalate compound, aluminum-boron oxalate, lithium aluminum-boron oxalate, calcium oxalate compound, lithium- Calcium oxalate compound, calcium-boron oxalate, lithium calcium-boron oxalate, manganese oxalate compound, lithium-manganese oxalate compound, manganese-boron oxalate, lithium manganese-boron oxalate, zirconium oxalate compound, lithium- Zirconium
  • the metal oxalate compound may be included in 0.01 to 5% by weight based on the total weight of the cathode active material.
  • a structurally stable coating layer may be formed on the surface of the lithium-nickel transition metal oxide.
  • a composite cathode active material having excellent thermal stability and capacity characteristics can be obtained. If the content of the metal oxalate compound contained in the coating layer exceeds 5% by weight, the thickness of the coating layer is increased by the excess metal oxalate compound, thereby acting as a resistance layer, thereby significantly reducing the cell capacity.
  • the thickness of the coating layer is too thin, so that the effect of reducing the content of lithium derivatives remaining on the surface of the cathode active material desired in the present invention and the effect of reducing water adsorption are insignificant.
  • the effect of preventing decomposition may be low.
  • the coating layer may be formed on the entire surface or part of the lithium-nickel-based transition metal oxide, the thickness may be 5nm to 1 ⁇ m. If the thickness is less than 5 nm, the thickness is so thin that the effect of reducing the lithium derivative content and the moisture adsorption reducing effect remaining on the surface of the positive electrode active material desired in the present invention may be insignificant, and the effect of preventing the decomposition of the electrolyte may be deteriorated. If it is 1 ⁇ m or more, the cell capacity can be greatly reduced by increasing the resistance.
  • the average particle diameter (D 50 ) of the cathode active material of the present invention including the coating layer is preferably 3 ⁇ m 30 ⁇ m. If the average particle size is less than 3 ⁇ m, it may be difficult to disperse in the slurry of the positive electrode active material, or there may be a problem that the positive electrode active material in the electrode agglomerates, if the average particle diameter exceeds 30 ⁇ m, particle cracking by rolling during electrode production May occur. Accordingly, the new surface that is not stabilized is in contact with the electrolyte solution, and the effect of preventing the electrolyte decomposition reaction is inadequate, so that the life of the battery can be reduced.
  • the average particle diameter (D 50 ) of the cathode active material may be measured by using a laser diffraction method.
  • the laser diffraction method can measure the particle diameter of several mm from the submicron region, and high reproducibility and high resolution can be obtained.
  • lithium diffused from the core portion is present in the form of a lithium derivative such as lithium carbonate (Li 2 CO 3 ) or lithium hydroxide (LiOH) on the surface of the lithium-nickel-based transition metal oxide.
  • a lithium derivative such as lithium carbonate (Li 2 CO 3 ) or lithium hydroxide (LiOH) on the surface of the lithium-nickel-based transition metal oxide.
  • These lithium derivatives react with the oxalic acid ion or oxalate group present in the oxalic acid or metal oxalate compound in the dissolved or molten state during the heat treatment to form a strong metal-oxygen covalent bond, and the surface of the lithium-nickel transition metal oxide A stable coating layer can be formed.
  • the positive electrode active material of the present invention can reduce the content of lithium derivatives while the lithium and lithium derivatives present on the surface of the lithium-nickel-based transition metal oxide to form a coating layer, thereby reducing the pH of the surface of the positive electrode active material By reducing the water adsorption during long-term storage, it is possible to prevent the phenomenon of the gelation of the slurry generated during the electrode production of the positive electrode active material.
  • the coating layer is formed on the surface of the lithium-nickel-based transition metal oxide, thereby inhibiting the surface activity by blocking direct contact with the electrolyte, thereby bringing the effect of inhibiting oxidation and side reactions by the electrolyte.
  • the positive electrode active material of the present invention may further include a boron compound to form a more stable coating layer of a single layer or a multi-layer structure, it is possible to implement an improved long-term life effect.
  • the secondary reaction with the lithium derivative and the moisture remaining on the surface of the cathode of the secondary battery and the resulting electrolyte and the resulting gas can be suppressed, the secondary battery with improved safety and cycle characteristics It can manufacture.
  • an embodiment of the present invention may provide a method for manufacturing a cathode active material for a lithium secondary battery.
  • the method for preparing the positive electrode active material may include one or more of the following methods.
  • the method for producing a cathode active material for a lithium secondary battery (1) comprises the steps of preparing lithium-nickel-based transition metal oxide particles;
  • lithium-nickel-based transition metal oxide particles can be produced by a conventional method.
  • the lithium-nickel-based transition metal oxide particles may be prepared by mixing and firing a transition metal precursor and a lithium raw material.
  • the oxalic acid or metal oxalate compound precursor may be in a liquid or powder state.
  • the oxalic acid or metal oxalate compound precursor When the oxalic acid or metal oxalate compound precursor is liquid, it may be prepared by dissolving the oxalic acid or metal-oxalate compound in a solvent.
  • the solvent is not particularly limited as long as it is an oil or an inorganic solvent capable of dissolving an oxalic acid or a metal-oxalate compound, and representative examples thereof include alcohols such as water, ethanol, methanol, isopropyl alcohol, ethylene glycol, butylene glycol, benzene, Toluene, dichloromethane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene chlorobenzene, ortho-dichlorobenzene, ethyl ether, dioxane, tetrahydrobutane, acetone, methyl Organic-inorganic solvents such as ethyl ketone (MEK), methyl butyl ketone (MBK), methyl isobutyl ketone (MIBK), ethylene glycol monomethyl ether, ethylene glycol mono
  • the liquid coating solution concentration is preferably 0.01% by weight to 50% by weight. If the concentration of the coating solution is less than 0.01% by weight, there is a disadvantage that the drying time and energy consumption is large, and when the concentration of the coating solution exceeds 50% by weight, the uniformity of the coating is deteriorated.
  • the oxalic acid or metal oxalate compound precursor is in the form of a powder
  • one prepared by pulverizing the oxalic acid or metal oxalate compound in a mortar and pestle may be used.
  • the oxalic acid or metal-oxalate compound precursor may be included in an amount of about 0.01 wt% to 5 wt% based on the total weight of the lithium-nickel transition metal oxide to be mixed.
  • the oxalic acid or metal oxalate compound precursor content is less than 0.01% by weight based on the total weight of the lithium-nickel transition metal oxides to be mixed, the effect of reducing the lithium derivative content on the surface of the lithium-nickel transition metal oxide particles is not sufficient. If the weight is greater than 5% by weight based on the weight of the lithium-nickel-based transition metal oxide to be mixed, there is a problem in that battery capacity and output characteristics are reduced.
  • the method may further include removing a solvent constituting the liquid solution before the heat treatment step for drying.
  • the solvent removal step is preferably carried out by heating to a temperature above the boiling point of the solvent so that the solvent can be easily removed, it is preferably carried out at a temperature range of about 130 °C or more, specifically 130 °C to 200 °C. .
  • the cathode active material manufacturing method (1) of the present invention may include a heat treatment step after the solvent removal step to impart a water removal effect at the same time as forming a metal oxalate compound-containing coating layer.
  • the heat treatment step may be carried out in a temperature range of 150 °C to 300 °C, if the heat treatment at a temperature of less than 150 °C, the reaction between the lithium and metal oxalate compound-containing coating layer formation, or water removal effect is not made sufficiently, There is a disadvantage in that the lithium and metal oxalate compounds decompose when heat treated at a temperature above 350 ° C.
  • the cathode active material manufacturing method (1) of the present invention may further include the step of crushing or sieving into the case after the heat treatment step in some cases.
  • the method for preparing a cathode active material (1) of the present invention further includes a boron precursor that can obtain a long-term life improvement effect in the step of mixing the lithium-nickel-based transition metal oxide particles with an oxalic acid or metal oxalate compound precursor. can do.
  • the boron precursor may include at least one selected from the group consisting of boric acid, boron oxide, lithium borate, magnesium borate, sodium borate, potassium borate, and calcium borate.
  • the coating effect of the metal boron oxalate compound may be improved to further implement a long-life effect.
  • the boron precursor is preferably contained in 0.01 to 10% by weight based on the total weight of the lithium transition metal oxide. If it is less than the above range can not implement the effect due to the boron precursor, if it exceeds the above range, there is a problem that the capacity of the positive electrode material is reduced and the resistance is increased by the formation of an excessive coating layer.
  • Preparing a coating solution by dissolving an oxalic acid or a metal-oxalate compound in a solvent;
  • the mixture may be heat-treated to form a coating layer including a metal oxalate compound on the surface of the lithium-nickel-based transition metal oxide particles.
  • the boron precursor, the oxalic acid or the metal oxalate compound precursor may be in a liquid or powder state, and the boron precursor is preferably in a powder state.
  • the oxalic acid or metal oxalate compound precursor may be included in an amount of 0.01 wt% to 5 wt% based on the total weight of the lithium-nickel-based transition metal oxide.
  • the oxalic acid or metal oxalate compound precursor content is less than 0.01% by weight based on the total weight of the lithium-nickel transition metal oxides to be mixed, the effect of reducing the lithium derivative content on the surface of the lithium-nickel transition metal oxide particles is not sufficient. If the weight is greater than 5% by weight based on the weight of the lithium-nickel-based transition metal oxide to be mixed, there is a problem in that battery capacity and output characteristics are reduced.
  • the method may further include removing the solvent before the second heat treatment.
  • the solvent removal step is preferably carried out by heating to a temperature above the boiling point of the solvent so that the solvent can be easily removed, it is preferably carried out at a temperature range of about 130 °C or more, specifically 130 °C to 200 °C. .
  • the boron precursor may include one or more selected from the group consisting of boric acid, boron oxide, lithium borate, magnesium borate, sodium borate, potassium borate, and calcium borate.
  • the boron precursor is preferably contained in 0.01 to 10% by weight based on the total weight of the lithium transition metal oxide.
  • the coating effect of the metal boron oxalate compound can be further improved. If it is less than the above range can not implement the effect due to the boron precursor, if it exceeds the above range, there is a problem that the capacity of the positive electrode material is reduced and the resistance is increased by the formation of an excessive coating layer.
  • the second coating layer may include an oxalate compound including metal and boron.
  • the boron included in the second coating layer may include boron included in the first coating layer in the process of forming the second coating layer. It may be diffused to the second coating layer.
  • the boron precursor may further include a long-term life improvement effect.
  • an oxalate compound including metal and boron on the surface thereof is formed.
  • a second coating layer including the same the capacity of the positive electrode material can be increased, and a cathode active material for a secondary battery can be manufactured with improved long-term life characteristics and cycle characteristics.
  • the first particles having the first coating layer including the boron compound are formed at 150 ° C. to The first heat treatment may be carried out at 450 °C temperature.
  • the cathode active material manufacturing method (2) of the present invention may include a secondary heat treatment step after the solvent removal step to impart a water removal effect at the same time as forming a metal oxalate compound-containing coating layer.
  • the second heat treatment step may be carried out in a temperature range of 150 °C to 300 °C, if the heat treatment at a temperature of less than 150 °C, the reaction of forming a coating layer containing lithium and metal oxalate compound, or diffusion in the second coating layer of boron It may not be made and the water removal effect is not made sufficiently, there is a disadvantage that the lithium and metal oxalate compound is decomposed when heat treatment at a temperature of more than 350 °C.
  • an embodiment of the present invention provides a lithium secondary battery positive electrode including the positive electrode active material.
  • the positive electrode according to an embodiment of the present invention may be prepared by applying a positive electrode active material slurry containing the positive electrode active material to a positive electrode current collector, drying and rolling.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery, for example, stainless steel, aluminum, nickel, titanium, calcined carbon or carbon, nickel on the surface of aluminum or stainless steel Surface treated with titanium, silver, or the like can be used.
  • the current collector may have a thickness of typically 3 ⁇ m to 500 ⁇ m, may form fine irregularities on the surface of the current collector to increase the 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 of the present invention may optionally further include at least one selected from a conductive material, a binder, and a filler.
  • 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, furnace black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can 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 mixture including the positive electrode active material.
  • the binder is not particularly limited as long as the component assists in bonding the active material and the conductive material and bonding to the current collector, and is not particularly limited.
  • the binder may typically be included in an amount of 1 wt% to 30 wt% based on the total weight of the mixture including the positive electrode active material.
  • the filler may be optionally used as a component for inhibiting the expansion of the electrode, and is not particularly limited as long as it is a fibrous material that does not cause chemical change in the battery, for example, an olefin polymer such as polyethylene, polypropylene; Fibrous materials, such as glass fiber and carbon fiber, can be used.
  • an olefin polymer such as polyethylene, polypropylene
  • Fibrous materials such as glass fiber and carbon fiber, can be used.
  • the coating may be performed by a method commonly known in the art, but for example, the positive electrode active material slurry may be distributed on an upper surface of one side of the positive electrode current collector, and then uniformly dispersed using a doctor blade or the like. Can be.
  • the method may be performed by a die casting method, a comma coating method, a screen printing method, or the like.
  • the drying is not particularly limited, but may be performed within one day in a vacuum oven at 50 °C to 200 °C.
  • a lithium secondary battery may include a cathode, an anode, a separator interposed between the cathode and an anode, and an electrolyte.
  • the negative electrode is not particularly limited, but may be prepared by coating a negative electrode active material slurry including a negative electrode active material on one side of a negative electrode current collector and then drying the negative electrode active material. Ingredients such as ash, binder, filler, and the like may be included.
  • 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 current collector may generally have a thickness of 3 ⁇ m 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 examples include carbon and graphite materials such as natural graphite, artificial graphite, expanded graphite, carbon fiber, non-graphitizable carbon, carbon black, carbon nanotube, fullerene, and activated carbon; Metals such as Al, Si, Sn, Ag, Bi, Mg, Zn, In, Ge, Pb, Pd, Pt, Ti which can be alloyed with lithium, and compounds containing these elements; Complexes of metals and compounds thereof with carbon and graphite materials; Lithium-containing nitrides; and the like.
  • carbon-based active materials, silicon-based active materials, tin-based active materials, or silicon-carbon-based active materials are more preferable, and these may be used alone or in combination of two or more.
  • Conductive materials, binders, fillers, and the like used in the negative electrode may be the same as or used in the aforementioned positive electrode manufacturing.
  • the separator is interposed between the anode and the cathode, an insulating thin film having high ion permeability and mechanical strength may be used.
  • the pore diameter of the separator is generally 0.01 ⁇ m to 10 ⁇ m, the thickness may be generally 5 ⁇ m to 300 ⁇ m.
  • the separator may be, for example, an olefin polymer such as polypropylene having chemical resistance and hydrophobicity; Sheets or non-woven fabrics made of glass fibers or polyethylene, etc. may be used.
  • the solid electrolyte may also serve as a separator.
  • the lithium salt-containing non-aqueous electrolyte solution consists of an electrolyte solution and a lithium salt, and a non-aqueous organic solvent or an organic solid electrolyte is used as the electrolyte solution.
  • non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma -Butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxolon, acetonitrile Nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxy methane, dioxoron derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, Aprotic organic solvents such as tetrahydrofuran derivatives, ethers, methyl propionate and ethyl propionate can be used.
  • organic solid electrolytes examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymerizers containing ionic dissociating groups and the like can be used.
  • the lithium salt is a material that is readily soluble in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10 C 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4-phenyl lithium borate, and imide Can be.
  • pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride, and the like may be added. .
  • halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics.
  • Lithium secondary battery of the present invention is not limited to the appearance according to the use of the battery, for example, it can be a cylindrical, square, pouch (coin) or coin type (coin) using a can.
  • the lithium secondary battery according to the present invention may not only be used in a battery cell used as a power source for a small device, but also preferably used as a unit battery in a medium-large battery module including a plurality of battery cells.
  • Preferred examples of the medium and large devices include, but are not limited to, electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, power storage systems, and the like.
  • a magnesium oxalate solution was prepared in the same manner as in Preparation Example 1, except that magnesium oxalate (MgC 2 O 4 ) was used in the amount of 5 g instead of oxalic acid in Preparation Example 1.
  • Oxalic acid (C 2 H 2 O 4 ) was added to the mortar and ground to prepare an oxalic acid powder.
  • Magnesium oxalate (MgC 2 O 4 ) was added to the mortar and ground to prepare magnesium oxalate powder.
  • Boric acid (Boric acid, H 3 BO 3 ) was added to the mortar and ground to prepare a boric acid powder.
  • the prepared precursor was placed in an alumina crucible and fired at about 860 ° C. for 6 hours in an air atmosphere.
  • the cake obtained after firing was pulverized, and then classified using a 400 mesh sieve (Tlyer standard screen scale in the United States) to carry out LiNi 0 , a lithium-nickel transition metal oxide . 6 Mn 0 . 2 Co 0 . 2 O 2 was obtained (average particle size (D 50) 10 ⁇ m).
  • the prepared precursor was placed in an alumina crucible, and calcining was performed at about 800 ° C. for 6 hours in an oxygen (O 2 ) atmosphere.
  • the cake obtained after firing was pulverized, and then classified using a 400 mesh sieve (Tlyer standard screen scale in the United States) to carry out LiNi 0 , a lithium-nickel transition metal oxide . 8 Mn 0 . 1 Co 0 . 1 O 2: was obtained (average particle size (D 50) 10 ⁇ m).
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • Table 1 dried at 150 °C for 6 hours, heat treated at 250 °C for 6 h, and induced and sieved to lithium-nickel transition metal oxide (... LiNi 0 6 Mn 0 2 Co 0 2 O 2) lithium oxalate compound to the surface
  • a cathode active material average particle diameter (D 50 ): 10 ⁇ m) having a coating layer formed thereon was prepared.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • Preparation Example 6 lithium-nickel transition metal oxide (LiNi 0.6 Mn 0.2 Co 0.2 O 2) lithium in place of Preparation 7-nickel transition metal oxide (LiNi 0 8 Mn 0 1 Co 0.. . 1 O 2) a but using the second embodiment in the same manner as the lithium - nickel transition metal oxide (LiNi 0 8 Mn 0 1 Co 0 1 O 2) include lithium oxalate compound to the surface
  • a cathode active material average particle diameter (D 50 ): 10 ⁇ m) having a coating layer formed thereon was prepared.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • the lithium-magnesium oxalate compound was prepared in the same manner as in Example 2, except that the 5% magnesium oxalate solution of Preparation Example 2 was used instead of the oxalic acid solution of Preparation Example 1.
  • a cathode active material (average particle diameter (D 50 ): 10 ⁇ m) having a coating layer formed thereon was prepared.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • Preparation Example 6 lithium-nickel transition metal oxide (LiNi 0.6 Mn 0.2 Co 0.2 O 2) lithium in place of Preparation 7-nickel transition metal oxide (LiNi 0 8 Mn 0 1 Co 0..
  • a positive electrode active material average particle diameter (D 50 ): 10 ⁇ m) having a coating layer including a lithium-magnesium oxalate compound was prepared in the same manner as in Example 5, except that 1 0 2 was used.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • the coating layer comprising a lithium-magnesium oxalate compound in the same manner as in Example 7 the positive electrode active material formed of: an (average particle size (D 50) 10 ⁇ m) was prepared.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • Preparation Example 6 lithium-nickel transition metal oxide (LiNi 0.6 Mn 0.2 Co 0.2 O 2) lithium in place of Preparation 7-nickel transition metal oxide (LiNi 0 8 Mn 0 1 Co 0.. It was prepared in the 10 ⁇ m): positive electrode active material (mean particle diameter (D 50) a coating layer is formed including the boron compound oxalate - 1 O 2) to conduct in the same manner as in example 10 except for the use of lithium.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • the positive electrode active material having a coating layer containing a lithium-magnesium boron oxalate compound (the average particle diameter (D 50): the 10 ⁇ m) was prepared.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • the lithium borate powder of Production Example 5 and Production Example 6 1.15g-nickel transition metal oxide (... Mn LiNi 0 6 2 0 0 Co 2 O 2) and then a mixture of 50g, 350 Primary particles were heat-treated at 6 ° C. for 6 hours, induced, and sieved to prepare first particles including a lithium-boron compound-containing first coating layer.
  • the first particle and 0.2 g of oxalic acid powder are mixed, subjected to secondary heat treatment, induction and sieving at 250 ° C. for 6 hours to form a two-layered coating layer including a second coating layer comprising a lithium-boron oxalate compound.
  • An active material (average particle diameter (D 50 ): 10 ⁇ m) was prepared.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • lithium borate powder of Production Example 5 Production Example 7 and 2.3g of nickel-transition metal oxide (... Mn LiNi 0 8 0 0 1 Co 1 O 2) and then a mixture of 50g, 350 First heat treatment at 6 ° C. for 6 hours, and then induced and sieved to prepare first particles including a coating layer containing a lithium-boron oxalate compound.
  • nickel-transition metal oxide ... Mn LiNi 0 8 0 0 1 Co 1 O 2
  • the first particle and 0.2 g of oxalic acid powder are mixed, heat treated at 250 ° C. for 6 hours, induced and sieved to form a cathode active material having a two-layer coating layer containing a lithium-boron oxalate compound (average particle diameter (D 50). ): 10 ⁇ m).
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • the lithium transition metal oxide of Preparation Example 6 was used as the cathode active material.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • the lithium transition metal oxide of Preparation Example 7 was used as the cathode active material.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • a lithium-nickel transition mixed metal oxide (... LiNi 0 6 Mn 0 2 Co 0 2 O 2) 50g , and then after the mixture was dried at 150 °C for 6 hours, heat treated at 250 °C for 6 h, and induced and sieved to lithium-nickel transition metal oxide (... LiNi 0 6 Mn 0 2 Co 0 2 O 2) of lithium to the surface
  • a cathode active material (average particle diameter (D 50 ): 10 ⁇ m) having a coating layer including an oxalate compound was prepared.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • Example 1 50 g - 2 g - - - 1-1
  • Example 2 50 g - 4 g - - 1-1
  • Example 3 50 g - 8 g - - - 1-1
  • Example 5 50 g - - - 4 g - 1-1
  • Example 6 50 g - - 4 g - - 1-1
  • Example 7 50 g - - 0.2 g - - - 1-2
  • Example 8 50 g - - - - 0.2 g - 1-2
  • Example 9 50 g - - 0.2 g - - 1.15 g 1-3
  • Example 10 50 g - - 0.2 g - - 2.3g 1-3
  • Example 11 50 g - 0.2 g - - - - 0.2 g 1.15 g 1-3
  • Example 13 50 g - - -
  • citric acid C 6 H 8 O 7
  • a citric acid solution having a concentration of 5%
  • a positive electrode active material (average particle diameter (D 50 ): 10 ⁇ m) having a coating layer containing a lithium citrate compound on the surface of a lithium-nickel transition metal oxide (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) was prepared by inducing and sieving.
  • a positive electrode slurry After preparing a positive electrode slurry by mixing carbon black and a binder with a carbon black and a binder in a 96: 2: 2 weight ratio, the slurry was coated on Al foil, followed by rolling and drying to prepare a secondary battery positive electrode.
  • the secondary battery was manufactured by using Li metal as the positive electrode and the negative electrode active material, and interposing a separator of porous polyethylene between the positive electrode and the negative electrode and injecting an electrolyte solution.
  • the lithium derivative remaining on the surface from which the cathode active material was removed was titrated with 1N HCl solution to measure the amount of lithium in the solution.
  • the amount of lithium in the solution is measured using an automatic titrator and the primary inflection point (EP1) of pH rapidly changing from pH 7 to 9 and the end point (FP) of pH reaching 5 are measured using Li 2 CO. Calculate the content of 3 and the content of LiOH.
  • the content of the lithium derivative remaining on the final surface was measured by adding the calculated Li 2 CO 3 content and LiOH content, and the content of the residual lithium derivative on the surface was converted into weight% based on the total weight of the positive electrode active material. 1 and 2 are shown.
  • 1 is a Preparation Example 6 of the lithium-nickel transition metal oxide (... LiNi 0 6 Mn 0 2 Co 0 2 O 2) of a graph showing the content of the lithium derivative remaining in the produced positive electrode active material surface with
  • Figure 2 is lithium of Preparation 7 - a graph showing the content of the lithium derivative remaining in the positive electrode active material surface prepared using the (8 Mn 0 1 Co 0 1 O 2 LiNi 0...) nickel transition metal oxide.
  • Example 4 of the present invention including a coating layer It can be seen that the contents of the lithium derivatives remaining on the surfaces of the cathode active materials of Example 11 and Example 14 were all reduced to 0.7 wt% or less.
  • the positive electrode active material of Comparative Example 5 in which the coating layer including the metal citrate was formed was found that the content of the lithium derivative remaining on the surface increased to 1.4 wt%.
  • the cathode active material of the present invention including the metal oxalate compound-containing coating layer as in the present invention can reduce the content of lithium derivative remaining on the surface.
  • Figure 3 is lithium of Preparation 6 - a graph showing the discharge capacity of the secondary battery using the positive electrode active material prepared using the (6 Mn 0 2 Co 0 2 O 2 LiNi 0...)
  • Nickel transition metal oxide 4 is lithium of Preparation 7 - a graph showing the discharge capacity of the secondary battery using the nickel transition produced by using a metal oxide (LiNi Mn 0 8 0 0 1 Co 1 O 2...) the positive electrode active material.
  • the discharge capacity is 180 mAh / g. .
  • the discharge capacity of the secondary battery of Reference Example 2 using the positive electrode active material including the coating layer on which the excessive metal oxalate compound was formed was the lowest as 165 mAh / g or less.
  • the secondary batteries of Examples 1 to 3, 5, 7 to 10, 12, and 13 using the cathode active material of the present invention including a coating layer containing a metal oxalate have a discharge capacity. It can be seen that these were all improved to 180 mAh / g or more.
  • the discharge capacity of the secondary batteries of Examples 4, 6, 11, and 14 of the present invention are all improved compared to those of Comparative Example 2 using the cathode active material without a coating layer. It can be seen that. On the contrary, it can be seen that the discharge capacity of the lithium secondary battery of Comparative Example 3, in which the coating layer containing lithium citrate was formed, was reduced compared to before the coating layer was formed.
  • Cycle life tests were performed on the secondary batteries of Examples 1 to 14, Comparative Examples 1 to 3, Reference Example 1, and Reference Example 2. Specifically, charging was carried out at 25 ° C. until a constant current (CC) of 4.35V was reached, followed by charging at a constant voltage (CV) of 4.35V, followed by a first charge until the charging current became 0.05C. Thereafter, the sample was left for 20 minutes, and then discharged until a constant current of 2C reached 3.0V and discharged until the discharge current reached 0.05C. This was repeated 1 to 50 cycles and the results obtained are shown in FIGS. 5 and 6.
  • CC constant current
  • CV constant voltage
  • Figure 5 is lithium in Production Example 6-nickel transition metal oxide (... LiNi 0 6 Mn 0 2 Co 0 2 O 2) the characteristic cycle life of the secondary battery using the produced positive electrode active material by (discharge capacity retention rate 6 is a graph showing the cycle life characteristics (discharge retention) of a secondary battery using a cathode active material manufactured using lithium-nickel transition metal oxide (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) of Preparation Example 7. The graph shown.
  • the secondary battery of Comparative Example 1 using the positive electrode active material having no coating layer formed thereon the secondary battery of Reference Example 1 using the positive electrode active material including a coating layer having a low metal oxalate content, and excess metal oxal
  • the cycle life of the secondary battery rapidly decreased from the 10th cycle, whereas Examples 1 to 3, 5, and 7 of the present invention were used. It can be seen that the cycle life characteristics of the secondary batteries of Examples 10, 12, and 13 were improved.
  • the cycle life characteristics of the secondary batteries of Examples 4, 6, 11, and 14 of the present invention are improved compared to those of Comparative Example 2 using the cathode active material without a coating layer. It can be seen that. On the contrary, the cycle life characteristics of the secondary battery of Comparative Example 3, in which the coating layer containing lithium citrate was formed, were found to be worse than before the coating.

Landscapes

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

Abstract

La présente invention concerne un matériau actif de cathode pour une batterie secondaire au lithium et son procédé de préparation, et, en particulier : un matériau actif de cathode pour une batterie secondaire au lithium, comprenant : un oxyde métallique de transition à base de lithium-nickel; une couche de revêtement formée sur l'oxyde métallique de transition à base de lithium-nickel, la couche de revêtement comprenant un composé d'oxalate métallique; et son procédé de préparation.
PCT/KR2017/002212 2016-03-03 2017-02-28 Matériau actif de cathode pour une batterie secondaire au lithium et son procédé de préparation WO2017150893A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780003476.2A CN108140820B (zh) 2016-03-03 2017-02-28 锂二次电池用正极活性材料及其制备方法
EP17760297.6A EP3333944B1 (fr) 2016-03-03 2017-02-28 Matériau actif de cathode pour une batterie secondaire au lithium et son procédé de préparation
US15/760,089 US10665857B2 (en) 2016-03-03 2017-02-28 Positive electrode active material for secondary battery, and method of preparing the same
US16/849,290 US11189829B2 (en) 2016-03-03 2020-04-15 Positive electrode active material for secondary battery, and method of preparing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160025626 2016-03-03
KR10-2016-0025626 2016-03-03
KR1020170025656A KR101980103B1 (ko) 2016-03-03 2017-02-27 리튬 이차전지용 양극활물질 및 이의 제조 방법
KR10-2017-0025656 2017-02-27

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US15/760,089 A-371-Of-International US10665857B2 (en) 2016-03-03 2017-02-28 Positive electrode active material for secondary battery, and method of preparing the same
US16/849,290 Division US11189829B2 (en) 2016-03-03 2020-04-15 Positive electrode active material for secondary battery, and method of preparing the same

Publications (1)

Publication Number Publication Date
WO2017150893A1 true WO2017150893A1 (fr) 2017-09-08

Family

ID=59744169

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/002212 WO2017150893A1 (fr) 2016-03-03 2017-02-28 Matériau actif de cathode pour une batterie secondaire au lithium et son procédé de préparation

Country Status (1)

Country Link
WO (1) WO2017150893A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114162814A (zh) * 2020-08-20 2022-03-11 洛阳月星新能源科技有限公司 一种石墨的改性方法
CN115954445A (zh) * 2022-10-31 2023-04-11 湖南驼峰新能源有限公司 一种纳米草酸钠复合的正极活性材料及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008277307A (ja) * 2001-10-16 2008-11-13 Hanyang Hak Won Co Ltd リチウム二次電池用正極活物質、その製造方法、及びそれを含むリチウム二次電池
US20120280171A1 (en) * 2011-05-03 2012-11-08 Ilias Belharouak Production of battery grade materials via an oxalate method
KR101372053B1 (ko) * 2013-04-09 2014-03-07 (주)이엠티 리튬이차전지용 양극활물질 전구체의 제조방법, 리튬이차전지용 양극활물질의 제조방법, 양극활물질을 포함하는 양극 및 리튬이차전지
KR20150037635A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 이차전지용 양극활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차전지용 양극

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008277307A (ja) * 2001-10-16 2008-11-13 Hanyang Hak Won Co Ltd リチウム二次電池用正極活物質、その製造方法、及びそれを含むリチウム二次電池
US20120280171A1 (en) * 2011-05-03 2012-11-08 Ilias Belharouak Production of battery grade materials via an oxalate method
KR101372053B1 (ko) * 2013-04-09 2014-03-07 (주)이엠티 리튬이차전지용 양극활물질 전구체의 제조방법, 리튬이차전지용 양극활물질의 제조방법, 양극활물질을 포함하는 양극 및 리튬이차전지
KR20150037635A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 이차전지용 양극활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차전지용 양극

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HASHEM, A. M. A. ET AL.: "Study of the Surface Modification of LiNi1/3Co1/3Mn1/3O2 Cathode Material for Lithium [on Battery", JOURNAL OF POWER SOURCES, vol. 196, no. 20, 2011, pages 8632 - 8637, XP055413333 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114162814A (zh) * 2020-08-20 2022-03-11 洛阳月星新能源科技有限公司 一种石墨的改性方法
CN114162814B (zh) * 2020-08-20 2024-05-10 洛阳月星新能源科技有限公司 一种石墨的改性方法
CN115954445A (zh) * 2022-10-31 2023-04-11 湖南驼峰新能源有限公司 一种纳米草酸钠复合的正极活性材料及其应用
CN115954445B (zh) * 2022-10-31 2024-01-02 湖南驼峰新能源有限公司 一种纳米草酸钠复合的正极活性材料及其应用

Similar Documents

Publication Publication Date Title
WO2017111542A1 (fr) Matériau actif d'anode pour une batterie rechargeable au lithium et anode pour une batterie rechargeable au lithium comprenant ce dernier
WO2021153916A1 (fr) Batterie secondaire entièrement solide et son procédé de préparation
WO2012148157A2 (fr) Matériau actif d'électrode positive pour pile au lithium rechargeable, son procédé de préparation et pile au lithium rechargeable le comprenant
WO2019013501A1 (fr) Additif de solution d'électrolyte non aqueux, solution d'électrolyte non aqueux destiné à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant un additif de solution d'électrolyte non aqueux
WO2019088805A2 (fr) Matériau actif d'électrode positive au lithium-manganèse comportant une structure de spinelle, ainsi qu'électrode positive et batterie secondaire au lithium la comprenant
WO2017209561A1 (fr) Matériau cathode actif, cathode le comprenant et batterie secondaire au lithium comprenant ce même matériau
WO2020167022A1 (fr) Dispositif électrochimique et son procédé de fabrication
WO2020242138A1 (fr) Cathode pour batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium la comprenant
WO2019088806A1 (fr) Matériau d'électrode positive comprenant un matériau actif d'électrode positive au lithium-manganèse ayant une structure de spinelle, électrode positive et batterie secondaire au lithium
WO2019088807A2 (fr) Batterie rechargeable au lithium
WO2017150893A1 (fr) Matériau actif de cathode pour une batterie secondaire au lithium et son procédé de préparation
WO2020256473A1 (fr) Matériau actif d'électrode positive possédant une partie de surface dopée avec des hétéro-éléments et son procédé de production
WO2015088252A1 (fr) Materiau actif d'anode pour batterie au lithium-ion et procede de fabrication associe
WO2021015535A1 (fr) Batterie secondaire au lithium
WO2023048550A1 (fr) Additif de cathode pour batterie secondaire au lithium, procédé pour le préparer, cathode le comprenant, et batterie secondaire au lithium
WO2017095152A1 (fr) Matériau actif de cathode pour accumulateur et accumulateur comprenant celui-ci
WO2022139116A1 (fr) Procédé de fabrication de matériau actif d'électrode positive pour batterie secondaire au lithium faisant appel à un matériau actif d'électrode positive de rebut
WO2022065855A1 (fr) Composé conducteur d'ions solides, électrolyte solide le contenant, cellule électrochimique le comprenant, et procédé de fabrication associé
WO2022119158A1 (fr) Matériau actif de cathode et batterie rechargeable au lithium le comprenant
WO2022139387A1 (fr) Matériau actif de cathode, et batterie au lithium-ion le comprenant
WO2022131852A1 (fr) Composition de liant pour batterie secondaire et mélange d'électrode
WO2019066403A2 (fr) Complexe de matériau actif d'électrode pour batterie secondaire au lithium et procédé de préparation de complexe de matériau actif d'électrode
WO2016052944A1 (fr) Matériau actif d'électrode positive et son procédé de fabrication
WO2015111801A1 (fr) Nanopâte de polyaniline et son procédé de préparation
WO2023282558A1 (fr) Matériau actif d'électrode négative composite, son procédé de préparation, électrode négative le comprenant, et batterie secondaire

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2017760297

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 15760089

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE