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WO2018124593A1 - Matériau actif de cathode pour batterie secondaire, sa méthode de production et batterie secondaire au lithium le comprenant - Google Patents

Matériau actif de cathode pour batterie secondaire, sa méthode de production et batterie secondaire au lithium le comprenant Download PDF

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Publication number
WO2018124593A1
WO2018124593A1 PCT/KR2017/015046 KR2017015046W WO2018124593A1 WO 2018124593 A1 WO2018124593 A1 WO 2018124593A1 KR 2017015046 W KR2017015046 W KR 2017015046W WO 2018124593 A1 WO2018124593 A1 WO 2018124593A1
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Prior art keywords
active material
positive electrode
lithium
electrode active
transition metal
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PCT/KR2017/015046
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English (en)
Korean (ko)
Inventor
김지혜
박병천
백소라
유태구
정왕모
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020170174131A external-priority patent/KR102133916B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP17886981.4A priority Critical patent/EP3473600B1/fr
Priority to ES17886981T priority patent/ES2992870T3/es
Priority to US16/316,554 priority patent/US11299401B2/en
Priority to CN201780048071.0A priority patent/CN109562957B/zh
Priority to JP2019501925A priority patent/JP6771804B2/ja
Publication of WO2018124593A1 publication Critical patent/WO2018124593A1/fr
Priority to US17/689,217 priority patent/US12180088B2/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a cathode active material for a secondary battery, a manufacturing method thereof, and a lithium secondary battery including the same.
  • lithium secondary batteries having high energy density and voltage, long cycle life, and low self discharge rate have been commercialized and widely used.
  • Lithium transition metal composite oxide is used as a positive electrode active material of a lithium secondary battery, and among these, lithium cobalt composite metal oxide of LiCoO 2 having a high operating voltage and excellent capacity characteristics is mainly used.
  • LiCoO 2 is very poor in thermal properties due to destabilization of crystal structure due to de-lithium and is expensive, there is a limit to using LiCoO 2 as a power source in fields such as electric vehicles.
  • lithium manganese composite metal oxides such as LiMnO 2 or LiMn 2 O 4
  • lithium iron phosphate compounds such as LiFePO 4
  • lithium nickel composite metal oxides such as LiNiO 2
  • research and development of lithium nickel composite metal oxides having a high reversible capacity of about 200 mAh / g, which is easy to implement a large-capacity battery have been actively studied.
  • LiNiO 2 has a poor thermal stability compared to LiCoO 2, and when an internal short circuit occurs due to pressure from the outside in a charged state, the positive electrode active material itself decomposes, causing a battery to rupture and ignite.
  • NiCobalt manganese-based lithium composite metal oxide in which a part of Ni is substituted with Mn and Co hereinafter, simply referred to as 'NCM-based lithium oxide'.
  • 'NCM-based lithium oxide' nickel cobalt manganese-based lithium composite metal oxide in which a part of Ni is substituted with Mn and Co
  • the present invention is to solve the above problems, high concentration nickel positive electrode active material that can simultaneously realize structural stability, excellent capacity characteristics and high temperature stability with a small amount of lithium by-products, a method of manufacturing the same, and a secondary battery positive electrode comprising the same And to provide a lithium secondary battery.
  • the present invention comprises the steps of preparing a lithium transition metal oxide containing nickel (Ni), cobalt (Co), at least one selected from the group consisting of manganese (Mn) and aluminum (Al); Washing the lithium transition metal oxide to remove lithium impurities present on the surface of the lithium transition metal oxide; And a high temperature heat treatment of the lithium transition metal oxide after washing with water, wherein the high temperature heat treatment includes: an elevated temperature section for heating and heating the temperature, a holding section for maintaining the elevated temperature, and cooling the temperature; It includes a section, the temperature rising section provides a method for producing a positive electrode active material for secondary batteries 20 to 30% of the total high temperature heat treatment time.
  • the present invention includes a lithium transition metal oxide containing nickel (Ni), cobalt (Co), at least one selected from the group consisting of manganese (Mn) and aluminum (Al), the lithium transition metal
  • the oxide is a positive electrode active material for secondary batteries having a nickel (Ni) content of at least 80 mol% of all transition metal elements, and a cation mixing ratio of Ni cations in the lithium layer in the lithium transition metal oxide structure is 1.1% or less. to provide.
  • the present invention provides a cathode and a lithium secondary battery including the cathode active material.
  • a positive electrode active material can be manufactured.
  • unlike the conventional high-concentration nickel positive electrode active material not only is structurally stable, but also may exhibit a secondary battery having excellent capacity characteristics and small resistance increase rate even when repeated charging.
  • FIG. 1 is a graph showing heat flow with respect to the temperature of a cathode active material according to Examples and Comparative Examples.
  • FIG. 2 is a graph showing capacity retention rates for charge and discharge cycles of battery cells manufactured using positive electrode active materials according to Examples and Comparative Examples.
  • FIG 3 is a graph illustrating a resistance increase rate with respect to a charge / discharge cycle of a battery cell manufactured using a cathode active material according to Examples and Comparative Examples.
  • the present invention reduces the residual amount of lithium by-products by washing the lithium transition metal oxide containing high concentration of nickel with high temperature and washing it at a specific condition, thereby reducing the residual amount of lithium by-products and recrystallization of the crystal structure in which lithium is released and destroyed.
  • This improved high concentration nickel-based cathode active material can be prepared.
  • the present invention comprises the steps of preparing a lithium transition metal oxide containing nickel (Ni), cobalt (Co), and at least one selected from the group consisting of manganese (Mn) and aluminum (Al); Washing the lithium transition metal oxide to remove lithium impurities present on the surface of the lithium transition metal oxide; And a high temperature heat treatment of the lithium transition metal oxide after washing with water, wherein the high temperature heat treatment includes: an elevated temperature section for heating and heating the temperature, a holding section for maintaining the elevated temperature, and cooling the temperature; It includes a section, the temperature rising section provides a method for producing a positive electrode active material for secondary batteries 20 to 30% of the total high temperature heat treatment time.
  • a lithium transition metal oxide including nickel (Ni) and cobalt (Co) and including at least one selected from the group consisting of manganese (Mn) and aluminum (Al) is prepared.
  • the lithium transition metal oxide may be represented by the following formula (1).
  • M 1 is at least one selected from the group consisting of Mn and Al
  • M 2 and M 3 are each independently Ba, Ca, Zr, Ti, Mg, Ta, Nb, W and Mo At least one selected from the group consisting of: 1.0 ⁇ a ⁇ 1.5, 0 ⁇ x1 ⁇ 0.2, 0 ⁇ y1 ⁇ 0.2, 0 ⁇ z1 ⁇ 0.1, 0 ⁇ q1 ⁇ 0.1, 0 ⁇ x1 + y1 + z1 ⁇ 0.2 to be.
  • 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 process, and the production of the positive electrode active material may be difficult. Considering the remarkable effect of improving the capacity characteristics of the positive electrode active material according to the control of the Li content and the balance of the sintering property during manufacturing of the active material, the Li may be more preferably included in a content of 1.0 ⁇ a ⁇ 1.15.
  • Ni may be included in an amount corresponding to 1-x1-y1-z1, that is, 0.8 ⁇ 1-x1-y1-z1 ⁇ 1. More preferably Ni may be included as 0.8 ⁇ 1-x1-y1-z1 ⁇ 0.9.
  • the Ni content in the lithium transition metal oxide of Formula 1 is 0.8 or more, the amount of Ni sufficient to contribute to charging and discharging may be secured, thereby achieving high capacity. If the content of Ni is less than 0.8, there may be a limit to the implementation of high capacity.In the composition of more than 0.9, part of the Li site may be replaced by Ni to obtain sufficient amount of Li to contribute to charge and discharge. There is a risk of deterioration.
  • Co may be included in an amount corresponding to x1, that is, 0 ⁇ x1 ⁇ 0.2.
  • content of Co in the lithium transition metal oxide of Formula 1 exceeds 0.2, efficiency of capacity improvement may be deteriorated compared to an increase in cost.
  • Co may be included in a content of 0.05 ⁇ x ⁇ 0.2 more specifically.
  • M 1 may be Mn or Al, or Mn and Al, and these metal elements may improve the stability of the active material and, as a result, improve the stability of the battery.
  • M 1 may be included in an amount corresponding to y1, that is, 0 ⁇ y1 ⁇ 0.2.
  • y1 in the lithium composite transition metal oxide of Formula 1 exceeds 0.2, there is a concern that the output characteristics and capacity characteristics of the battery may be lowered, and M 1 may be included in an amount of 0.05 ⁇ y1 ⁇ 0.2.
  • M 2 may be a doping element included in the crystal structure of the lithium composite transition metal oxide, and M 2 may be included in an amount corresponding to z 1, that is, 0 ⁇ z 1 ⁇ 0.1. have.
  • the metal element of M 3 may not be included in the lithium composite transition metal oxide structure, and when the precursor and the lithium source are mixed and calcined, the M 3 source may be mixed together and calcined.
  • a lithium composite transition metal oxide doped on the surface of the M 3 lithium composite transition metal oxide may be prepared by separately adding an M 3 source and firing.
  • the M 3 may be included in an amount corresponding to q1, that is, in an amount of 0 ⁇ q1 ⁇ 0.1, so as not to degrade the characteristics of the positive electrode active material.
  • the lithium transition metal oxide used in the present invention may be an NCM-based lithium composite transition metal oxide including nickel (Ni), cobalt (Co) and manganese (Mn), or nickel (Ni), cobalt (Co) and It may be an NCA-based lithium composite transition metal oxide including aluminum (Al).
  • the positive electrode active material may be a four-component lithium composite transition metal oxide including essentially four components of nickel (Ni), cobalt (Co), manganese (Mn), and aluminum (Al).
  • the lithium transition metal oxide used in the present invention may be a high-nickel-based lithium transition metal oxide having a molar ratio of nickel of 0.8 or more in the total molar ratio of the transition metal in the lithium transition metal oxide.
  • the lithium transition metal oxide of Chemical Formula 1 is not limited thereto, but may be, for example, a mixture of a precursor represented by Chemical Formula 2 and a lithium-containing raw material, and then fired at 700 to 900 ° C. . More preferably, it can bake in oxygen atmosphere at the said baking temperature.
  • M 1 is at least one selected from the group consisting of Mn and Al
  • the preferred composition of Ni, Co, M 1 and M 2 may be the same as the range of the composition of the lithium transition metal oxide described above.
  • the lithium-containing raw material material may be lithium-containing carbonate (e.g., lithium carbonate), hydrate (e.g., lithium hydroxide I hydrate (LiOH, H 2 O), etc.), hydroxide (e.g., lithium hydroxide, etc.), nitrate (Eg, lithium nitrate (LiNO 3 ), etc.), chlorides (eg, lithium chloride (LiCl), and the like), and the like, and one of these may be used alone or a mixture of two or more thereof may be used.
  • Lithium carbonate may be used.
  • the lithium transition metal oxide prepared as described above is washed with water to remove lithium by-products remaining in the lithium transition metal oxide.
  • the lithium transition metal oxide containing a high concentration of nickel such as the lithium transition metal oxide of the present invention
  • the structural unstable compared to the lithium transition metal oxide having a low nickel content and unreacted lithium hydroxide or lithium carbonate in the manufacturing process More lithium by-products are produced.
  • the amount of lithium by-products after synthesis is about 0.5 to 0.6 wt%, whereas in the case of a lithium composite metal oxide having a nickel content of 80 mol% or more, lithium after synthesis
  • the amount of by-products appears as high as 1% by weight.
  • the washing step may be performed, for example, by adding a lithium transition metal oxide to pure water and stirring.
  • the washing with water may be performed using 50 to 100 parts by weight of pure water with respect to 100 parts by weight of lithium transition metal oxide.
  • the amount of pure water is less than 50 parts by weight based on 100 parts by weight of the lithium transition metal oxide during washing, insufficient cleaning may be insufficient, and if the amount of pure water exceeds 100 parts by weight, lithium in the crystal structure may be insufficient.
  • the amount of dissolved water may increase, particularly in the case of a lithium transition metal oxide having a high nickel content of at least 80 mol%, the amount of lithium dissolved in the crystal structure is significantly reduced when the pure water content is too large. Increasingly, a sudden decrease in the capacity and life of the battery may occur.
  • the washing temperature may be 30 °C or less, preferably -10 °C to 30 °C, the washing time may be about 10 minutes to 1 hour.
  • the water washing temperature and the water washing time satisfy the above range, lithium by-products can be effectively removed.
  • the washed lithium transition metal oxide is subjected to high temperature heat treatment.
  • the step of the high temperature heat treatment, the temperature increase and the heat treatment section for heat treatment includes a maintenance section for heat treatment while maintaining the elevated temperature and a cooling section for cooling the temperature.
  • the temperature increase section is preferably 20 to 30% of the total high temperature heat treatment time.
  • the high temperature heat treatment step is to improve the structural stability and thermal stability by further removing lithium by-products, and recrystallization of the metal elements in the positive electrode active material through high temperature heat treatment.
  • the lithium transition metal oxide containing high concentration of nickel washing with water is performed to remove residual lithium by-products.
  • the present invention is a high-temperature heat treatment of the washed transition metal oxide under the above conditions, thereby recrystallizing the metal elements of the lithium transition metal oxide to fill the vacancy of lithium, and improved surface stability.
  • the elevated temperature range is less than 20% of the total high temperature heat treatment time, the remaining moisture may not be sufficiently removed after the washing process, and thus, battery performance may be deteriorated, such as a decrease in electrical conductivity. If the temperature exceeds 30%, the crystallization may not be effectively performed.
  • the cation mixing ratio of the Ni cation may increase.
  • the holding section may be 40 to 50% of the total high temperature heat treatment time.
  • the cooling section may be 20 to 30% of the total high temperature heat treatment time.
  • the total time of the high temperature heat treatment is preferably within 10 hours, specifically, the total high temperature heat treatment time may be 6 hours to 10 hours.
  • the temperature increase rate of the temperature increase section may be 2 to 7 °C / min, more preferably 3 to 6 °C / min.
  • the heat treatment temperature of the organic section may be 600 ° C or more, more preferably 600 to 900 ° C.
  • the cooling section may be cooled in a natural cooling manner.
  • the thermal stability improvement effect is excellent. According to the researches of the present inventors, it was found that there is little effect of improving the thermal stability when the heat treatment temperature of the holding section is less than 600 °C.
  • the high temperature heat treatment may be performed in an oxygen atmosphere, specifically, an oxygen partial pressure of 80% or more, more preferably 80 to 99%, even more preferably 90 to 95%.
  • an oxygen partial pressure of 80% or more, more preferably 80 to 99%, even more preferably 90 to 95%.
  • the effect of removing lithium by-products is remarkably decreased when the heat treatment is performed in the air.
  • the heat treatment is performed at 600 ° C. or higher, the amount of lithium by-products is increased rather than before heat treatment.
  • the high temperature heat-treated lithium transition metal oxide is H 3 BO 3 , B 2 O 3 And it may be mixed with at least one selected from the group consisting of Al 2 O 3 and heat treatment to form a coating layer on the surface of the lithium transition metal oxide.
  • the heat treatment may be performed at a temperature of 200 to 500 °C.
  • the cathode active material for a secondary battery of the present invention manufactured by the above method includes nickel (Ni) and cobalt (Co), and includes at least one or more selected from the group consisting of manganese (Mn) and aluminum (Al).
  • the lithium transition metal oxide has a nickel (Ni) content of 80 mol% or more in all transition metal elements, and a cation mixing ratio of Ni cations in the lithium layer in the lithium transition metal oxide structure is 1.1% or less.
  • the lithium transition metal oxide may be represented by the following Chemical Formula 1.
  • M 1 is at least one selected from the group consisting of Mn and Al
  • M 2 and M 3 are each independently Ba, Ca, Zr, Ti, Mg, Ta, Nb, W and Mo At least one selected from the group consisting of: 1.0 ⁇ a ⁇ 1.5, 0 ⁇ x1 ⁇ 0.2, 0 ⁇ y1 ⁇ 0.2, 0 ⁇ z1 ⁇ 0.1, 0 ⁇ q1 ⁇ 0.1, 0 ⁇ x1 + y1 + z1 ⁇ 0.2 to be.
  • Specific specifications of the lithium transition metal oxide represented by Chemical Formula 1 are the same as those described in the manufacturing method, and thus, detailed description thereof will be omitted.
  • the present invention in order to produce a positive electrode active material having excellent electrochemical characteristics such as discharge capacity and lifespan, after washing the lithium transition metal oxide containing a high concentration of nickel, and then heat treatment under high temperature in an oxygen atmosphere of the lithium transition metal oxide
  • the layered structure was well developed and the amount of cation mixing of Ni cations in the lithium layer was 1.1% or less. More preferably, the amount of cation mixing may be 1.0% or less.
  • the amount of cation mixing in which the Ni cation is incorporated in the lithium layer satisfies the above range, the capacity characteristics of the lithium transition metal oxide may be excellent, but the high temperature stability and the life characteristics may be effectively improved.
  • the cathode active material according to the present invention as described above is manufactured through a process of high temperature heat treatment in an oxygen atmosphere after washing with water, the residual amount of lithium by-products can be significantly reduced.
  • the content of lithium by-product present in the positive electrode active material may be more than 0.3% to 1% by weight, more preferably more than 0.3% to 0.6% by weight, more preferably more than 0.35% to 0.5% by weight It may be less than or equal to%.
  • the cathode active material according to the present invention satisfies the amount of residual lithium by-products within the above range, thereby effectively forming a coating layer by reaction between the lithium by-products and the coating source, thereby effectively suppressing gas generation and swelling during charging and discharging.
  • Lithium by-products can lead to capacity and lifetime inferiority and gas evolution.
  • the cathode active material according to the present invention may have a crystal density of 4.76 g / cm 3 or more. More preferably 4.765 g / cm 3 or more.
  • Conventional high-concentration nickel-containing positive electrode active material has a significant decrease in structure stability and high temperature stability after washing with water, but the positive electrode active material according to the present invention has a crystal density due to recrystallization of metal elements by high temperature heat treatment in an oxygen atmosphere after washing with water. Can increase to 4.76 g / cm 3 or more. Through this, the calorific value is significantly reduced, and the high temperature life characteristics and the high temperature resistance increase rate can be significantly improved.
  • the cathode active material according to the present invention may have a BET specific surface area of 0.5 m 2 / g or less.
  • Conventional high-concentration nickel-containing positive electrode active material while the lithium in the surface crystal structure withdraws through the water, the specific surface area is significantly increased and the structural stability and high temperature stability is deteriorated, but the positive electrode active material according to the present invention is a high temperature heat treatment in an oxygen atmosphere after water washing
  • the specific surface area may be reduced to 0.5 m 2 / g or less, more preferably 0.35 m 2 / g or less due to recrystallization of the metal elements. Through this, the calorific value is significantly reduced, and the high temperature life characteristics and the high temperature resistance increase rate can be significantly improved.
  • the positive electrode active material according to the present invention when measured the heat flow (Heat Flow) by differential scanning calorimetry (DSC), the maximum temperature in the temperature range of 220 °C to 250 °C, preferably 225 °C to 245 °C A peak may appear and the maximum value of the heat flow may be 200 mW or less (based on a sample of 15 mg). If the high temperature heat treatment is not performed after washing with water or if the heat treatment temperature and atmosphere do not satisfy the conditions of the present invention even after high temperature heat treatment, the maximum peak appears at a lower temperature, that is, less than 220 ° C., and a high heat flow value exceeding 200 mW (sample 15 mg standard).
  • the maximum peak appears in the low temperature range and the cathode active material having a high maximum heat flow amount is used, when the temperature inside the battery increases due to overcharging or the like, an explosion may occur while the heat flow rate increases rapidly.
  • the positive electrode active material of the present invention since the positive electrode active material of the present invention has a relatively high temperature range in which the maximum peak appears and a small maximum amount of heat flow, the explosion risk is small even when the internal temperature of the battery increases due to overcharge or the like.
  • the cathode active material according to the present invention may include the lithium transition metal oxide in a layered structural phase and a spinel-like structural phase.
  • the spinel-like structure phase may be formed by a phase transition from the layered structure phase.
  • the phase transition may occur by high temperature heat treatment.
  • a cathode including the cathode active material is provided.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer positioned on at least one surface of the positive electrode current collector and including the positive electrode active material.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change 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 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 layer may include a conductive material and a binder together with the cathode active material described above.
  • the positive electrode active material may be included in the weight of 80 to 99% by weight, more specifically 85 to 98% by weight relative to the total weight of the positive electrode active material layer. When included in the above content range may exhibit excellent capacity characteristics.
  • 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, summer 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 be included in an amount of 1 to 30 wt% based on the total weight of the positive electrode active material layer.
  • the binder serves to improve adhesion between the positive electrode active material particles and the adhesion between the positive electrode 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 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 prepared by dissolving or dispersing a binder and a conductive material in a solvent may be applied onto 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 3 ⁇ m to 500 ⁇ m, and similarly to 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.
  • 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;
  • 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 negative electrode active material layer is, for example, coated with a negative electrode active material, and optionally a composition for forming a negative electrode active material layer prepared by dissolving or dispersing a binder and a conductive material in a solvent and dried, or for forming the negative electrode active material layer
  • the composition may be prepared by casting the composition on a separate support, and then laminating the film obtained by peeling from the support onto a negative electrode current collector.
  • 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 for ion transfer 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; Dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (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-C20 linear, branched or cyclic hydrocarbon group, which may include
  • 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.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type 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.
  • Lithium transition metal oxide is Li (Ni 0. 86 Co 0 . 1 Mn 0. 02 Al 0. 02) O 2 300 g of pure water was added to 240 mL of water, stirred for 30 minutes, and washed for 20 minutes. The filtered lithium transition metal oxide was dried at 130 ° C. in a vacuum oven, followed by sieving.
  • the washed lithium transition metal oxide was subjected to high temperature heat treatment in an oxygen atmosphere with an oxygen partial pressure of 95%.
  • the temperature was raised to 700 ° C. at 5 ° C./min for 2 hours and 15 minutes, and heat-treated at 700 ° C. for 3 hours and 40 minutes, and then heated at a high temperature for 2 hours and 30 minutes.
  • Example 1 The positive electrode active material was prepared in the same manner as the above.
  • the high temperature heat treatment was carried out in the same manner as in Example 1 except that the temperature was raised to 200 °C for 45 minutes, the heat treatment at 200 °C for 10 hours, the cooling process for 60 minutes to prepare a positive electrode active material.
  • the cathode active material was prepared in the same manner as in Example 1 except that the mixture was heated to 300 ° C. for 70 minutes, heat-treated at 300 ° C. for 3 hours and 40 minutes, and cooled at 90 ° C. for 90 minutes. It was.
  • the high temperature heat treatment was carried out in the same manner as in Example 1 except that the temperature was raised to 400 °C for 80 minutes, the heat treatment for 4 hours at 400 °C, and the high temperature heat treatment for 2 hours to prepare a cathode active material.
  • a high temperature heat treatment was carried out in the same manner as in Example 1 except that the temperature was elevated to 500 ° C. for 90 minutes, heat treated at 500 ° C. for 4 hours, and cooled for 2 hours and 20 minutes to prepare a cathode active material. It was.
  • the high temperature heat treatment was carried out in the same manner as in Example 1 except that the temperature was raised to 700 °C for 3 hours, the heat treatment for 10 hours at 700 °C, and the high temperature heat treatment for 3 hours to prepare a cathode active material.
  • a positive electrode active material was prepared in the same manner as in Example 1 except that the high temperature heat treatment was performed in an air atmosphere instead of an oxygen atmosphere.
  • Example 1 The cathode active materials prepared in Example 1 and Comparative Example 1 were analyzed by XRD using Bruker AXS D4 Endeavor XRD, and the crystal size, crystal density, and Ni cations in the lithium layer were analyzed.
  • the results of cation mixing are shown in Table 1.
  • the BET surface area was measured using BELSORP-mini, the results are shown in Table 1.
  • Example 1 subjected to high temperature heat treatment according to the present invention, the amount of cation mixture was decreased, the crystal density was increased, and the BET specific surface area was reduced compared to Comparative Example 1, which was not subjected to high temperature heat treatment. .
  • the positive electrode active materials of Examples 1 and 2 have a maximum heat flow value of less than 200 mW, whereas the positive active materials of Comparative Examples 1 to 7 have a maximum heat flow value of more than 400 mW, and particularly, in the case of Comparative Example 1, 600 mW. It can be confirmed that the excess. This shows that the positive electrode active materials of Examples 1 and 2 have excellent high temperature stability compared to the positive electrode active materials of Comparative Examples 1 to 7.
  • Each positive electrode active material, carbon black conductive material, and PVdF binder prepared in Examples and Comparative Examples were mixed in an N-methylpyrrolidone solvent in a ratio of 95: 2.5: 2.5 by weight in a positive electrode mixture (viscosity: 5000 mPa ⁇ s ) was applied to one surface of an aluminum current collector, dried at 130 ° C., and then rolled to prepare a positive electrode.
  • a negative electrode active material a natural graphite, a carbon black conductive material, and a PVdF binder were mixed in an N-methylpyrrolidone solvent in a ratio of 85: 10: 5 in a weight ratio to prepare a composition for forming a negative electrode active material layer, and a copper current collector It was applied to one side of 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.
  • the measurement results are shown in FIGS. 2 and 3. 2 is a graph showing a capacity retention rate, and FIG. 3 is a graph showing a resistance increase rate.

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Abstract

La présente invention concerne un matériau actif de cathode pour une batterie secondaire, comprenant : un oxyde de métal de transition de lithium contenant du nickel (Ni), du cobalt (Co), et au moins un élément choisi dans le groupe constitué par le manganèse (Mn) et l'aluminium (Al), la teneur en nickel (Ni) dans l'élément de métal de transition total dans l'oxyde de métal de transition de lithium étant de 80 % en moles ou plus, et le rapport de mélange de cations des cations de Ni dans une couche de lithium, dans la structure d'oxyde de métal de transition de lithium est de 1,1 % ou moins.
PCT/KR2017/015046 2016-12-28 2017-12-19 Matériau actif de cathode pour batterie secondaire, sa méthode de production et batterie secondaire au lithium le comprenant WO2018124593A1 (fr)

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EP17886981.4A EP3473600B1 (fr) 2016-12-28 2017-12-19 Méthode de production d`un matériau électrode actif positive pour batterie secondaire
ES17886981T ES2992870T3 (en) 2016-12-28 2017-12-19 Method for manufacturing a positive electrode active material for a secondary battery
US16/316,554 US11299401B2 (en) 2016-12-28 2017-12-19 Positive electrode active material for secondary battery, manufacturing method thereof, and secondary battery including same
CN201780048071.0A CN109562957B (zh) 2016-12-28 2017-12-19 二次电池用正极活性材料、其制造方法以及包括其的锂二次电池
JP2019501925A JP6771804B2 (ja) 2016-12-28 2017-12-19 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
US17/689,217 US12180088B2 (en) 2016-12-28 2022-03-08 Positive electrode active material for secondary battery, manufacturing method thereof, and secondary battery including same

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020208963A1 (fr) * 2019-04-12 2020-10-15 住友化学株式会社 Poudre d'oxyde composite de métal de lithium, et matériau actif d'électrode positive pour batterie secondaire au lithium
CN113711389A (zh) * 2019-05-13 2021-11-26 株式会社Lg化学 二次电池用正极活性材料、其制备方法以及包含所述正极活性材料的锂二次电池
WO2025058414A1 (fr) * 2023-09-15 2025-03-20 주식회사 엘지에너지솔루션 Matériau de cathode mixte et son procédé de préparation
KR20250040519A (ko) * 2023-09-15 2025-03-24 주식회사 엘지에너지솔루션 혼합 양극재 및 이의 제조 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012022995A (ja) * 2010-07-16 2012-02-02 Tdk Corp 活物質、これを含む電極、当該電極を備えるリチウム二次電池、及び活物質の製造方法
KR20130102718A (ko) * 2012-03-08 2013-09-23 비나텍주식회사 층상 구조의 양극 활물질 제조 방법과 이 제조 방법에 의해 제조된 양극 활물질 및 이를 포함하는 하이브리드 커패시터
KR20160046292A (ko) * 2014-10-20 2016-04-28 히타치 긴조쿠 가부시키가이샤 리튬 이온 이차전지용 양극 활물질, 그 제조 방법 및 리튬 이온 이차전지
KR20160086228A (ko) * 2015-01-09 2016-07-19 주식회사 에코프로비엠 리튬 이차 전지용 양극활물질의 제조 방법 및 이에 의하여 제조된 리튬 이차 전지용 양극활물질

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012022995A (ja) * 2010-07-16 2012-02-02 Tdk Corp 活物質、これを含む電極、当該電極を備えるリチウム二次電池、及び活物質の製造方法
KR20130102718A (ko) * 2012-03-08 2013-09-23 비나텍주식회사 층상 구조의 양극 활물질 제조 방법과 이 제조 방법에 의해 제조된 양극 활물질 및 이를 포함하는 하이브리드 커패시터
KR20160046292A (ko) * 2014-10-20 2016-04-28 히타치 긴조쿠 가부시키가이샤 리튬 이온 이차전지용 양극 활물질, 그 제조 방법 및 리튬 이온 이차전지
KR20160086228A (ko) * 2015-01-09 2016-07-19 주식회사 에코프로비엠 리튬 이차 전지용 양극활물질의 제조 방법 및 이에 의하여 제조된 리튬 이차 전지용 양극활물질

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PARK, KANG-JOON ET AL.: "A High-capacity Li[Ni0.8Co0.06Mn0.14]O2 Positive Electrode with a Dual Concentration Gradient for Next -generation Lithium-ion Batteries", JOURNAL OF MATERIALS CHEMISTRY A, vol. 3, 21 September 2015 (2015-09-21), pages 22183 - 22190, XP055427733 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020208963A1 (fr) * 2019-04-12 2020-10-15 住友化学株式会社 Poudre d'oxyde composite de métal de lithium, et matériau actif d'électrode positive pour batterie secondaire au lithium
JP2020172422A (ja) * 2019-04-12 2020-10-22 住友化学株式会社 リチウム金属複合酸化物粉末及びリチウム二次電池用正極活物質
US12155070B2 (en) 2019-04-12 2024-11-26 Sumitomo Chemical Company, Limited Lithium metal composite oxide powder and positive electrode active material for lithium secondary battery
CN113711389A (zh) * 2019-05-13 2021-11-26 株式会社Lg化学 二次电池用正极活性材料、其制备方法以及包含所述正极活性材料的锂二次电池
CN113711389B (zh) * 2019-05-13 2024-12-13 株式会社Lg化学 二次电池用正极活性材料、其制备方法以及包含所述正极活性材料的锂二次电池
WO2025058414A1 (fr) * 2023-09-15 2025-03-20 주식회사 엘지에너지솔루션 Matériau de cathode mixte et son procédé de préparation
KR20250040519A (ko) * 2023-09-15 2025-03-24 주식회사 엘지에너지솔루션 혼합 양극재 및 이의 제조 방법
KR102847784B1 (ko) 2023-09-15 2025-08-19 주식회사 엘지에너지솔루션 혼합 양극재 및 이의 제조 방법

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