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WO2018160023A1 - Matériau actif de cathode pour pile rechargeable au lithium, son procédé de fabrication et pile rechargeable au lithium comprenant ledit matériau - Google Patents

Matériau actif de cathode pour pile rechargeable au lithium, son procédé de fabrication et pile rechargeable au lithium comprenant ledit matériau Download PDF

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Publication number
WO2018160023A1
WO2018160023A1 PCT/KR2018/002505 KR2018002505W WO2018160023A1 WO 2018160023 A1 WO2018160023 A1 WO 2018160023A1 KR 2018002505 W KR2018002505 W KR 2018002505W WO 2018160023 A1 WO2018160023 A1 WO 2018160023A1
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Prior art keywords
active material
lithium
transition metal
metal oxide
secondary battery
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PCT/KR2018/002505
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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 KR1020180023733A external-priority patent/KR102176633B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18760273.5A priority Critical patent/EP3522272B1/fr
Priority to PL18760273.5T priority patent/PL3522272T3/pl
Priority to JP2019529180A priority patent/JP6786146B2/ja
Priority to US16/347,742 priority patent/US11152617B2/en
Priority to CN201880010581.3A priority patent/CN110268561B/zh
Publication of WO2018160023A1 publication Critical patent/WO2018160023A1/fr
Priority to US17/476,673 priority patent/US11532815B2/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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a cathode active material for a secondary battery, 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 LiFePO 4 Etc.
  • lithium nickel composite metal oxides such as LiNiO 2
  • LiNiO 2 has a poor thermal stability as 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 is decomposed to cause the battery to rupture and ignite.
  • the present invention is to solve the above problems, suppresses the rapid increase in crystal size even at high firing temperature, improve the crystallinity, reduce the residual amount of lithium by-products excellent capacity characteristics, life characteristics, resistance characteristics and high temperature
  • the present invention provides a cathode active material for a lithium secondary battery that can implement safety, a method of manufacturing the same, and a lithium secondary battery including the same.
  • the present invention includes a lithium composite transition metal oxide including nickel (Ni), cobalt (Co) and manganese (Mn), the lithium composite transition metal oxide is a portion of the nickel (Ni) site is substituted with tungsten (W).
  • the present invention provides a cathode active material for a lithium secondary battery having a content of lithium tungsten oxide remaining on the surface of the lithium composite transition metal oxide particle of 1,000 ppm or less.
  • the present invention comprises the steps of preparing a metal solution comprising a nickel (Ni) containing raw material, a cobalt (Co) containing raw material, a manganese (Mn) containing raw material and a tungsten (W) containing raw material; Preparing a cathode active material precursor by coprecipitation reaction of the metal solution; Mixing and firing the positive electrode active material precursor and the lithium raw material to prepare a lithium composite transition metal oxide in which a portion of a nickel (Ni) site is substituted with tungsten (W); And removing lithium tungsten oxide remaining on the surface of the lithium transition metal oxide by washing the calcined lithium composite transition metal oxide.
  • the present invention provides a cathode and a lithium secondary battery including the cathode active material.
  • the cathode active material for a lithium secondary battery a part of the nickel (Ni) site of the lithium composite transition metal oxide is substituted with tungsten (W), and the content of lithium by-products, particularly lithium tungsten oxide is reduced, so that the particle size of the cathode active material is While increasing, crystal size can be reduced, resulting in high capacity, improved resistance, longevity and high temperature safety.
  • Ni nickel
  • W tungsten
  • Example 1 is a graph showing a 2C profile of a secondary battery manufactured using the cathode active materials of Example 2 and Comparative Example 1.
  • FIG. 2 is a graph illustrating a resistance increase rate according to charge and discharge cycles of secondary batteries manufactured using the cathode active materials of Example 2 and Comparative Example 1.
  • FIG. 2 is a graph illustrating a resistance increase rate according to charge and discharge cycles of secondary batteries manufactured using the cathode active materials of Example 2 and Comparative Example 1.
  • the cathode active material for a lithium secondary battery of the present invention includes a lithium composite transition metal oxide including nickel (Ni), cobalt (Co) and manganese (Mn), and the lithium composite transition metal oxide is a part of a nickel (Ni) site.
  • the content of lithium tungsten oxide substituted by tungsten (W) and remaining on the surface of the lithium composite transition metal oxide particle is 1,000 ppm or less.
  • the particle size of the positive electrode active material is increased in order to realize a high capacity by increasing the energy density.
  • the firing temperature is increased to achieve the normal capacity, and the crystallinity is increased as the firing temperature is increased. As this was reduced, there was a problem in that it was difficult to implement a normal capacity of the cathode active material having a large particle size.
  • the amount of nickel (Ni) in the positive electrode active material increases, the amount of residual lithium by-products increases on the surface of the positive electrode active material, which causes a problem such that the capacity of the battery decreases due to such lithium by-products.
  • the present invention is to do the tungsten (W) through the coprecipitation reaction to replace the tungsten (W) to a part of the nickel (Ni) site of the lithium composite transition metal oxide, and through the water washing process after firing
  • the content of lithium by-products, particularly lithium tungsten oxide, remaining on the surface of the lithium composite transition metal oxide particles is reduced, and thus high capacity can be achieved, resistance can be improved, life characteristics and high temperature safety can be ensured.
  • the cathode active material for a lithium secondary battery of the present invention is characterized in that tungsten (W) is substituted for a part of a nickel (Ni) site of a lithium composite transition metal oxide.
  • tungsten (W) is substituted for a part of the nickel site (Ni) in the crystal structure of the lithium composite transition metal oxide than the case where tungsten (W) is doped on the surface outside the crystal structure
  • a positive electrode active material having a large particle size is used. Even when the firing temperature is increased for manufacturing, it is possible to more effectively suppress the size of the crystals from increasing drastically, to prevent the lowering of the crystallinity, and to improve the effect of high capacity and resistance.
  • the lithium composite transition metal oxide may be represented by the following Chemical Formula 1.
  • M 1 is at least 1 selected from the group consisting of Mn and Al. It is at least one species, and M 2 may be at least one species selected from the group consisting of Ba, Ca, Zr, Ti, Mg, Ta, Nb, and Mo.
  • the lithium composite transition metal oxide used in the present invention may include essentially four components of nickel (Ni), cobalt (Co), manganese (Mn), and aluminum (Al), among which the nickel (Ni) It may be a lithium composite transition metal oxide in which tungsten (W) is substituted at a portion of the site. Or nickel (Ni), cobalt (Co), manganese (Mn), and tungsten (W) is substituted in a portion of the nickel (Ni) site, and Ba, Ca, Zr, Ti, Mg, Ta in addition to the crystal structure , Nb and Mo may be a lithium composite transition metal oxide further comprising one or more selected from the group consisting of.
  • the lithium composite transition metal oxide used in the present invention may be a lithium composite transition metal oxide satisfying 0 ⁇ x1 + y1 + z1 ⁇ 0.2 in Formula 1. That is, the lithium composite transition metal oxide may be a high-nickel based lithium composite transition metal oxide having a molar ratio of nickel (Ni) of 0.8 or more of the total molar ratio of the transition metal.
  • Li in the lithium composite transition metal oxide of Formula 1, 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 content of Ni in the lithium composite transition metal oxide of Formula 1 is 0.8 or more, sufficient amount of Ni 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, and 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 composite transition metal oxide of Formula 1 exceeds 0.2, efficiency of capacity improvement may be deteriorated as compared to an increase in cost.
  • Co may be included in a content of 0.05 ⁇ x ⁇ 0.2 more specifically.
  • the elements of Ni and Co in the lithium composite transition metal oxide of Formula 1 may be partially substituted or doped by the metal element M 1 to improve the structural stability of the positive electrode active material.
  • M 1 may be at least one or more selected from the group consisting of Mn and Al.
  • the metal element M 1 may be included in a content corresponding to y1, that is, 0 ⁇ y1 ⁇ 0.2 have.
  • 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 deteriorated.
  • W may be included in an amount corresponding to z1, that is, 0 ⁇ z1 ⁇ 0.2.
  • the crystal size may be increased, the crystallinity may be lowered, and the resistance may be increased.
  • W may be included in an amount of 0.0005 ⁇ z1 ⁇ 0.1. In this case, W means that the content is substituted in the Ni site in the crystal structure.
  • M 2 in order to improve battery characteristics by controlling distribution of transition metal elements in the positive electrode active material, another element other than elements of Ni, Co, W, and M 1 , that is, M 2 is doped.
  • M 2 may be any one or more elements specifically selected from the group consisting of Ba, Ca, Zr, Ti, Mg, Ta, Nb, and Mo.
  • the element of M 2 may be included in an amount corresponding to q1, that is, 0 ⁇ q1 ⁇ 0.1 in a range that does not lower the characteristics of the positive electrode active material.
  • the lithium composite transition metal oxide may contain 10 to 5,000 ppm of tungsten (W) in the crystal structure, more preferably 1,000 to 3,500 ppm of tungsten (W) in the crystal structure, most preferably crystal It may contain 2,000 to 3,000 ppm of tungsten (W) in the structure.
  • W tungsten
  • the lithium composite transition metal oxide when the content of tungsten (W) in the crystal structure is less than 10 ppm, it is difficult to control the crystal size. In particular, in the case of a high nickel (Ni) content and a large particle size active material, the crystal size rapidly increases to increase resistance.
  • Capacity may be lowered, and if the content of tungsten (W) in the crystal structure exceeds 5,000ppm, there may be a problem of capacity decrease, resistance increase, and gas generation due to W dissolution.
  • the content of tungsten (W) in the crystal structure is 2,000 to 3,000 ppm.
  • d / 1,000c is 0.05 or more, more preferably 0.06 to 0.10, most preferably 0.06 to 0.095.
  • the positive electrode active material of the lithium composite transition metal oxide according to an embodiment of the present invention can realize a high capacity by preventing the crystal size from increasing rapidly while increasing the particle size in order to increase energy density.
  • the firing temperature is increased to increase the particle size of the positive electrode active material to achieve a high capacity, the crystallinity may be lowered, the crystal size may be rapidly increased, and the d / 1,000c may be formed to be less than 0.05. If the d / 1,000c is less than 0.05, it is difficult to implement a normal capacity, and the initial resistance value and the resistance increase may become large.
  • the average particle diameter (D 50 ) may be defined as a particle size corresponding to 50% of the cumulative volume in the particle size distribution curve.
  • the average particle diameter D 50 may be measured using, for example, Particle Size Distribution.
  • the measuring method of the average particle diameter (D 50 ) of the positive electrode active material is dispersed in the dispersion medium particles in a dispersion medium, and then introduced into a commercially available laser diffraction particle size measuring apparatus (for example, Microtrac MT 3000) to After irradiating an ultrasonic wave of 28 kHz with an output of 60 W, the average particle diameter D 50 corresponding to 50% of the volume accumulation amount in the measuring device can be calculated.
  • the crystal size may be defined as one domain having aromaticity in the primary particles.
  • the crystal size may be derived through XRD measurement.
  • the crystal size of the lithium composite transition metal oxide may be 100 to 200 nm, more preferably 130 to 180 nm, and most preferably 140 to 160 nm.
  • the crystal size of the lithium composite transition metal oxide is less than 100nm, because the crystallinity is low, the storage properties may deteriorate sharply at high temperatures, or the gas generation may increase due to side reaction with the electrolyte due to the high specific surface area, or the structure of the positive electrode active material The instability may deteriorate the safety of the positive electrode active material, and when it exceeds 200 nm, the capacity and life characteristics may be significantly reduced.
  • the average particle diameter (D 50 ) of the positive electrode active material particles according to an embodiment of the present invention may be 3 to 50 ⁇ m, more preferably 7 to 20 ⁇ m, most preferably 14 to 18 ⁇ m.
  • the cathode active material according to another embodiment of the present invention may have an average particle diameter (D 50 ) of 3 to 6 ⁇ m, and ⁇ (D 90 ⁇ D 10 ) / D 50 ⁇ may be 0.6 or less.
  • the positive electrode active material of the lithium composite transition metal oxide of the present invention may have a lithium tungsten oxide content of 1,000 ppm or less, more preferably 100 to 700 ppm, most preferably 500 ppm or less.
  • the residual amount of lithium by-products increases on the surface of the positive electrode active material, and the positive electrode active material according to the present invention is washed with water to form lithium tungsten oxide on the surface of the lithium composite transition metal oxide.
  • the content of the remaining lithium tungsten oxide can be 1,000 ppm or less.
  • the method for manufacturing a cathode active material for a lithium secondary battery of the present invention provides a metal solution containing a nickel (Ni) -containing raw material, a cobalt (Co) -containing raw material, a manganese (Mn) -containing raw material, and a tungsten (W) -containing raw material. Doing; Preparing a cathode active material precursor by coprecipitation reaction of the metal solution; Mixing and firing the positive electrode active material precursor and the lithium raw material to prepare a lithium composite transition metal oxide in which a portion of a nickel (Ni) site is substituted with tungsten (W); And washing the calcined lithium composite transition metal oxide to remove lithium tungsten oxide remaining on the surface of the lithium transition metal oxide.
  • the cathode active material for a lithium secondary battery of the present invention dissolves a tungsten (W) -containing raw material in a metal solution in order to replace tungsten (W) at a nickel (Ni) site in a crystal structure, and prepares a cathode active material precursor through a coprecipitation reaction. .
  • the nickel (Ni) -containing raw material may be, for example, nickel-containing acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides or oxyhydroxides, and specifically, Ni (OH) 2 , NiO, NiOOH, NiCO 3 ⁇ 2Ni (OH) 2 ⁇ 4H 2 O, NiC 2 O 2 ⁇ 2H 2 O, Ni (NO 3 ) 2 ⁇ 6H 2 O, NiSO 4 , NiSO 4 ⁇ 6H 2 O, fatty acid nickel salts, nickel halides Or a combination thereof, but is not limited thereto.
  • the cobalt-containing raw material may be cobalt-containing acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide, and the like, specifically, Co (OH) 2 , CoOOH, Co (OCOCH 3 ) 2. 4H 2 O, Co (NO 3 ) 2 6H 2 O, Co (SO 4 ) 2 It may be a combination of 7H 2 O or a combination thereof, but is not limited thereto.
  • the manganese-containing raw material may be, for example, manganese-containing acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides, oxyhydroxides, or combinations thereof, specifically Mn 2 O 3 , MnO 2 Manganese oxides such as Mn 3 O 4 and the like; Manganese salts such as MnCO 3 , Mn (NO 3 ) 2 , MnSO 4 , manganese acetate, manganese dicarboxylic acid, manganese citrate, fatty acid manganese; Manganese oxy hydroxide, manganese chloride or a combination thereof, but is not limited thereto.
  • the tungsten (W) -containing raw material may be, for example, tungsten-containing acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides, oxyhydroxides, or combinations thereof, specifically sodium tungstate (Na 2).
  • WO 4 tungsten oxide
  • WO 3 tungstic acid
  • H 2 WO 4 tungstic acid
  • aluminum (Al) -containing raw materials may be further included.
  • it may be aluminum containing acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides, oxyhydroxides or combinations thereof, and specifically, AlSO 4 , AlCl 3 , Al-isopropoxide. , AlNO 3 Or combinations thereof, but is not limited thereto.
  • the metal solution may be a mixture of a nickel (Ni) -containing raw material, a cobalt (Co) -containing raw material, a manganese (Mn) -containing raw material and a tungsten (W) -containing raw material uniformly mixed with a solvent, specifically water or water.
  • a solvent specifically water or water.
  • the metal solution may contain 0.01 to 1.0 tungsten (W) -containing raw material for the entire nickel (Ni) -containing raw material, cobalt (Co) -containing raw material, manganese (Mn) -containing raw material, and tungsten (W) -containing raw material.
  • Mol% more preferably 0.01 to 0.8 mol%, most preferably 0.05 to 0.5 mol%.
  • the positive electrode active material precursor may be prepared by co-precipitation reaction by adding an ammonium cation-containing complex forming agent and a basic compound to the metal solution.
  • the ammonium cation-containing complex former may be, for example, NH 4 OH, (NH 4 ) 2 SO 4 , NH 4 NO 3 , NH 4 Cl, CH 3 COONH 4 , NH 4 CO 3, or a combination thereof. It is not limited to this.
  • the ammonium cation-containing complex forming agent may be used in the form of an aqueous solution, wherein a solvent may be a mixture of water or an organic solvent (specifically, alcohol, etc.) that can be uniformly mixed with water.
  • the basic compound is NaOH, KOH or Ca (OH) 2 Hydroxides of alkali metals or alkaline earth metals, such as hydrates thereof, or combinations thereof.
  • the basic compound may also be used in the form of an aqueous solution, and as the solvent, a mixture of water or an organic solvent (specifically, alcohol, etc.) that can be uniformly mixed with water may be used.
  • the basic compound is added to adjust the pH of the reaction solution, and may be added in an amount such that the pH of the metal solution is 11 to 13.
  • the coprecipitation reaction may be carried out at a temperature of 40 to 70 °C under an inert atmosphere such as nitrogen or argon.
  • the cathode active material precursor prepared as described above may be represented by the following Chemical Formula 2.
  • 0 ⁇ x2 ⁇ 0.2, 0 ⁇ y2 ⁇ 0.2, 0 ⁇ z2 ⁇ 0.2, and M 1 may be at least one selected from the group consisting of Mn and Al.
  • the positive electrode active material precursor prepared in the present invention is a high concentration of nickel (Ni) that satisfies 0 ⁇ x2 + y2 + z2 ⁇ 0.2, that is, the molar ratio of nickel (Ni) in the total molar ratio of the transition metal is 0.8 or more ( high-nickel) positive electrode active material precursor.
  • the content of Ni, Co, Mn and W may be applied in the same manner as in the cathode active material of the lithium composite transition metal oxide described above.
  • the positive electrode active material precursor and the lithium-containing raw material are mixed and calcined to produce a lithium composite transition metal oxide in which a portion of the nickel (Ni) site is substituted with tungsten (W).
  • 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 alone or a mixture of two or more thereof may be used.
  • 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
  • the firing temperature may be 700 to 900 °C, more preferably 750 to 850 °C, most preferably 780 to 820 °C. If the firing temperature is less than 700 °C due to insufficient reaction, the raw material remains in the particles may reduce the high temperature stability of the battery, the bulk density and crystallinity may be lowered structural stability, may exceed 900 °C Uneven growth of the particles can occur.
  • Lithium composite transition metal oxide prepared as described above has a large crystal size, even though it contains a high content of nickel (Ni) when firing at a high temperature because part of the nickel (Ni) site in the crystal structure is replaced by tungsten (W). Can be prevented.
  • the lithium composite transition metal oxide is prepared as described above, the lithium composite transition metal oxide is washed with water to remove lithium by-products, particularly lithium tungsten oxide, remaining on the surface of the lithium transition metal oxide.
  • the washing step may be performed, for example, by adding a lithium composite transition metal oxide to pure water and stirring.
  • the water washing may be performed using 50 to 100 parts by weight of pure water based on 100 parts by weight of the lithium composite transition metal oxide.
  • the amount of pure water is less than 50 parts by weight with respect to 100 parts by weight of the lithium composite transition metal oxide during washing, insufficient cleaning may be insufficient to remove lithium by-products.
  • the amount of lithium dissolving in the wash water may be increased.
  • the amount of lithium dissolving in the crystal structure when the pure water content is too large This remarkably increases, leading to a sharp decrease in battery capacity and lifespan.
  • 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 cathode active material of the lithium composite transition metal oxide according to the embodiment of the present invention prepared as described above may contain 10 to 5,000 ppm of tungsten (W) in the crystal structure, and the content of lithium tungsten oxide remaining on the particle surface is 1,000. By lowering it to ppm, it is possible to realize high capacity, improve resistance, and to ensure lifetime characteristics and high temperature safety.
  • 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 cathode active material may be included in an amount of 80 to 99 wt%, more specifically 85 to 98 wt%, based on the total weight of the cathode 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 wt% based on the total weight of the cathode 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 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.
  • the molar ratio of NiSO 4 , CoSO 4 , MnSO 4 , AlSO 4 and Na 2 WO 4 is nickel: cobalt: manganese: aluminum: tungsten 85.857: 9.995: 1.999: 1.999
  • a metal solution of 2M concentration was prepared by mixing in water in an amount such that a molar ratio of: 0.15.
  • the metal solution was poured into 300 ml / min, NaOH aqueous solution 300 ml / min, and NH 4 OH aqueous solution at a rate of 60 ml / min, and the coprecipitation reaction was carried out for 12 hours to obtain a positive electrode active material precursor Ni 0.85857 Co 0.09995 Mn 0.01999 W 0.0015 Al 0.01999 (OH) 2 was prepared.
  • Lithium hydroxide (LiOH) was mixed in the positive electrode active material precursor at a molar ratio of 1: 1.02, and then calcined at 800 ° C. for about 10 hours to form lithium composite transition metal oxide Li (Ni 0.85857 Co 0.09995 Mn 0.01999 W 0.0015 Al 0.01999 ) O 2 was prepared.
  • NiSO 4 , CoSO 4 , MnSO 4 And AlSO 4 were mixed in water in an amount such that the molar ratio of nickel: cobalt: manganese: aluminum was 86: 10: 2: 2 to prepare a metal solution of 2M concentration.
  • the metal solution was added to 300 ml / min, NaOH aqueous solution to 300 ml / min, and NH 4 OH aqueous solution at a rate of 60 ml / min, and the coprecipitation reaction was performed for 12 hours to obtain a cathode active material precursor Ni 0.86 Co 0.1 Mn 0.02 Al 0.02 (OH 2 ) was prepared.
  • Lithium hydroxide (LiOH) was mixed in the positive electrode active material precursor at a molar ratio of 1: 1.02, and then calcined at 800 ° C. for about 10 hours to prepare a lithium composite transition metal oxide Li (Ni 0.86 Co 0.1 Mn 0.02 Al 0.02 ) O 2 . It was.
  • Lithium composite transition metal oxide, and Li is carried out in the same manner as in Example 1, except that the (Ni 0. 85857 Co 0. 09995 Mn 0 .01999 W 0. 0015 Al 0. 01999) O 2 did not proceed to the manufacture, and washed with water To prepare a positive electrode active material.
  • LiOH Lithium hydroxide
  • the positive electrode active material samples prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were aliquoted to about 0.05 g in the vial, and weighed accurately. Then, 2 mL of hydrochloric acid and 0.5 mL of hydrogen peroxide were added, followed by heating at 130 ° C. for 4 hours. The sample was completely dissolved. When the sample was sufficiently dissolved, 0.1 mL of Internal STD (Sc) was added and diluted to 10 mL with ultrapure water. Then, the ICP analysis measured value using ICP-OES (Perkin Elmer, OPTIMA 7300DV) is shown in Table 1 below.
  • ICP-OES Perkin Elmer, OPTIMA 7300DV
  • lithium tungsten oxide (Li 2 WO 4 ) of the positive electrode active material prepared in Examples 1, 2 and Comparative Examples 1 to 3 was measured and shown in Table 1 below.
  • the positive electrode active materials of Examples 1 and 2 had a crystal size of 200 nm or less, whereas in Comparative Examples 1 and 3, the crystal size increased significantly above 200 nm, resulting in d / 1,000c of less than 0.05.
  • Each positive electrode active material, carbon black conductive material and PVdF binder prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were mixed in an N-methylpyrrolidone solvent at a ratio of 95: 2.5: 2.5 by weight in a positive electrode mixture. (Viscosity: 5000 mPa ⁇ s) was prepared and applied to one surface of an aluminum current collector, dried at 130 ° C., and rolled to prepare a positive electrode.
  • a negative electrode active material 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 by weight to prepare a composition for forming a negative electrode active material layer, and the 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 discharge capacity of the lithium secondary battery manufactured as described above is shown in Table 2 below.
  • Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Discharge Capacity (mAh / g) 199-200 200-210 180-190 190-195 180-185
  • the 2C discharge terminal profile resistance was improved as compared to the lithium secondary battery prepared by using the cathode active material of Comparative Example 1, which was not doped with tungsten (W). You can check it.
  • the lithium secondary battery prepared by using the positive electrode active materials of Example 2 and Comparative Example 1 was subjected to 30 cycles of charge and discharge at 45 ° C. under a charge end voltage of 4.25V, a discharge end voltage of 2.5V, and 0.3C. %]) was measured, and the measurement results are shown in FIG. 2.

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Abstract

La présente invention concerne un matériau actif de cathode qui est destiné à une pile rechargeable au lithium et qui comprend un oxyde de métal de transition composite de lithium contenant du nickel (Ni), du cobalt (Co) et du manganèse (Mn), l'oxyde de métal de transition composite de lithium ayant une partie d'un emplacement de nickel (Ni) substitué par du tungstène (W) et une teneur inférieure ou égale à 1 000 ppm d'un oxyde de lithium-tungstène restant sur la surface de ses particules.
PCT/KR2018/002505 2017-02-28 2018-02-28 Matériau actif de cathode pour pile rechargeable au lithium, son procédé de fabrication et pile rechargeable au lithium comprenant ledit matériau WO2018160023A1 (fr)

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EP18760273.5A EP3522272B1 (fr) 2017-02-28 2018-02-28 Matériau actif de cathode pour pile rechargeable au lithium, son procédé de fabrication et pile rechargeable au lithium comprenant ledit matériau
PL18760273.5T PL3522272T3 (pl) 2017-02-28 2018-02-28 Materiał czynny katody dla akumulatora litowego, sposoby ich wytwarzania oraz akumulator litowy
JP2019529180A JP6786146B2 (ja) 2017-02-28 2018-02-28 リチウム二次電池用正極活物質、その製造方法、およびそれを含むリチウム二次電池
US16/347,742 US11152617B2 (en) 2017-02-28 2018-02-28 Positive electrode active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including the positive electrode active material
CN201880010581.3A CN110268561B (zh) 2017-02-28 2018-02-28 锂二次电池用正极活性材料、其制备方法及包含该正极活性材料的锂二次电池
US17/476,673 US11532815B2 (en) 2017-02-28 2021-09-16 Positive electrode active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including the positive electrode active material

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CN113490644A (zh) * 2019-03-05 2021-10-08 株式会社Lg化学 制备锂二次电池用正极活性材料前体的方法和通过所述方法制备的正极活性材料前体
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CN115053367A (zh) * 2020-02-21 2022-09-13 宁德新能源科技有限公司 正极材料和包含所述正极材料的电化学装置
CN115881907A (zh) * 2022-09-30 2023-03-31 巴斯夫杉杉电池材料有限公司 一种锂离子电池正极活性材料及其制备方法和NiO的检测方法
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