WO2015053580A1 - Matière active d'anode pour batterie rechargeable au lithium, son procédé de fabrication et batterie rechargeable au lithium comprenant ladite matière - Google Patents

Matière active d'anode pour batterie rechargeable au lithium, son procédé de fabrication et batterie rechargeable au lithium comprenant ladite matière Download PDF

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WO2015053580A1
WO2015053580A1 PCT/KR2014/009516 KR2014009516W WO2015053580A1 WO 2015053580 A1 WO2015053580 A1 WO 2015053580A1 KR 2014009516 W KR2014009516 W KR 2014009516W WO 2015053580 A1 WO2015053580 A1 WO 2015053580A1
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lithium
active material
phosphorus
positive electrode
electrode active
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English (en)
Korean (ko)
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최수안
이승원
최창민
권수연
조성우
안지선
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주식회사 엘앤에프신소재
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • It relates to a positive electrode active material for a lithium secondary battery, a production method thereof and a lithium secondary battery.
  • Lithium-containing cobalt oxide (LiCoO 2 ) is mainly used as a positive electrode active material of a lithium secondary battery.
  • lithium-containing manganese oxides such as LiMnO 2 in a layered crystal structure and LiMn 2 O 4 in a spinel crystal structure, and lithium-containing nickel oxide
  • (LiNiO 2 ) is also contemplated.
  • LiCoO 2 is widely used due to its excellent physical properties such as excellent cycle characteristics, but it is low in safety and expensive due to resource limitations of cobalt as a raw material, and is a large power source for fields such as electric vehicles and hybrid electric vehicles. There is a limit to use.
  • Lithium manganese oxides such as LiMnO 2 and LiMn 2 O 4 have the advantage of using a resource-rich and environmentally friendly manganese as a raw material, attracting a lot of attention as a cathode active material that can replace LiCoO 2 .
  • lithium manganese oxides have the disadvantages of low capacity and poor cycle characteristics at high temperatures.
  • lithium nickel-based oxides are less expensive than cobalt-based oxides and exhibit high discharge capacity when charged to 4.3 V.
  • the reversible capacity of doped lithium nickel-based oxides exceeds the capacity of LiCoO 2 (about 165 mAh / g). Approx. 200 mAh / g. Therefore, despite the slightly lower discharge voltage and volumetric density, commercialized batteries including nickel-based positive electrode active materials have improved energy density, and thus, researches on such nickel-based positive electrode active materials have recently been conducted to develop high capacity batteries. It is actively underway.
  • the nickel-based positive electrode active material has a problem in that a volume change occurs during a charge and discharge cycle and a sudden phase transition occurs thereby causing crystal structure collapse.
  • a volume change occurs during a charge and discharge cycle and a sudden phase transition occurs thereby causing crystal structure collapse.
  • LG Chem in this case lithium by excess lithium source
  • the present invention provides a positive electrode active material for a lithium secondary battery having a reduced amount of residual lithium and a method of manufacturing the same, and provides a lithium secondary battery having improved performance such as life characteristics.
  • the core comprising a compound represented by the following formula (1); And a solid solution disposed on the surface of the core and containing lithium (Li), phosphorus (P), and oxygen (O).
  • M 1 and M 2 are different from each other, Al, B, Mg, Ti, or Zr, 95 ⁇ x ⁇ 1.2, 0 ⁇ a ⁇ 0.4, 0 ⁇ b ⁇ 0.4, 0 ⁇ c ⁇ 0.01, 0 ⁇ d ⁇ 0.01, and 0 ⁇ a + b + c + d ⁇ 0.4.
  • the solid solution contains lithium (Li) and phosphorus (P) and oxygen (O), and may be, for example, in the form of Li 3 PO 4 , Li 4 P 2 O 7 or other compound in which Li, P, and O are bonded.
  • the position of the energy at which the intensity of the peak due to the phosphorus (P) atom of the solid solution becomes maximum is 133 eV to 135 eV. Which is an important requirement in the present invention.
  • the amount of lithium remaining in the cathode active material may be 50% or less than the amount of lithium remaining in the core before including the solid solution.
  • Total Lithium, TTL Total Lithium
  • the compound additive containing lithium and phosphorus It may be in the form of a compound in which lithium (Li), phosphorus (P), and oxygen (O) are essentially bound and hydrogen (H) is selectively bonded.
  • the compound additive containing the lithium and phosphorus is, for example Li 2 P 2 O 6, LiH 2 PO 4 , or a combination thereof.
  • the compound additive containing lithium and phosphorus may be added so that the content of phosphorus (P) is 0.05 to 0.5 parts by weight based on 100 parts by weight of the compound represented by Chemical Formula 1.
  • a solid solution containing lithium, phosphorus, and oxygen may be formed on the surface of the compound represented by Chemical Formula 1 by the heat treatment.
  • the heat treatment may be performed at 300 ° C to 500 ° C.
  • Another embodiment of the present invention provides a lithium secondary battery including a cathode, an anode, and an electrolyte including the cathode active material.
  • the content of lithium remaining on the surface of the positive electrode active material is reduced to improve performance such as life characteristics of the lithium secondary battery.
  • Example 1 is an X-ray photoelectron spectroscopic analysis graph of the positive electrode active material of Example 3 and Comparative Example 3.
  • a positive electrode active material for a lithium secondary battery including a core including a compound represented by Chemical Formula 1, and a solid solution disposed on a surface of the core and containing lithium (Li), phosphorus (P), and oxygen (O).
  • M 1 and M 2 are different from each other, Al, B, Mg, Ti, or Zr, 0.95 ⁇ x ⁇ 1.2, 0 ⁇ a ⁇ 0.4, 0 ⁇ b ⁇ 0.4, 0 ⁇ c ⁇ 0.01, 0 ⁇ d ⁇ 0.01, and 0 ⁇ a + b + c + d ⁇ 0.4
  • the amount of lithium remaining in the cathode active material is significantly reduced.
  • the lithium secondary battery including the same has improved life characteristics.
  • the compound represented by Chemical Formula 1 is a lithium nickel metal composite oxide, and is a nickel rich oxide.
  • 1-a-b-c-d which is a molar ratio of nickel
  • the molar ratio of nickel may be 0.65 to 1.0, 0.7 to 1.0, 0.8 to 1.0, 0.6 to 0.9, and 0.7 to 0.9.
  • 0 ⁇ a + b + c + d ⁇ 0.4 0 ⁇ a + b + c + d ⁇ 0.3
  • 0 ⁇ a + b + c + d ⁇ 0.2 0 ⁇ a + b + c + d ⁇ 0.4
  • 0.1 ⁇ a + b + c + d ⁇ 0.4 0.1 ⁇ a + b + c + d ⁇ 0.3.
  • Such a nickel-rich cathode active material can implement high rate charge / discharge characteristics and high rate output characteristics, and particularly, as the nickel content increases, the energy density is high and it is advantageous in terms of price.
  • the nickel-rich cathode active material may have problems such as side reactions with the electrolyte due to the lithium-containing compound remaining as the charge and discharge cycle proceeds.
  • the cathode active material according to the embodiment may contain 60% or more of nickel, and the remaining lithium content may be significantly reduced.
  • x is a molar ratio of lithium (Li), wherein 0.95 ⁇ x ⁇ 1.2.
  • Formula 1 may include cobalt (Co), a may be a molar ratio of cobalt 0 ⁇ a ⁇ 0.4 and specifically 0.1 ⁇ a ⁇ 0.4, 0.1 ⁇ a ⁇ 0.3.
  • Formula 1 may include manganese (Mn), b may be a mole ratio of manganese 0 ⁇ a ⁇ 0.4 and specifically 0.1 ⁇ b ⁇ 0.4, 0.1 ⁇ b ⁇ 0.3.
  • Formula 1 may further contain one or more elements from Al, B, Mg, Ti, or Zr. Due to the doping, the low temperature (approximately 5 ° C.) life characteristics are greatly improved, and the thermal stability is improved, thereby moving the maximum heat generation temperature toward the high temperature and reducing the amount of heat generated.
  • One example may include zirconium Zr.
  • the core may be a Ni-based positive electrode active material containing an excessive amount of Ni in an active material of 60% or more.
  • a cathode active material has a structure in which a solid solution is formed on a surface of the core, and the solid solution includes lithium, phosphorus, and oxygen.
  • the solid solution may be, for example, Li 3 PO 4 , Li 4 P 2 O 7 or another compound in which Li, P, and O are bonded.
  • the position of the energy at which the intensity of the peak due to the phosphorus (P) atom of the solid solution becomes maximum may be 133 eV to 135 eV.
  • the position of energy that maximizes the peak intensity varies depending on the bonding state of lithium (Li), phosphorus (P), and oxygen (O).
  • the energy at which the peak intensity attributable to the phosphorus (P) atom is maximized is at a position in the range of 133 eV to 135 eV, and the lithium (Li) and phosphorus (P) atoms present on the surface of the compound represented by Formula 1 This means that the oxygen (O) atom has a chemical bond.
  • the remaining lithium may be present in the form of Li 2 CO 3 , LiOH, and the like.
  • the amount of lithium remaining in the cathode active material may be 50% or less than the amount of lithium remaining in the core before including the solid solution. That is, the amount of lithium remaining in the positive electrode active material including the solid solution and the core represented by Formula 1 is 50 of the amount of lithium remaining in the positive electrode active material including the core represented by Formula 1 without including the solid solution. It may be less than or equal to%.
  • total lithium, TTL total lithium
  • the cathode active material according to the exemplary embodiment may reduce the amount of lithium remaining, thereby inhibiting side reactions with the electrolyte and improving battery life characteristics.
  • a method of manufacturing a cathode active material for a lithium secondary battery comprising mixing the compound represented by Chemical Formula 1, and a compound additive containing lithium and phosphorus, and heat treating the mixture of the above steps.
  • a cathode active material including a core including the compound represented by Formula 1 and a solid solution containing lithium, phosphorus, and oxygen on the surface of the core may be manufactured.
  • the cathode active material according to the manufacturing method of the present invention may reduce the amount of lithium remaining to improve the performance of the battery.
  • the compound additive containing lithium and phosphorus is, for example, Li 2 P 2 O 6, LiH 2 PO 4 or other compounds in which Li and P and O are essential and H is selectively bonded.
  • the compound additive containing lithium and phosphorus may be added in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of the compound represented by Chemical Formula 1. Specifically, 0.1 to 0.3 parts by weight may be added. In this case, lithium remaining in the cathode active material may be effectively reduced.
  • the mixing step may be specifically carried out by a dry mixing method.
  • the compound additive containing lithium and phosphorus may be attached to the surface of the compound represented by the formula (1).
  • a solid solution containing lithium, phosphorus, and oxygen may be formed on the surface of the compound represented by Chemical Formula 1.
  • the solid solution thus formed may be, for example, Li 3 PO 4 , Li 4 P 2 O 7, or the like.
  • the compound containing lithium (Li) and phosphorus (P) is Li 2 CO 3 and LiOH remaining on the surface of the compound represented by the formula (1) than the compound containing only phosphorus (P) except lithium (Li) and Has high reactivity.
  • the heat treatment may be performed at 300 ° C to 500 ° C, specifically 350 ° C to 450 ° C.
  • This is a temperature range for producing a solid solution
  • the compound additive containing lithium and phosphorus may be fused to the surface of the compound represented by Formula 1 in the process of heating up to the range, in the process of maintaining the temperature range
  • Compound additives containing lithium and phosphorus may form a solid solution by reacting with lithium remaining on the surface of the compound represented by Chemical Formula 1.
  • the dry mixed powder was heat-treated at 890 ° C. for 8 hours to prepare a lithium composite compound.
  • LiH 2 PO 4 1000 ppm of LiH 2 PO 4 was added to the Zr-doped lithium composite compound obtained in Preparation Example 1 as a compound additive including lithium (Li) and phosphorus (P), followed by dry mixing to uniformly adhere to the surface of the lithium composite compound. . Thereafter, the mixed powder was heat treated at 400 ° C. for 6 hours to prepare a cathode active material in which a compound including lithium (Li), phosphorus (P), and oxygen (O) was dissolved in the surface.
  • a positive electrode active material was prepared in the same manner as in Example 1, except that 2000 ppm of the compound additive LiH 2 PO 4 including Li and P was added.
  • a positive electrode active material was manufactured in the same manner as in Example 1, except that 3000 ppm of LiH 2 PO 4 was added as a compound additive including lithium (Li) and phosphorus (P).
  • a positive electrode active material was manufactured in the same manner as in Example 3, except that the compound additive including lithium (Li) and phosphorus (P) was added through Preparation Example 4.
  • LiH 2 PO 4 1000 ppm of LiH 2 PO 4 was added to the Zr-doped lithium composite compound obtained in Preparation Example 2 as a compound additive including lithium (Li) and phosphorus (P), followed by dry mixing to uniformly adhere to the surface of the lithium composite compound. . Thereafter, the mixed powder was heat treated at 400 ° C. for 6 hours to prepare a cathode active material in which a compound including lithium (Li), phosphorus (P), and oxygen (O) was dissolved in the surface.
  • a positive electrode active material was manufactured in the same manner as in Example 5, except that 2000 ppm of LiH 2 PO 4 was added as a compound additive including lithium (Li) and phosphorus (P) in Example 5.
  • a positive electrode active material was manufactured in the same manner as in Example 5, except that 3000 ppm of LiH 2 PO 4 was added as a compound additive including lithium (Li) and phosphorus (P) in Example 5.
  • a positive electrode active material was manufactured in the same manner as in Example 7, except for adding the compound additive obtained through Preparation Example 4 as a compound additive including lithium (Li) and phosphorus (P) in Example 7.
  • LiH 2 PO 4 1000 ppm of LiH 2 PO 4 was added to the Zr-doped lithium composite compound obtained in Preparation Example 3 as a compound additive including lithium (Li) and phosphorus (P), followed by dry mixing to uniformly adhere to the surface of the lithium composite compound. . Thereafter, the mixed powder was heat treated at 400 ° C. for 6 hours to prepare a cathode active material in which a compound including lithium (Li), phosphorus (P), and oxygen (O) was dissolved in the surface.
  • a positive electrode active material was manufactured in the same manner as in Example 9, except that 2000 ppm of LiH 2 PO 4 was added as a compound additive including lithium (Li) and phosphorus (P) in Example 9.
  • a positive electrode active material was manufactured in the same manner as in Example 9, except that 3000 ppm of LiH 2 PO 4 was added as a compound additive including lithium (Li) and phosphorus (P) in Example 9.
  • a positive electrode active material was manufactured in the same manner as in Example 11, except that Example 11 was added as a compound additive including lithium (Li) and phosphorus (P).
  • the material obtained in Preparation Example 1 was used as a cathode active material.
  • the material obtained in Preparation Example 2 was used as a cathode active material as it is.
  • the material obtained in Preparation Example 3 was used as a cathode active material as it is.
  • the material obtained in Preparation Example 1 was calcined once more at 700 ° C. for 6 hours without adding a compound additive including lithium (Li) and phosphorus (P) to be used as a cathode active material.
  • the material obtained in Preparation Example 3 was calcined once more at 700 ° C. for 6 hours without adding compound additives including lithium (Li) and phosphorus (P) to be used as a cathode active material.
  • a positive electrode active material was prepared in the same manner as in Example 3, except that (NH 4 ) 3 PO 4 was used instead of the compound additive including lithium (Li) and phosphorus (P) in Example 3.
  • a cathode active material was manufactured in the same manner as in Example 7, except that (NH 4 ) 3 PO 4 was used instead of the compound additive including lithium (Li) and phosphorus (P) in Example 7.
  • a positive electrode active material was prepared in the same manner as in Example 11, except that (NH 4 ) 3 PO 4 was used instead of the compound additive including Li and P in Example 11.
  • Example 1 Li content Metal content Doping element M Li and P-containing compound additives Refiring Temperature (°C) Remarks Ni Co Mn Kinds Content (ppm) Kinds Content (ppm)
  • Example 1 1.02 0.6 0.2 0.2 Zr 1500 LiH 2 PO 4 1000 400 60, 1000
  • Example 2 1.02 0.6 0.2 0.2 Zr 1500 LiH 2 PO 4 2000 400 60, 2000
  • Example 3 1.02 0.6 0.2 0.2 Zr 1500 LiH 2 PO 4 3000 400 60, 3000
  • Example 4 1.02 0.6 0.2 0.2 Zr 1500 Li 2 P 2 O 6 3000 400 LiP source change
  • Example 5 1.02 0.7 0.15 0.15 Zr 1500 LiH 2 PO 4 1000 400 70, 1000
  • Example 6 1.02 0.7 0.15 0.15 Zr 1500 LiH 2 PO 4 2000 400 70, 2000
  • Example 7 1.02 0.7 0.15 0.15 Zr 1500 LiH 2 PO 4 3000 400 70, 3000
  • Example 8 1.02 0.7 0.15 0.15 Zr 1500 Li 2 P 2 O 6 3000 400
  • Evaluation example 1 X-ray photoelectron spectroscopy (X- ray Photoelectron Spectroscopy ; XPS )
  • Example 3 XPS analysis of the cathode active materials prepared in Example 3 and Comparative Example 3 shows the results in FIG. 1.
  • FIG. 1 in the case of Example 3, it can be seen that the position of the energy at which the peak intensity due to the phosphorus (P) atom becomes the maximum ranges from 133 eV to 135 eV. Through this, it can be seen that lithium, phosphorus and oxygen atoms remaining on the surface of the positive electrode active material are in a chemical bonding state.
  • the amount of lithium remaining in the cathode active materials prepared in Examples and Comparative Examples is measured separately for each compound containing Li (eg, LiOH or Li 2 CO 3 ) remaining by the potentiometric neutralization method, and then separately calculates the total amount of Li alone. It was set as the value (TTL, Total Lithium).
  • Li eg, LiOH or Li 2 CO 3
  • Equation 1 The calculation method is shown in Equation 1 below.
  • a positive electrode slurry was prepared by adding to 5.0 wt%.
  • the positive electrode slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of 20 to 40 ⁇ m, vacuum dried, and roll pressed to prepare a positive electrode.
  • Al aluminum
  • Li-metal was used as the negative electrode.
  • a half cell of a coin cell type was prepared by using a cathode and a lithium metal as described above, and 1.15 M LiPF 6 and ethylene carbonate (EC): dimethyl carbonate (DMC) (1: 1 vol%) as an electrolyte. .
  • Capacity of 1 cycle, 20 cycles and 30 cycles was measured under the conditions of 1 C, and the capacity retention rates at 20 cycles and 30 cycles compared to 1 cycle were evaluated. The results are shown in Table 2 below.
  • Example 9 to 12 are cathode active materials containing 80% of nickel, and it can be seen that the residual lithium content is reduced compared to Comparative Example 3 containing 80% of nickel.

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Abstract

La présente invention concerne une matière active d'anode, son procédé de fabrication et une batterie rechargeable au lithium comprenant ladite matière, la matière active d'anode comportant : un noyau comprenant un composé représenté par la formule chimique 1 ci-dessous ; et une solution solide qui est placée sur la surface du noyau et qui contient du lithium (Li), du phosphore (P) et de l'oxygène (O). [Formule chimique 1] LixNi(1-a-b-c-d)CoaMnbM1 cM2 dO2, la définition de la formule chimique 1 étant telle que spécifiée dans la description.
PCT/KR2014/009516 2013-10-11 2014-10-10 Matière active d'anode pour batterie rechargeable au lithium, son procédé de fabrication et batterie rechargeable au lithium comprenant ladite matière WO2015053580A1 (fr)

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KR102179968B1 (ko) 2017-10-20 2020-11-17 주식회사 엘지화학 리튬 이차전지용 양극 활물질의 제조방법, 이에 의해 제조된 양극 활물질, 이를 포함하는 리튬 이차전지용 양극 및 리튬 이차전지
KR102178876B1 (ko) 2017-10-20 2020-11-13 주식회사 엘지화학 이차전지용 양극활물질의 제조방법 및 이를 이용하는 이차전지
KR102165118B1 (ko) * 2017-10-26 2020-10-14 주식회사 엘지화학 이차전지용 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지
KR102288290B1 (ko) 2018-02-23 2021-08-10 주식회사 엘지화학 이차전지용 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지
KR102231062B1 (ko) * 2018-03-09 2021-03-23 주식회사 엘지화학 양극 활물질, 그 제조 방법, 이를 포함하는 양극 및 이차전지
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