US20140212749A1 - Method for Preparing Positive Electrode Active Material for Lithium Secondary Battery, Positive Electrode Active Material for Lithium Secondary Battery, and Lithium Secondary Battery Including Same - Google Patents

Method for Preparing Positive Electrode Active Material for Lithium Secondary Battery, Positive Electrode Active Material for Lithium Secondary Battery, and Lithium Secondary Battery Including Same Download PDF

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US20140212749A1
US20140212749A1 US14/227,820 US201414227820A US2014212749A1 US 20140212749 A1 US20140212749 A1 US 20140212749A1 US 201414227820 A US201414227820 A US 201414227820A US 2014212749 A1 US2014212749 A1 US 2014212749A1
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chemical formula
positive electrode
electrode active
active material
lithium
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Su An Choi
Seung-Won Lee
Sang-Hoon Jeon
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L&F Co Ltd
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    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
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    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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    • C01D15/02—Oxides; Hydroxides
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    • H01M4/04—Processes of manufacture in general
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    • 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
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    • 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
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    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
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    • Y02E60/10—Energy storage using batteries
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Definitions

  • the present invention relates to a method for preparing a positive electrode active material for a lithium secondary battery, a positive electrode active material for a lithium secondary battery, and a lithium secondary battery including the same.
  • the batteries used as power for the devices need to be have high performance and high capacity.
  • Batteries generate electric power by using materials capable of having an electrochemical reaction at positive and negative electrodes.
  • a representative example is a lithium secondary battery in which electric energy is generated due to a change in a chemical potential when lithium ions are intercalated/deintercalated at positive and negative electrodes.
  • the lithium secondary battery is manufactured by using a material capable of reversibly intercalating/deintercalating lithium ions for positive electrode and negative electrode active materials and charging an organic electrolyte or a polymer electrolyte between a positive electrode and a negative electrode.
  • a lithium composite compound As for the positive electrode active material for the lithium secondary battery, a lithium composite compound is used, and examples thereof may include metal composite oxides such as LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , and LiMnO 2 , which have been researched.
  • Mn-based positive electrode active materials such as LiMn 2 O 4 and LiMnO 2
  • LiMn 2 O 4 and LiMnO 2 are attractive since they are easy to synthesize, are relatively cheap, have relatively excellent thermal stability at the time of overcharging as compared with the other active materials, and have less pollution on environment.
  • these materials have a drawback in that the capacity is small.
  • LiCoO 2 is a representative positive electrode active material that is currently commercialized on the market since it has favorable electrical conductivity and a high battery voltage of about 3.7 V as well as excellent cycle lifespan characteristics, stability, and discharge capacity. However, LiCoO 2 is not priced competitively since it is expensive and thus accounts for 30% or more of the battery price.
  • LiNiO 2 is difficult to synthesize even though it provides the highest charge capacity in the above-mentioned positive electrode active materials. Moreover, the high oxidation state of nickel is a causative factor of deteriorating battery and electrode lifespan characteristics. Moreover, the self discharge of nickel is severe and reversibility of nickel is deteriorated. Moreover, nickel insufficiently secures stability and thus is difficult to commercialize.
  • JP 2011-216485 discloses a positive electrode active material for a lithium secondary battery, in which lithium nickel composite oxides having different particle size distributions and different compositions are mixed.
  • the degree of improvement is explained as a synergy effect due to the physical mixing of different positive electrode active materials.
  • KR2012-0017004 discloses a positive electrode active material for a lithium secondary battery, which is prepared by mixing precursors having different compositions and firing the mixture together with a lithium compound.
  • the firing temperature needs to be varied depending on the compositional ratio of Ni/Co/Mn in order to exhibit the maximum performance for the compositions, the corresponding technology is restricted to a mixture of precursors having very similar compositions.
  • the present invention has been made in an effort to provide a positive electrode active material having advantages of having high capacity and high efficiency as well as improved high-rate characteristic and long lifespan characteristics.
  • An exemplary embodiment of the present invention provides a method for preparing a positive electrode active material for a lithium secondary battery, the method including: preparing a mixture of a precursor represented by Chemical Formula 1 below, a lithium composite oxide represented by Chemical Formula 2 below and capable of intercalating/deintercalating lithium ions, and a lithium feed material; and firing the prepared mixture:
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; and ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05, 0.35 ⁇ 0.5, 0.19 ⁇ 0.34, and 0.31 ⁇ 0.46.
  • the weight ratio of the precursor represented by Chemical Formula 1 to the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be 95/5 to 70/30.
  • the precursor represented by Chemical Formula 1 may have a particle diameter of 8 to 12 ⁇ m.
  • the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may have a particle diameter of 3 to 8 ⁇ m.
  • the lithium feed material may be nitrate, carbonate, acetate, oxalate, oxide, hydroxide, or sulfate, which contains lithium, or a combination thereof.
  • the precursor represented by Chemical Formula 1 may be represented by Chemical Formula 3 below:
  • the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be represented by Chemical Formula 4 below:
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; and ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05, 0.43 ⁇ 0.5, 0.19 ⁇ 0.26, and 0.31 ⁇ 0.38.
  • the firing temperature may be 800 to 1000° C.
  • the particle diameter of the precursor represented by Chemical Formula 1 may be larger than the particle diameter of the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions.
  • the amount of remaining water-soluble lithium after the firing of the prepared mixture may be reduced to 20 to 50% based on the amount of remaining water-soluble lithium when the precursor represented by Chemical Formula 1 is fired alone.
  • the surface Ni content of a positive electrode active material derived from Chemical Formula 1 may be further reduced than the surface Ni content of a positive electrode active material prepared by firing the precursor represented by Chemical Formula 1 alone.
  • the surface Ni content of the positive electrode active material derived from Chemical Formula 1 may be further reduced by less than 5% than the surface Ni content of the positive electrode active material prepared by firing the precursor represented by Chemical Formula 1 alone.
  • the standard deviation of the Ni content may be smaller than 1.00.
  • a positive electrode active material for a lithium secondary battery including: a lithium composite oxide represented by Chemical Formula 5 below and capable of intercalating/deintercalating lithium ions; and a lithium composite oxide represented by Chemical Formula 2 below and capable of intercalating/deintercalating lithium ions, wherein the lithium composite oxide represented by Chemical Formula 5 below and capable of intercalating/deintercalating lithium ions is prepared from a precursor, and wherein the surface Ni content of the lithium composite oxide represented by Chemical Formula 5 below and capable of intercalating/deintercalating lithium ions is further reduced than the surface Ni content of a lithium composite oxide prepared by firing the precursor alone:
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; and ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05, 0.5 ⁇ 0.64, 0.15 ⁇ 0.29, and 0.21 ⁇ 0.35, and
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; and ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05, 0.35 ⁇ 0.5, 0.19 ⁇ 0.34, and 0.31 ⁇ 0.46.
  • the particle diameter of the lithium composite oxide represented by Chemical Formula 5 and capable of intercalating/deintercalating lithium ions may be larger than the particle diameter of the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions.
  • the lithium composite oxide expressed by Chemical Formula 5 and capable of intercalating/deintercalating lithium ions may have a particle diameter of 8 to 12 ⁇ m.
  • the lithium composite oxide expressed by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may have a particle diameter of 3 to 8 ⁇ m.
  • the weight ratio of the lithium composite oxide represented by Chemical Formula 5 and capable of intercalating/deintercalating lithium ions to the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be 95/5 to 70/30.
  • the lithium composite oxide represented by Chemical Formula 5 and capable of intercalating/deintercalating lithium ions may be represented by Chemical Formula 6 below:
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; and ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05, 0.50 ⁇ 0.61, 0.15 ⁇ 0.26, and 0.24 ⁇ 0.35.
  • the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be represented by Chemical Formula 4 below:
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; and ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05, 0.43 ⁇ 0.5, 0.19 ⁇ 0.26, and 0.31 ⁇ 0.38.
  • Yet another embodiment of the present invention provides a lithium secondary battery including a positive electrode, an anode, and an electrolyte, wherein the positive electrode includes a current collector and a positive electrode active material layer formed on the current collector, and wherein the positive electrode active material layer contains the above-described positive electrode active material according to an embodiment of the present invention.
  • a positive electrode active material having high capacity and high efficiency as well as improved high-rate characteristics and long lifespan characteristics.
  • FIG. 1 is a schematic view of a lithium secondary battery
  • FIG. 2 is a discharge graph showing rate characteristics of a battery of Example 1.
  • a method for preparing a positive electrode active material for a lithium secondary battery including: preparing a mixture of a precursor represented by Chemical Formula 1 below, a lithium composite oxide represented by Chemical Formula 2 below and capable of intercalating/deintercalating lithium ions, and a lithium feed material; and firing the prepared mixture:
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; and ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05, 0.35 ⁇ 0.5, 0.19 ⁇ 0.34, and 0.31 ⁇ 0.46.
  • the prepared positive electrode active material has two different composition groups of Ni ⁇ Co ⁇ Mn ⁇ , and, of the particles having the two compositions, a particle having a higher Ni content may be a positive electrode active material particle in which the Ni content is higher in an inside than a surface.
  • the lithium feed material when the lithium feed material is added to the mixture of the precursor and the lithium composite oxide and then the firing is conducted, the lithium feed material reacts with the precursor and the lithium composite oxide.
  • the mixing of active materials according to the conventional art corresponds to simple physical mixing, which has some limitations in the improvement of powder characteristics and battery characteristics.
  • the chemical reaction of the precursor, the lithium composite compound (e.g., heterogeneous active material), and Li is performed by mixing a lithium feed material with the precursor and the lithium composite compound, which have different compositions of Ni ⁇ Co ⁇ Mn ⁇ , followed by firing, so that the chemical reaction of the precursor, lithium composite oxide, and lithium leads to a concentration gradient between two different compositions of Ni ⁇ Co ⁇ Mn ⁇ .
  • lithium reacts with a composition having a higher Mn content more selectively due to the presence of Mn which has been known to have excellent reactivity with lithium, thereby fundamentally preventing the generation of remaining water-soluble lithium in the composition having a higher Ni content.
  • the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions has a higher Mn content and a smaller particle diameter than the precursor represented by Chemical Formula 1, Mn elution is more likely to occur. Therefore, the Mn elution can be controlled by appropriately adjusting the mixed ratio of the lithium composite oxide having a higher Mn content.
  • the particle diameter of the precursor represented by Chemical Formula 1 may be 8 to 12 ⁇ m.
  • the particle diameter of the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be 3 to 8 ⁇ m.
  • the lithium feed material is nitrate, carbonate, acetate, oxalate, oxide, hydroxide, or sulfate, which contains lithium, or a combination thereof, but is not limited thereto.
  • Chemical Formula 1 More specifically, the precursor represented by Chemical Formula 1 may be represented by Chemical Formula 3 below:
  • lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be represented by Chemical Formula 4 below:
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, and 0 ⁇ b ⁇ 0.05; and 0.43 ⁇ 0.5, 0.19 ⁇ 0.26, and 0.31 ⁇ 0.38.
  • the firing temperature may be 800 to 1000° C.
  • the range may be appropriate to simultaneously fire the precursor and the lithium composite oxide according to an embodiment of the present invention.
  • the amount of remaining water-soluble lithium after the firing of the prepared mixture may be 20 to 50% based on the amount of remaining water-soluble lithium when the precursor represented by Chemical Formula 1 is fired alone.
  • the reduction of the remaining lithium can solve many of problems, such as instability of electrode plate slurry and gas generation after application to the battery, which result from a high amount of remaining lithium in the conventional art.
  • the surface Ni content of a positive electrode active material derived from Chemical Formula 1 may be further reduced than the surface Ni content of a positive electrode active material prepared by firing the precursor represented by Chemical Formula 1 alone.
  • the surface Ni content of the positive electrode active material derived from Chemical Formula 1 may be further reduced by less than 5% than the surface Ni content of the positive electrode active material prepared by firing the precursor represented by Chemical Formula 1 alone.
  • the standard deviation of the Ni content may be smaller than 1.00.
  • a positive electrode active material for a lithium secondary battery including: a lithium composite oxide represented by Chemical Formula 5 below and capable of intercalating/deintercalating lithium ions; and a lithium composite oxide represented by Chemical Formula 2 below and capable of intercalating/deintercalating lithium ions, wherein the lithium composite oxide represented by Chemical Formula 5 below and capable of intercalating/deintercalating lithium ions is prepared from a precursor, and wherein the surface Ni content of the lithium composite oxide represented by Chemical Formula 5 below and capable of intercalating/deintercalating lithium ions is further reduced than the surface Ni content of a lithium composite oxide prepared by firing the precursor alone:
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; and ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05, 0.5 ⁇ 0.64, 0.15 ⁇ 0.29, and 0.21 ⁇ 0.35, and
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; and ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05, 0.35 ⁇ 0.5, 0.19 ⁇ 0.34, and 0.31 ⁇ 0.46.
  • the particle diameter of the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be smaller than the particle diameter of the lithium composite oxide represented by Chemical Formula 5 and capable of intercalating/deintercalating lithium ions.
  • the particle diameter of the lithium composite oxide represented by Chemical Formula 5 and capable of intercalating/deintercalating lithium ions may be 8 to 12 ⁇ m.
  • the particle diameter of the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be 3 to 8 ⁇ m.
  • the weight ratio of the lithium composite oxide represented by Chemical Formula 5 and capable of intercalating/deintercalating lithium ions to the lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be 95/5 to 70/30.
  • lithium composite oxide represented by Chemical Formula 5 and capable of intercalating/deintercalating lithium ions may be represented by Chemical Formula 6 below.
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; ⁇ 0.05 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.05, 0 ⁇ b ⁇ 0.05; and 0.50 ⁇ 0.61, 0.15 ⁇ 0.26, and 0.24 ⁇ 0.35.
  • lithium composite oxide represented by Chemical Formula 2 and capable of intercalating/deintercalating lithium ions may be represented by Chemical Formula 4 below:
  • A Ni ⁇ Co ⁇ Mn ⁇ ;
  • D is at least one element selected from the group consisting of Mg, Al, B, Zr, and Ti;
  • E is at least one element selected from the group consisting of P, F, and S; ⁇ 0.05 ⁇ z ⁇ 0.1; 0 ⁇ a ⁇ 0.05; 0 ⁇ b ⁇ 0.05; and 0.43 ⁇ 0.5, 0.19 ⁇ 0.26, and 0.31 ⁇ 0.38.
  • a lithium secondary battery including a positive electrode, an anode, and an electrolyte, wherein the positive electrode includes a current collector and a positive electrode active material layer formed on the current collector, and wherein the positive electrode active material layer contains the above-described positive electrode active material according to an embodiment of the present invention.
  • the positive electrode active material layer may contain a binder and a conductor.
  • the binder serves to favorably bind positive electrode active material particles to each other and favorably bind the positive electrode active material to the current collector.
  • examples thereof may include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, a polymer including ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, a styrene-butadiene rubber, an acrylated styrene-butadiene rubber, an epoxy resin, nylon, and the like, but are not limited thereto.
  • the conductor is used to give conductivity to the electrodes, and any material that does not cause a chemical change and corresponds to an electronically conductive material may be used in batteries.
  • a conductive material containing a carbon based material such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, or carbon fiber
  • a metal based material such as a metal powder or a metal fiber of copper, nickel, aluminum, silver, or the like
  • a conductive polymer such as a polyphenylene derivative; or a mixture thereof, may be used.
  • Examples of the negative electrode active material may include a material capable of reversibly intercalating/deintercalating lithium ions, lithium, a lithium alloy, a material capable of doping and dedoping lithium, and a transition metal oxide.
  • the material capable of reversibly intercalating/deintercalating lithium ions is a carbon-based material.
  • Any carbon-based negative electrode active material that can be generally used in a lithium ion secondary battery may be used, and representative examples thereof may include crystalline carbon, amorphous carbon, and a mixture thereof.
  • the crystalline carbon may include formless, plate type, flake type, spherical, or fiber type natural graphite and artificial graphite.
  • Examples of the amorphous carbon may include soft carbon (low-temperature fired carbon), hard carbon, mesophase pitch carbide, fired coke, and the like.
  • the lithium alloy may be an alloy of lithium and a metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn.
  • Examples of the material capable of doping and dedoping lithium may include Si, SiO x (0 ⁇ x ⁇ 2), Si—Y alloys (wherein Y is an element selected from the group consisting of alkali metals, alkali earth metals, Group 13 elements, Group 14 elements, transition elements, rare earth elements, and combinations thereof, but is not Si), Sn, SnO 2 , Sn—Y (wherein Y is an element selected from the group consisting of alkali metals, alkali earth metals, Group 13 elements, Group 14 elements, transition elements, rare earth elements, and combinations thereof, but is not Si), and the like, and at least one of these materials may be used in a mixture with SiO 2 .
  • the element Y may be selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof.
  • transition metal oxide examples include vanadium oxides, lithium-vanadium oxides, and the like.
  • the negative electrode active material layer also contains a binder, and may further optionally contain a conductor.
  • the conductor is used to give conductivity to the electrodes, and any material that does not cause a chemical change and corresponds to an electronically conductive material may be used in batteries.
  • a conductive material containing a carbon based material such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, or carbon fiber
  • a metal based material such as a metal powder or a metal fiber of copper, nickel, aluminum, silver, or the like
  • a conductive polymer such as a polyphenylene derivative; or a mixture thereof, may be used.
  • At least one selected from the group consisting of a copper foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, or a combination thereof may be used.
  • Al may be used for the current collector, but is not limited thereto.
  • the negative electrode and positive electrode are manufactured by mixing an active material, a conductor, and a binder in a solvent to prepare an active material composition and then coating the active material composition on a current collector. Since the electrode manufacturing method is well known in the art, detailed descriptions thereof will be omitted in the present specification. Examples of the solvent may include
  • N-methylpyrrolidone but are not limited thereto.
  • the electrolyte contains a non-aqueous organic solvent and a lithium salt.
  • non-aqueous organic solvent may include carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, and aprotic solvent.
  • carbonate based solvent may include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like.
  • ester-based solvent examples include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, and the like.
  • ether-based solvent examples include dibutyl ether, tetraglyme, diglyme, dimethoxy ethane, 2-methyl tetrahydrofuran, tetrahydrofuran, and the like.
  • ketone-based solvent may include cyclohexanone and the like.
  • examples of the alcohol-based solvent may include ethyl alcohol, isopropyl alcohol, and the like.
  • examples of the aprotic solvent may include nitriles including R—CN(R is a C2-C20 straight, branched, or cyclic hydrocarbon group which may include a double bonded aromatic ring or an ether bond), amides including dimethylformamide, dioxolanes including 1,3-dioxolane, sulfolanes, and the like.
  • the non-aqueous organic solvents may be used alone or in a combination of two or more. When they are used in a combination of two or more, the mixing ratio thereof may be appropriately controlled according to the desired battery performance, which may be widely understood by those worked in the art.
  • the carbonate-based solvent when used, it is favorable to use cyclic carbonate and chained carbonate in a mixture thereof.
  • the cyclic carbonate and the chained carbonate are mixed at a volume ratio of 1:1 to 1:9, so that the performance of the electrolyte can be favorably exhibited.
  • the non-aqueous organic solvent according to an embodiment of the present invention may further contain an aromatic hydrocarbon-based organic solvent in addition to the carbonate-based solvent.
  • the carbonate-based solvent and the aromatic hydrocarbon based organic solvent may be mixed at a volume ratio of 1:1 to 30:1.
  • aromatic hydrocarbon-based organic solvent an aromatic hydrocarbon-based compound of Chemical Formula 7 below may be used:
  • R 1 to R 6 each are independently hydrogen, halogen, C 1 -C 10 alkyl group, a holoalkyl group, or a combination thereof).
  • the aromatic hydrocarbon-based organic solvent may be selected from the group consisting of benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, Iodo benzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4-triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-
  • the non-aqueous electrolyte may further contain vinylene carbonate or an ethylene carbonate-based compound of Chemical Formula 8 below in order to improve the battery lifespan:
  • R 7 and R 8 each are independently hydrogen, a halogen group, a cyano group (CN), a nitro group (NO 2 ), or a C 1 -C 5 fluoroalkyl group, and at least one of R 7 and R 8 is a halogen group, a cyano group (CN), a nitro group (NO 2 ), or a C 1 -C 5 fluoroalkyl group).
  • ethylene carbonate-based compound may include difluoroethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate, and the like.
  • these lifespan improving additives are further used, the use amounts thereof may be appropriately controlled.
  • the lithium salt is dissolved in the organic solvent to act as a lithium ion supply source in the battery, thereby enabling a basic operation of a lithium secondary battery and promoting the movement of lithium ions between a positive electrode and a negative electrode.
  • Representative examples of the lithium salt include, as a supporting electrolyte salt, at least one selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LIC 4 F 9 SO 3 , LIClO 4 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2 x+1SO 2 , C y F 2 y+1SO 2 , here, x and y are a natural number), LiCl, LiI, and LiB(C 2 O 4 ) 2 (lithium bis(oxalato) borate; LiBOB).
  • the concentration of the lithium salt is preferably 0.1 to 2.0 M. If the concentration of the lithium salt falls within the above range, the electrolyte has appropriate electrical conductivity and viscosity, so that the electrolyte performance can be excellent and the lithium ions can be effectively moved.
  • a separator may be disposed between the positive electrode and the negative electrode depending on the kind of lithium secondary battery.
  • the separator polyethylene, polypropylene, polyvinylidene fluoride or multi-layers of two or more layers thereof may be used.
  • Mixed multi-layers thereof such as a polyethylene/polypropylene double-layered separator, a polyethylene/polypropylene/polyethylene triple-layered separator, polypropylene/polyethylene/polypropylene triple-layered separator, and the like may be used.
  • Lithium secondary batteries may be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries according to the kinds of a separator and an electrolyte used therein.
  • the lithium secondary batteries may be classified into cylindrical, prismatic, coin-type, and pouch-type batteries according to the shape.
  • the secondary batteries may be classified into bulk type and thin film type batteries according to the size. Since structures and manufacturing methods of these batteries are widely known in the art, descriptions thereof will be omitted.
  • FIG. 1 is a schematic view showing a representative structure of a lithium secondary battery of the present invention.
  • a lithium secondary battery 1 includes a battery container 5 having a positive electrode 3 , a negative electrode 2 , and a separator 4 disposed between the positive electrode 3 and the negative electrode 2 , which are impregnated with an electrolyte, and a sealing member 6 sealing the battery container 5 .
  • Li 2 CO 3 (Product name: SQM) and Ni 0.47 Co 0.20 Mn 0.33 (OH) 2 (D50: 5 ⁇ m) were mixed at a weight ratio of 1:1.03 (Metal:Li) using a mixer.
  • the obtained mixture was fired for a total of 20 hours while the time rise reaction time was 6 hours in air and the time for a maintenance period was 7 hours at 950° C., thereby preparing a fired material.
  • the obtained fired material was slowly cooled and then reduced to powder, thereby obtaining a lithium composite oxide powder for mixing and firing according to an embodiment of the present invention.
  • Li 2 CO 3 (Product name: SQM) and Ni 0.55 Co 0.20 Mn 0.25 (OH) 2 were mixed at a weight ratio of 1:1.03 (Metal:Li) using a mixer.
  • LiNi 0.47 Co 0.20 Mn 0.33 O 2 was further added thereto such that the weight ratio of LiNi 0.55 Co 0.20 Mn 0.25 O 2 and Li 0.47 Co 0.20 Mn 0.33 O 2 of Synthetic Example 1 was 90:10.
  • the obtained mixture was fired for a total of 20 hours while the time rise reaction time was 6 hours in air and the time for a maintenance period was 7 hours at 940° C., thereby preparing a fired material.
  • the obtained fired material was slowly cooled and then reduced to powder, thereby preparing a positive electrode active material.
  • a positive electrode active material was prepared by the same method as in Example 1, except that LiNi 0.47 CO 0.20 Mn 0.33 O 2 was added such that the weight ratio of LiNi 0.55 CO 0.20 Mn 0.25 O 2 and LiNi 0.47 CO 0.20 Mn 0.33 O 2 was 80:20, followed by mixing and firing.
  • a positive electrode active material was prepared by the same method as in Example 1, except that LiNi 0.47 CO 0.20 Mn 0.33 O 2 was added such that the weight ratio of LiNi 0.55 CO 0.20 Mn 0.25 O 2 and LiNi 0.47 CO 0.20 Mn 0.33 O 2 was 70:30, followed by mixing and firing.
  • a positive electrode active material was prepared by the same method as in Example 1, except that Ti—Zr-codoped Li 0.47 Co 0.20 Mn 0.33 O 2 prepared by further dry-mixing Ni 0.47 Co 0.20 Mn 0.33 (OH) 2 with ZrO 2 powder and TiO 2 powder at a weight ratio of 100:0.27:0.33 and firing the mixture was used.
  • Li 2 CO 3 (Product name: SQM) and LiNi 0.55 CO 0.20 Mn 0.25 O 2 (OH) 2 were mixed at a weight ratio of 1:1.03 (Metal:Li) using a mixer.
  • the obtained mixture was fired for a total of 20 hours while the time rise reaction time was 6 hours in air and the time for a maintenance period was 7 hours at 940° C., thereby preparing a fired material.
  • the obtained fired material was slowly cooled, and then reduced to powder, thereby preparing a positive electrode active material.
  • Li 2 CO 3 (Product name: SQM) and Ni 0.55 Co 0.20 Mn 0.25 (OH) 2 and Ni 0.47 Co 0.20 Mn 0.33 (OH) 2 were mixed at a weight ratio of 1:1.03 (Metal:Li) using a mixer.
  • the mixing was conducted such that the weight ratio of Ni 0.55 Co 0.20 Mn 0.25 (OH) 2 and Ni 0.47 Co 0.20 Mn 0.33 (OH) 2 was 90:10.
  • the obtained mixture was fired for a total of 20 hours while the time rise reaction time was 6 hours in air and the time for a maintenance period was 7 hours at 940° C., thereby preparing a fired material.
  • Each positive electrode slurry was prepared by adding 95 wt % of the positive electrode active material prepared in each of Examples 1 to 4 and Comparative Examples 1 to 4, 2.5 wt % of carbon black as a conductor, and 2.5 wt % of PVDF as a binder to 5.0 wt % of N-methyl-2-pyrolidone (NMP) as a solvent.
  • NMP N-methyl-2-pyrolidone
  • Examples 1 to 3 showed equivalent or higher Formation discharge capacity as compared with Comparative Example 1 using a single composition.
  • Examples 1 to 3 showed excellent efficiency and rate characteristics and equivalent or higher lifespan characteristics, as compared with Comparative Example 1.
  • Comparative Example 3 in which precursors having different compositions were mixed and then fired at a particular temperature, which corresponds one of the conventional arts, showed reduced efficiency, rate characteristics and/or lifespan characteristics as compared with Examples 1 to 4.
  • Example 1 Ten particles having relatively a higher Ni content were randomly selected from the positive electrode active material obtained in Example 1. The surface analysis results thereof were expressed as Examples 1-1 to 1-10. Ten particles having relatively a higher Ni content were randomly selected from the positive electrode active material obtained in Comparative Example 3. The surface analysis results thereof were expressed as Comparative Examples 3-1 to 3-10.
  • Example 1 as an embodiment of the present invention, in which the positive electrode active material was prepared by mixing and firing the precursor and the lithium composite oxide, has two different composition groups of Ni ⁇ Co ⁇ Mn ⁇ , and Table 2 obtained from EDS analysis results showed that, of the particles having the two compositions, the surface Ni content of particles having a higher Ni content was further reduced as compared with Comparative Example 1 in which the mixing and firing were not performed.
  • Comparative Example 3 as one of the conventional arts, in which precursors having different compositions were mixed and fired, has two different composition groups of Ni ⁇ Co ⁇ Mn ⁇ , and, it can be seen that, of the particles having the two compositions, the surface Ni content of particles having a higher Ni content was largely reduced.
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