WO2006137673A1 - Cathode active material added with fluorine compound for lithium secondary batteries and method of producing thereof - Google Patents

Cathode active material added with fluorine compound for lithium secondary batteries and method of producing thereof Download PDF

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WO2006137673A1
WO2006137673A1 PCT/KR2006/002362 KR2006002362W WO2006137673A1 WO 2006137673 A1 WO2006137673 A1 WO 2006137673A1 KR 2006002362 W KR2006002362 W KR 2006002362W WO 2006137673 A1 WO2006137673 A1 WO 2006137673A1
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cathode active
active material
fluorine compound
lithium secondary
secondary battery
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PCT/KR2006/002362
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French (fr)
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Yang Kook Sun
Jung Min Han
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Daejung Chemicals & Metals Co., Ltd.
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Publication of WO2006137673A1 publication Critical patent/WO2006137673A1/en

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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
    • H01M4/58—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/58—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • 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
    • 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
    • H01M4/58—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
    • H01M4/582—Halogenides
    • 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
    • H01M4/58—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
    • 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 fluorine compound- added cathode active material for lithium secondary battery and a method of producing the same, and in particular, to a fluorine compound-added cathode active material for lithium secondary battery having improved charging/discharging characteristics, life span characteristics, high voltage characteristics and high rate capability, by synthesizing a powdered fluorine compound as an additive for cathode active materials for lithium secondary battery and adding the powdered fluorine compound to a cathode active material for lithium secondary battery, and a method of producing the same.
  • Lithium secondary batteries are classified into lithium batteries employing lithium metal for the cathode, and lithium ion batteries employing intercalation compounds, such as graphite intercalation compounds, in which lithium ions can undergo insertion/extraction between the interlayer spacing. Furthermore, lithium secondary batteries may also be classified according to the electrolyte used, into liquid type batteries employing liquid electrolytes, gel type polymer batteries employing mixtures of liquids and polymers, and solid type polymer batteries employing solid polymers only.
  • LiCoO 2 for the anode and carbon for the cathode.
  • MoIi Energy Corp. in Japan uses LiMn 2 O 4 for the anode, but the quantity being used is negligible compared to that of LiCo ⁇ 2.
  • LiNiO 2 , LiCo x Nii_ x ⁇ 2 and LiMn 2 O 4 may be mentioned.
  • LiCoO 2 is a material which is excellent in stable charging/discharging characteristics, electronic conductivity, high thermal stability and flat and smooth discharging voltage characteristics.
  • cobalt (Co) is less abundant in the earth's crust, expensive and toxic to human body, it is highly desired to develop other cathode materials.
  • LiNiO 2 is difficult to be synthesized and is thermally unstable, and thus commercialization thereof is hardly achievable.
  • LiMn 2 O 4 is supplied as products of relatively low prices, and thus, some of the products are currently marketed.
  • LiMn 2 O 4 having a spinel structure, has a relatively small theoretical capacity of about 148 mAh/g compared with other materials, and has a three-dimensional tunnel structure.
  • the material upon insertion/extraction of lithium ions, the material exhibits a large resistance to diffusion, thus having a lower diffusion coefficient than LiCoO 2 and LiNiO 2 , which have two-dimensional structure, and has poor cycle characteristics due to the Jahn-Teller effect.
  • the high temperature properties at a temperature of 55 0 C or above are poor when compared with LiCoO 2 , and thus this material is in fact not commonly used in batteries. Therefore, as a material to overcome such problems, extensive research has been conducted on materials having layered crystal structure.
  • Li [Nii /2 Mni /2 ] O 2 and Li [Nii /3 C ⁇ /3 Mni / 3] O 2 in which nickel and manganese, and nickel, cobalt and manganese are mixed in equal proportions, respectively, may be mentioned as the representative materials having layered crystal structure, which are attracting public interest.
  • These materials have features such as low price, high capacity, excellent thermal stability and the like, compared with LiCoO 2 .
  • these materials have lower electronic conductivity than LiCoO 2 , and thus have poor high rate capabilities and low temperature properties.
  • the materials have low tap densities, which suppress an enhancement of energy density in batteries in spite of the high capacities of the materials.
  • lithium secondary batteries have a problem that repeated charging and discharging processes rapidly deteriorate the life span of the batteries. This problem becomes more serious particularly at high temperatures.
  • the reason for this problem is believed to be that under the effect of moisture or other factors within the batteries, the electrolytes are decomposed or the active materials become deteriorated, and also, the internal resistance of the batteries increases. Attempts have been made to solve this problem, and for example, a method of improving the energy density and high rate capability of batteries by adding Ti ⁇ 2 to LiCo ⁇ 2 (Electrochemical and Solld-State Letters, 4(6), A65-A67 (2001)).
  • the present invention aims to provide an improved cathode active material for lithium secondary battery by adding an additive to a cathode active material, and thus to prevent the phenomenon that the life span characteristics of batteries, and particularly the battery performance at high pressures and high rates, are deteriorated.
  • the present invention provides a cathode active material for lithium secondary battery, comprising a fluorine compound in a complex salt form added thereto.
  • the fluorine compound may include at least one selected from the group consisting of CsF, KF, LiF, NaF, RbF, TiF, AgF, AgF2 , BaF 2 , CaF 2 , CuF 2 , CdF 2 , FeF 2 , HgF 2 , Hg 2 F 2 , MnF 2 , MgF 2 , NiF 2 , PbF 2 , SnF 2 , SrF 2 , XeF 2 , ZnF 2 , AlF 3 , BF 3 , BiF 3 , CeF 3 , CrF 3 , DyF 3 , EuF 3 , GaF 3 , GdF 3 , FeF 3 , HoF 3 , InF 3 , LaF 3 , LuF 3 , MnF 3 , NdF 3 , VOF 3 , PrF 3 , SbF 3 , ScF 3 , SmF 3 , TbF 3 , TiF 3 ,
  • M is at least one metal selected from the group consisting of Mg, Ca, Cu and Zn;
  • N is F or S
  • M is at least one metal selected from the group consisting of Mg, Ca, Cu and Zn;
  • N is F or S
  • M is at least one metal selected from the group consisting of B, Al, Fe and Cr; and N is F or
  • Li Li [Li a (Ni x C ⁇ i_2 ⁇ -yMn x _ z/ 2MyN 2 ) i_ a ] O2-bNb having a hexagonal layered rock-salt structure (0.01 ⁇ a ⁇ 0.2, 0.01 ⁇ x ⁇ 0.5, 0.01 ⁇ y ⁇ 0.1, 0.01 ⁇ b ⁇ 0.1; M is at least one metal selected from the group consisting of B, Al, Fe and Cr; and N is Mg or Ca; N is F or S) ,
  • LiM x Fei- x P ⁇ 4 having an olivine structure (0 ⁇ x ⁇ 1; and M is at least one metal selected from the group consisting of Co, Ni and Mn) ,
  • the present invention also provides a method of producing a cathode active material for lithium secondary- battery, the method comprising adding a solution of dissolved fluorine (F) to a solution of powdered elemental precursor of high dispersibility; allowing the mixture to react at a temperature of 5O 0 C to 150 0 C for 1 to 48 hours to form a powdered fluorine compound of high dispersibility in a complex salt form; drying the formed powdered fluorine compound at 110 0 C for 6 to 24 hours; subsequently thermally treating the powdered fluorine compound at a temperature of 150 0 C to 900 0 C for 1 to 20 hours in any of an oxidizing atmosphere, a reducing atmosphere and a vacuum; and then adding 0.05 to 10 parts by weight of the powdered fluorine compound to 100 parts by weight of a cathode active material for lithium secondary battery, and uniformly mixing the mixture.
  • F dissolved fluorine
  • the solution of elemental precursor may be at a concentration of 0.1 to 3 M, and the solution of dissolved fluorine (F) may be at a concentration of 0.1 to 18 M.
  • the method of the present invention is characterized in that the mixture of the solution and the solution is allowed to react at a temperature of 50 0 C to 150 0 C for 1 to 48 hours, thus to form a powdered fluorine compound of high dispersibility in a complex salt form.
  • the elemental precursor may be any one compound selected from alkoxides, sulfates, nitrates, acetates, chlorides and phosphates of at least one element selected from the group consisting of Cs, K, Li, Na, Rb, Ti, Ag(I), Ag(II), Ba, Ca, Cu, Cd, Fe, Hg(II), Hg(I), Mn(II), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi(III), Ce(III), Cr, Dy, Eu, Ga, Gd, Fe, Ho, In, La, Lu, Mn(III), Nd, VO, Pr, Sb(III), Sc, Sm, Tb, Ti(III), Tm, Y, Yb, TI, Ce(IV), Ge, Hf, Si, Sn, Ti(IV), V, Zr, Nb, Sb(V), Ta, Bi(V), Mo, Re, S and W.
  • the solution of dissolved fluorine (F) to precipitate the elemental precursor in a complex salt form may be a solution of a compound selected from the group of compounds which can provide fluorine (F) so as to precipitate the elemental precursor in a complex salt form, such as HN 4 F, HF, AHF (anhydrous HF) and the like.
  • a compound selected from the group of compounds which can provide fluorine (F) so as to precipitate the elemental precursor in a complex salt form such as HN 4 F, HF, AHF (anhydrous HF) and the like.
  • the present invention relates to a cathode active material prepared by forming a powdered fluorine compound and adding this to a cathode active material, in order to prevent the phenomenon that the life span characteristics of lithium secondary batteries, and particularly the battery performance at high pressures and high rates, are deteriorated.
  • the method of producing a cathode active material of the present invention comprises synthesizing a powdered fluorine compound to be used as an additive for the cathode active material for lithium secondary battery, and the fluorine compound to be synthesized may be at least one selected from the group consisting of CsF, KF, LiF, NaF, RbF, TiF, AgF, AgF 2 , BaF 2 , CaF 2 , CuF 2 , CdF 2 , FeF 2 , HgF 2 , Hg 2 F 2 , MnF 2 , MgF 2 , NiF 2 , PbF 2 , SnF 2 , SrF 2 , XeF 2 , ZnF 2 , AlF 3 , BF 3 , BiF 3 , CeF 3 , CrF 3 , DyF 3 , EuF 3 , GaF 3 , GdF 3 , FeF 3 , HoF 3 , InF 3 , LaF 3 , Lu
  • the powdered fluorine compound of the present invention may be in an amorphous phase, a crystalline phase, or a mixed phase of amorphous and crystalline phases.
  • a solution of dissolved fluorine (F) is added to a solution of powdered elemental precursor of high dispersibility, the mixture is allowed to react at a temperature of 5O 0 C to 15O 0 C for 1 to 48 hours to form a powdered fluorine compound of high dispersibility in a complex salt form, subsequently the formed powdered fluorine compound is dried at HO 0 C for 6 to 24 hours, and then the dried powdered fluorine compound is thermally treated at a temperature of 15O 0 C to 900 0 C for 1 to 20 hours in any of an oxidizing atmosphere, a reducing atmosphere and a vacuum, so as to provide a powdered fluorine compound.
  • the reason for raising the temperature for co-immersion reaction as such is because a precipitate of high dispersibility can be obtained in a complex salt form by means of co-immersion of elemental precursors at high temperatures .
  • a solution containing fluorine (F) when added to a solution of an elemental precursor, a powdered fluorine compound is formed after a certain length of time, and this powdered fluorine compound can be used, after being thermally treated, as an additive for the cathode active material for lithium secondary battery.
  • a fluorine compound is formed by mixing a solution of elemental precursor and a solution containing fluorine (F), it is not necessary to control the precipitation rate, and thus it is advantageous, as compared with the case of adding small amounts of the solution containing fluorine (F) .
  • mixing an elemental precursor and fluorine (F) in advance to form a fluorine compound allows reduction of the amount of the solvent used. For example, if the solvent being used is alcohol or ethylene glycol, since these are more expensive reagents than distilled water, reduction of the amount of solvent would be advantageous in view of reducing the production costs in the process of synthesizing the fluorine compound.
  • a solution of elemental precursor at a concentration of 0.1 to 3 M
  • a solution of fluorine (F) at a concentration of 0.1 to 18 M.
  • the concentration of the elemental precursor is too high that a fluorine compound of very large crystals may be formed instead of the desired powdered fluorine compound. This is because the rate of fluoride ions binding with the elemental precursor molecules is very high. Fluoride ion is an anion having the fastest binding ability among others.
  • the reason for using a solution containing fluorine (F) at a concentration of 0.1 M to 18 M is that, when a solution of elemental precursor at a concentration of 0.1 M to 3 M is used, the valency of the cation of the elemental precursor is in the range of +1 to +6, while the fluoride anion to bind with the cation is F ⁇ , and thus, the concentration of the fluoride ion should be at least equal to the concentration of the cation of the elemental precursor (for example, in the case of producing LiF) , or should be at most 6 times the concentration of the cation of the elemental precursor (for example, in the case of producing W +6 + 6F ⁇ ⁇ WF 6 ) .
  • alkoxides such as methoxides, ethoxides, isopropoxides and butoxides, sulfates, nitrates, acetates, chlorides or oxides can be used.
  • the solution containing fluorine (F) which is added to precipitate the elemental precursor in the complex salt form, may be a solution of NH 4 F, HF, AHF (anhydrous HF) or the like.
  • the solution of elemental precursor and the solution containing fluorine (F) are mixed and reacted at a temperature of 50 0 C to 15O 0 C for 1 to 48 hours.
  • a method of producing a powdered fluorine compound comprising adding a solution containing fluorine (F) to a solution of dissolved powdered elemental precursor of high dispersibility at a constant rate, and allowing the mixture to react at a temperature of 5O 0 C to 150 0 C for 1 to 48 hours, thus to form a powdered fluorine compound in a complex salt form.
  • F fluorine
  • the reason for increasing the temperature of the co-immersion reaction is that co-immersion of the elemental precursor can result in a precipitate of high dispersibility in a complex salt form at high temperatures.
  • a fluorine compound is formed by mixing an elemental precursor and fluorine (F) as described above, there may be occurrences in which the resulting fluorine compound cannot attain a powdered form of high dispersibility due to the characteristics of the elemental precursor, and rather aggregates with strong tendency to form large granules of the fluorine compound.
  • addition of the fluorine compound to a cathode active material may lead to an effect of improving the properties of the cathode active material, which is negligible. Therefore, in such a case, it is desirable to add the solution containing fluorine (F) at a constant rate as described above, thus to control the precipitation rate and to form the fluorine compound in a powdered form of high dispersibility.
  • the formed powdered fluorine compound is dried at 110 0 C for ⁇ to 24 hours, and then thermally treated at a temperature of 15O 0 C to 900 0 C for 1 to 20 hours in any of an oxidizing atmosphere, a reducing atmosphere and a vacuum.
  • thermal treatment allows removal of any impurities that have not been removed previously, so that a powdered fluorine compound in the desired form can be obtained.
  • the synthesized powdered fluorine compound When the synthesized powdered fluorine compound is added to a cathode active material, the effect of the acid generated in the vicinity of the cathode active material may be reduced, or the reactivity of the cathode active material with the electrolyte may be suppressed, and thereby the phenomenon that the battery capacity rapidly decreases can be improved. It is also possible to provide a cathode active material having improved charging/discharging characteristics, life span characteristics, high voltage characteristics, and high rate capability.
  • a cathode active material for lithium secondary battery to which a synthesized powdered fluorine compound is added, the method comprising uniformly mixing 0.05 to 10 parts by weight of the powdered fluorine compound with 100 parts by weight of the cathode active material for lithium secondary battery.
  • the powdered fluorine compound is mixed in an amount of less than 0.05 parts by weight, the amount added is insufficient, and it is difficult to achieve the effect of the present invention sufficiently.
  • the fluorine compound when the powdered fluorine compound is mixed in an amount of more than 10 parts by weight, the fluorine compound is added to the cathode active material in excess, and acts as a resistance factor, thus causing a rapid decrease in the initial capacity.
  • a cathode active material having excellent charging/discharging characteristics, life span characteristics, high voltage characteristics, and high rate capability cannot be provided.
  • This can be understood as an occurrence similar to a phenomenon found in an already known technology for surface treatment of cathode active materials, that when surface treatment is performed using an excess of a material, the material in excess acts as a resistance factor, and deteriorates the charging/discharging characteristics, life span characteristics and high rate capability.
  • the most important reason for operating the cathode active material at high voltages is to increase the capacity, and the most important reason for increasing the capacity of the cathode active material is to provide more storage for energy in the produced batteries. From this point of view, the rapid decrease in the initial capacity is contradictory to the object of the present invention to solve the problem of improving the performance of batteries.
  • a uniform mixture of the cathode active material and the synthesized powdered fluorine compound is further thermally treated at a temperature of 150 0 C to 600 0 C for 1 to 20 hours in any of an oxidizing atmosphere, a reducing atmosphere and a vacuum to obtain a powdered fluorine compound-added cathode active material for lithium secondary battery.
  • the process of thermal treatment allows increasing the binding power of the fluorine compound and the cathode active material.
  • a fluorine compound-added cathode active material for lithium secondary battery is prepared by synthesizing a powdered fluorine compound as an additive for cathode active materials for lithium secondary battery, and adding the obtained fluorine compound to a cathode active material for lithium secondary battery.
  • This powdered fluorine compound-added cathode active material for lithium secondary battery exhibits excellent charging/discharging characteristics, life span characteristics, high voltage characteristics and high rate capability, which characteristics are obtained by reducing the effect of acid generated in the vicinity of the cathode active material, or suppressing the reactivity of the cathode active material and the electrolyte, thereby to improve the phenomenon that the battery capacity rapidly decreases .
  • the fluorine compound thus obtained was washed several times with distilled water, and was dried in a constant temperature air dryer at 110 0 C for 12 hours. Then, the product was thermally treated at 400 0 C in an inert atmosphere to produce AIF 3 .
  • ZrF 4 -added LiCoO 2 The ZrF 4 produced as described above was added to a commercially available cathode active material for lithium secondary battery, LiCoO 2 , in a proportion of 2 mol% based on the cathode active material, and the mixture was uniformly mixed to produce ZrF 4 -added LiCoO 2 . 3. Production of coin cell and properties evaluation
  • a cathode was produced in the same manner as in Example 1, and a coin cell containing this cathode was produced.
  • Mg (NO 3 ) 2 - 6H 2 O was dissolved in 100 ml of distilled water to a concentration of 0.25 M, and then 100 ml of a 0.5 M solution of NH 4 F was produced.
  • the two solutions were mixed at a flow rate of 1 ml/min, and were subjected to a co-immersion reaction, followed by stirring for 12 hours.
  • the average temperature of the reactor was maintained at about 8O 0 C.
  • the reason for increasing the temperature of the co-immersion reaction is because co- immersion of MgF 2 results in a precipitate of high dispersibility in a complex salt form at high temperatures.
  • the fluorine compound thus obtained was washed several times with distilled water, and was dried in a constant temperature air dryer at 110 0 C for 12 hours. Then, the product was thermally treated in an inert atmosphere to produce MgF 2 .
  • the MgF 2 produced as described above was added to a commercially available cathode active material for lithium secondary battery, LiCoO 2 , in a proportion of 2 mol% based on the cathode active material, and the mixture was uniformly mixed to produce MgF 2 -added LiCoO 2 . 3. Production of coin cell and properties evaluation
  • a cathode was produced in the same manner as in Example 1, and a coin cell containing this cathode was produced.
  • the ZnF 2 produced as described above was added to a commercially available cathode active material for lithium secondary battery, LiCoO 2 , in a proportion of 2 mol% based on the cathode active material, and the mixture was uniformly mixed to produce ZnF 2 -added LiCoO 2 .
  • a coin cell was produced using the AlF 3 -added LiNi 0 . 5 Mn 0-S O 2 .
  • a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 30 0 C in a potential region of from 2.8 to 4.5 V and at current densities of 0.2 mA/cm 2 and 0.8 mA/cm 2 .
  • the changes in capacity with the number of cycles are presented in Fig. 12 and Fig. 13.
  • the coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics.
  • AlF 3 -added LiNii /3 C ⁇ i /3 Mni / 3 ⁇ 2 was produced in the same manner as in Example 1, and the properties were evaluated. Then, a coin cell was produced using the AlF 3 - added LiNii /3 C ⁇ i / 3Mni / 3 ⁇ 2. To evaluate the properties of the produced coin cell, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 3O 0 C in a potential region of from 2.8 to 4.6 V and at current densities of 0.2 mA/cm 2 and 0.8 mA/cm 2 . The changes in capacity with the number of cycles are presented in Fig. 15 and Fig. 16. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [EXAMPLE 7]
  • AlF3-added LiNi 0 .4C0 0 .2Mn 0-4 O 2 was produced in the same manner as in Example 1, and the properties were evaluated. Then, a coin cell was produced using the AlF 3 -added LiNi 0-4 Co 0 . 2 Mn 0-4 O 2 . To evaluate the properties of the produced coin cell, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 3O 0 C in a potential region of from 2.8 to 4.6 V and at current densities of 0.2 mA/cm 2 and 0.8 mA/cm 2 . The changes in capacity with the number of cycles are presented in Fig. 18 and Fig. 19. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [EXAMPLE 8]
  • FIG. 4 shows X-ray diffraction (XRD) patterns of the cathode active materials obtained in Example 1 and Comparative Example 1. Furthermore, a field emission scanning electron microscopic (FE-SEM) photograph of the cathode active material obtained in Comparative Example 1 is presented in Fig. 6.
  • the cycling curves of half cells which are obtained by performing an experiment using the cathode active materials of Example 1 and Comparative Example 1 at 3O 0 C in a voltage range of from 3.0 to 4.5 V and at a constant current density of 0.2 mA/cm 2 , are presented in Fig.
  • Fig. 11 shows XRD patterns of the cathode active materials obtained in Example 5 and Comparative Example 2.
  • the cycling curves of half cells which are obtained by performing an experiment using the cathode active materials of Example 5 and Comparative Example 2 at 30 0 C in a voltage range of from 2.8 to 4.5 V and at a constant current density of 0.2 mA/cm 2 , are presented in Fig.
  • Fig. 14 shows XRD patterns of the cathode active materials obtained in Example 6 and Comparative Example 3.
  • the cycling curves of half cells which are obtained by performing an experiment using the cathode active materials of Example 6 and Comparative Example 3 at 3O 0 C in a voltage range of from 2.8 to 4.6 V and at a constant current density of 0.2 mA/cm 2 , are presented in Fig.
  • Fig. 20 shows XRD patterns of the cathode active materials obtained in Example 8 and Comparative Example 5.
  • the cycling curves of half cells which are obtained by performing an experiment using the cathode active materials of Example 8 and Comparative Example 5 at 3O 0 C in a voltage range of from 3.0 to 4.5 V and at a constant current density of 0.2 mA/cm 2 , are presented in Fig.
  • a fluorine compound-added cathode active material for lithium secondary battery is produced by synthesizing a powdered fluorine compound as an additive for cathode active materials for lithium secondary battery, and adding this powdered fluorine compound to a cathode active material for lithium secondary battery.
  • This powdered fluorine compound-added cathode active material for lithium secondary battery exhibits excellent charging/discharging characteristics, life span characteristics, high voltage characteristics and high rate capability, which characteristics are obtained by reducing the effect of acid generated in the vicinity of the cathode active material, or suppressing the reactivity of the cathode active material and the electrolyte, to thereby improve the phenomenon that the battery capacity rapidly decreases .

Abstract

The present invention relates to a cathode active material for lithium secondary battery, and provides a structurally stable cathode active material for lithium secondary battery having improved battery charging/discharging characteristics, life span characteristics, high voltage characteristics and high rate capability, by synthesizing a powdered fluorine compound as an additive for cathode active materials, and adding the powdered fluorine compound to a cathode active material for lithium secondary battery to produce a fluorine compound-added cathode active material for lithium secondary battery.

Description

[DESCRIPTION]
[invention Title]
CATHODE ACTIVE MATERIAL ADDED WITH FLUORINE COMPOUND FOR LITHIUM SECONDARY BATTERIES AND METHOD OF PRODUCING THEREOF
[Technical Field]
The present invention relates to a fluorine compound- added cathode active material for lithium secondary battery and a method of producing the same, and in particular, to a fluorine compound-added cathode active material for lithium secondary battery having improved charging/discharging characteristics, life span characteristics, high voltage characteristics and high rate capability, by synthesizing a powdered fluorine compound as an additive for cathode active materials for lithium secondary battery and adding the powdered fluorine compound to a cathode active material for lithium secondary battery, and a method of producing the same.
[Background Art] As a power source of portable electronic instruments for personal telecommunication such as PDAs, mobile telephones and notebook computers, electric bicycles, electric automobiles and the like, a demand on secondary batteries which can be used with repeated charging and discharging, is rapidly increasing. In particular, since the performances of the aforementioned products are highly dependent on secondary batteries, which are the core elements of the products, there is a strong demand for high performance batteries. There are a variety of characteristics required from batteries, such as charging/discharging characteristics, life span characteristics, high rate capability, high temperature stability and the like. Lithium secondary batteries are currently batteries of the greatest interest, due to their features such as high voltage and high energy density.
Lithium secondary batteries are classified into lithium batteries employing lithium metal for the cathode, and lithium ion batteries employing intercalation compounds, such as graphite intercalation compounds, in which lithium ions can undergo insertion/extraction between the interlayer spacing. Furthermore, lithium secondary batteries may also be classified according to the electrolyte used, into liquid type batteries employing liquid electrolytes, gel type polymer batteries employing mixtures of liquids and polymers, and solid type polymer batteries employing solid polymers only.
The currently marketed small-sized lithium ion secondary batteries use LiCoO2 for the anode and carbon for the cathode. MoIi Energy Corp. in Japan uses LiMn2O4 for the anode, but the quantity being used is negligible compared to that of LiCoθ2. As the cathode material that is currently a subject of active research and development, LiNiO2, LiCoxNii_ xθ2 and LiMn2O4 may be mentioned.
LiCoO2 is a material which is excellent in stable charging/discharging characteristics, electronic conductivity, high thermal stability and flat and smooth discharging voltage characteristics. However, since cobalt (Co) is less abundant in the earth's crust, expensive and toxic to human body, it is highly desired to develop other cathode materials. LiNiO2 is difficult to be synthesized and is thermally unstable, and thus commercialization thereof is hardly achievable. LiMn2O4 is supplied as products of relatively low prices, and thus, some of the products are currently marketed. However, LiMn2O4, having a spinel structure, has a relatively small theoretical capacity of about 148 mAh/g compared with other materials, and has a three-dimensional tunnel structure. Thus, upon insertion/extraction of lithium ions, the material exhibits a large resistance to diffusion, thus having a lower diffusion coefficient than LiCoO2 and LiNiO2, which have two-dimensional structure, and has poor cycle characteristics due to the Jahn-Teller effect. In particular, the high temperature properties at a temperature of 550C or above are poor when compared with LiCoO2, and thus this material is in fact not commonly used in batteries. Therefore, as a material to overcome such problems, extensive research has been conducted on materials having layered crystal structure. Among those, Li [Nii/2Mni/2] O2 and Li [Nii/3Cθχ/3Mni/3] O2, in which nickel and manganese, and nickel, cobalt and manganese are mixed in equal proportions, respectively, may be mentioned as the representative materials having layered crystal structure, which are attracting public interest. These materials have features such as low price, high capacity, excellent thermal stability and the like, compared with LiCoO2. However, these materials have lower electronic conductivity than LiCoO2, and thus have poor high rate capabilities and low temperature properties. Further, the materials have low tap densities, which suppress an enhancement of energy density in batteries in spite of the high capacities of the materials. Especially in the case of
Li [Nii/2Mni/2] O2, the electronic conductivity is very low, and it is difficult to put the material into practical use
(Journal of Power Sources, 112, 41-48 (2002)). In particular, these materials are inferior to LiCoO2 or LiMn2O4 in the high output characteristics, in the aspect of use in the hybrid power sources for electric automobiles. In order to solve these problems, a method of treating the materials with conductive carbon black (Japanese Unexamined Patent Application No. 2003-59491) has been proposed, but there are no reports on significant improvements resulting therefrom.
Meanwhile, lithium secondary batteries have a problem that repeated charging and discharging processes rapidly deteriorate the life span of the batteries. This problem becomes more serious particularly at high temperatures. The reason for this problem is believed to be that under the effect of moisture or other factors within the batteries, the electrolytes are decomposed or the active materials become deteriorated, and also, the internal resistance of the batteries increases. Attempts have been made to solve this problem, and for example, a method of improving the energy density and high rate capability of batteries by adding Tiθ2 to LiCoθ2 (Electrochemical and Solld-State Letters, 4(6), A65-A67 (2001)).
In addition, techniques of improving battery performance by directly mixing electrolyte solutions with other compounds have been reported. For example, US Patent No. 5,709,968 discloses a method of preventing overcharged current and thermal runaway resulting therefrom by adding benzene compounds; US Patent No. 5,879,834 discloses a method of improving the stability of batteries by adding small amounts of aromatic compounds; and Korean Unexamined Patent Application No. 2003-0061219 discloses a method of electrochemically improving the stability of batteries by adding cyclohexylbenzene. Still, the problems of life span deterioration, or gas generation due to the decomposition of electrolytes and the like during the process of charging and discharging, have not been completely solved. Furthermore, a phenomenon has been reported that active materials in the batteries are dissolved in the acids produced when electrolytes under oxidation during the process of charging, thus causing a decrease in the capacity of batteries (Journal of Electrochemical Society, 143, 2204 (1996)). [Disclosure] [Technical Problem]
In order to address the problem of deterioration of battery performance as described above, the present invention aims to provide an improved cathode active material for lithium secondary battery by adding an additive to a cathode active material, and thus to prevent the phenomenon that the life span characteristics of batteries, and particularly the battery performance at high pressures and high rates, are deteriorated. [Technical Solution]
In order to achieve the object, the present invention provides a cathode active material for lithium secondary battery, comprising a fluorine compound in a complex salt form added thereto.
The fluorine compound may include at least one selected from the group consisting of CsF, KF, LiF, NaF, RbF, TiF, AgF, AgF2 , BaF2, CaF2, CuF2, CdF2, FeF2, HgF2, Hg2F2, MnF2, MgF2, NiF2, PbF2, SnF2, SrF2, XeF2, ZnF2, AlF3, BF3, BiF3, CeF3, CrF3, DyF3, EuF3, GaF3, GdF3, FeF3, HoF3, InF3, LaF3, LuF3, MnF3, NdF3, VOF3, PrF3, SbF3, ScF3, SmF3, TbF3, TiF3, TmF3, YF3, YbF3, TIF3, CeF4, GeF4, HfF4, SiF4, SnF4, TiF4, VF4, ZrF4, NbF5, SbF5, TaF5, BiF5, MoF6, ReF6, SF6 and WF6. The cathode active material to which these fluorine compounds are added may be any one of the following:
Lii+a[Cθi-xMx]02-bNb having a hexagonal layered rock-salt structure (0.01 < a < 0.2, 0.01 < b < 0.2, 0.01 < x ≤ 0.1; M is at least one metal selected from the group consisting of Mg, Al, Ni, Mn, Zn, Fe, Cr, Ga, Mo and W; and N is F or S) ,
Lii+a[Nii-xMχ]O2-bNb having a hexagonal layered rock-salt structure (0.01 < a < 0.2, 0.01 < b < 0.2, 0.01 < x < 0.5, M is at least one metal selected from the group consisting of Mg, Al, Co, Mn, Zn, Fe, Cr, Ga, Mo and W; and N is F or S) , Lii+a [Nii-x_yCoxMny] 02-bNb having a hexagonal layered rock-salt structure (0.01 ≤ a ≤ 0.2, 0.01 ≤ b ≤ 0.1, 0.05 < x < 0.3, 0.1 < y < 0.35, 0.15 < x+y < 0.6; and N is F or S),
Li [Lia (NixCθi_2χMnx) i_a]θ2-bNb having a hexagonal layered rock-salt structure (0.01 ≤ a ≤ 0.2, 0.01 ≤ x ≤ 0.5, 0.01 ≤ b < 0.1; and N is F or S) ,
Li [Lia (NixCθi-2χMnx-y/2My) i_a]θ2-bNb having a hexagonal layered rock-salt structure (0.01 < a < 0.2, 0.01 < x < 0.5,
0.01 ≤ Y < 0.1, 0.01 < b < 0.1; M is at least one metal selected from the group consisting of Mg, Ca, Cu and Zn; and
N is F or S) ,
Li [Lia(Nii/3Cθ(1/3-2x)Mn(1/3+χ)Mx)1-.a]02-bNb having a hexagonal layered rock-salt structure (0.01 < a < 0.2, 0.01 ≤ x ≤ 0.5,
0.01 < y < 0.1, 0.01 < b < 0.1; M is at least one metal selected from the group consisting of Mg, Ca, Cu and Zn; and
N is F or S) ,
Li [Lia (NixCθi-2X-yMnxMy) !_a] U2-bNb having a hexagonal layered rock-salt structure (0.01 < a ≤ 0.2, 0.01 ≤ x ≤ 0.5, 0.01 ≤
Y ≤ 0.1, 0.01 ≤ b ≤ 0.1; M is at least one metal selected from the group consisting of B, Al, Fe and Cr; and N is F or
S),
Li [Lia (NixCθi_2χ-yMnx_z/2MyN2) i_a] O2-bNb having a hexagonal layered rock-salt structure (0.01 ≤ a ≤ 0.2, 0.01 ≤ x ≤ 0.5, 0.01 < y < 0.1, 0.01 ≤ b ≤ 0.1; M is at least one metal selected from the group consisting of B, Al, Fe and Cr; and N is Mg or Ca; N is F or S) ,
LiMxFei-xPθ4 having an olivine structure (0 ≤ x ≤ 1; and M is at least one metal selected from the group consisting of Co, Ni and Mn) ,
Lii+a [Mn2-XMX] O4-bNb having a cubic spinel structure (0.01 < a < 0.15, 0.01 ≤ b < 0.2, 0.01 < x < 0.1; M is at least one metal selected from the group consisting of Co, Ni, Cr, Mg, Al, Zn, Mo and W; and N is F or S) , and Lii+a[Ni0.5Mni.5_χMχ]θ4-bNb having a cubic spinel structure (0.01 < a < 0.15, 0.01 < b < 0.2, 0.01 ≤ x < 0.1; M is at least one metal selected from the group consisting of Co, Ni, Cr, Mg, Al, Zn, Mo and W; and N is F or S) .
The present invention also provides a method of producing a cathode active material for lithium secondary- battery, the method comprising adding a solution of dissolved fluorine (F) to a solution of powdered elemental precursor of high dispersibility; allowing the mixture to react at a temperature of 5O0C to 1500C for 1 to 48 hours to form a powdered fluorine compound of high dispersibility in a complex salt form; drying the formed powdered fluorine compound at 1100C for 6 to 24 hours; subsequently thermally treating the powdered fluorine compound at a temperature of 1500C to 9000C for 1 to 20 hours in any of an oxidizing atmosphere, a reducing atmosphere and a vacuum; and then adding 0.05 to 10 parts by weight of the powdered fluorine compound to 100 parts by weight of a cathode active material for lithium secondary battery, and uniformly mixing the mixture.
The solution of elemental precursor may be at a concentration of 0.1 to 3 M, and the solution of dissolved fluorine (F) may be at a concentration of 0.1 to 18 M. The method of the present invention is characterized in that the mixture of the solution and the solution is allowed to react at a temperature of 500C to 1500C for 1 to 48 hours, thus to form a powdered fluorine compound of high dispersibility in a complex salt form.
The elemental precursor may be any one compound selected from alkoxides, sulfates, nitrates, acetates, chlorides and phosphates of at least one element selected from the group consisting of Cs, K, Li, Na, Rb, Ti, Ag(I), Ag(II), Ba, Ca, Cu, Cd, Fe, Hg(II), Hg(I), Mn(II), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi(III), Ce(III), Cr, Dy, Eu, Ga, Gd, Fe, Ho, In, La, Lu, Mn(III), Nd, VO, Pr, Sb(III), Sc, Sm, Tb, Ti(III), Tm, Y, Yb, TI, Ce(IV), Ge, Hf, Si, Sn, Ti(IV), V, Zr, Nb, Sb(V), Ta, Bi(V), Mo, Re, S and W.
The solution of dissolved fluorine (F) to precipitate the elemental precursor in a complex salt form may be a solution of a compound selected from the group of compounds which can provide fluorine (F) so as to precipitate the elemental precursor in a complex salt form, such as HN4F, HF, AHF (anhydrous HF) and the like. Hereinafter, the present invention will be described in more detail.
The present invention relates to a cathode active material prepared by forming a powdered fluorine compound and adding this to a cathode active material, in order to prevent the phenomenon that the life span characteristics of lithium secondary batteries, and particularly the battery performance at high pressures and high rates, are deteriorated.
The method of producing a cathode active material of the present invention comprises synthesizing a powdered fluorine compound to be used as an additive for the cathode active material for lithium secondary battery, and the fluorine compound to be synthesized may be at least one selected from the group consisting of CsF, KF, LiF, NaF, RbF, TiF, AgF, AgF2 , BaF2, CaF2, CuF2, CdF2, FeF2, HgF2, Hg2F2, MnF2, MgF2, NiF2, PbF2, SnF2, SrF2, XeF2, ZnF2, AlF3, BF3, BiF3, CeF3, CrF3, DyF3, EuF3, GaF3, GdF3, FeF3, HoF3, InF3, LaF3, LuF3, MnF3, NdF3, VOF3, PrF3, SbF3, ScF3, SmF3, TbF3, TiF3, TmF3, YF3, YbF3, TIF3, CeF4, GeF4, HfF4, SiF4, SnF4, TiF4, VF4, ZrF4, NbF5, SbF5, TaF5, BiF5, MoF6, ReF6, SF6 and WF6.
The powdered fluorine compound of the present invention may be in an amorphous phase, a crystalline phase, or a mixed phase of amorphous and crystalline phases. In a preferred method of producing a powdered fluorine compound as an additive for the cathode active material for lithium secondary battery, a solution of dissolved fluorine (F) is added to a solution of powdered elemental precursor of high dispersibility, the mixture is allowed to react at a temperature of 5O0C to 15O0C for 1 to 48 hours to form a powdered fluorine compound of high dispersibility in a complex salt form, subsequently the formed powdered fluorine compound is dried at HO0C for 6 to 24 hours, and then the dried powdered fluorine compound is thermally treated at a temperature of 15O0C to 9000C for 1 to 20 hours in any of an oxidizing atmosphere, a reducing atmosphere and a vacuum, so as to provide a powdered fluorine compound.
The reason for raising the temperature for co-immersion reaction as such is because a precipitate of high dispersibility can be obtained in a complex salt form by means of co-immersion of elemental precursors at high temperatures .
As described in the above, when a solution containing fluorine (F) is added to a solution of an elemental precursor, a powdered fluorine compound is formed after a certain length of time, and this powdered fluorine compound can be used, after being thermally treated, as an additive for the cathode active material for lithium secondary battery. When a fluorine compound is formed by mixing a solution of elemental precursor and a solution containing fluorine (F), it is not necessary to control the precipitation rate, and thus it is advantageous, as compared with the case of adding small amounts of the solution containing fluorine (F) . Furthermore, mixing an elemental precursor and fluorine (F) in advance to form a fluorine compound allows reduction of the amount of the solvent used. For example, if the solvent being used is alcohol or ethylene glycol, since these are more expensive reagents than distilled water, reduction of the amount of solvent would be advantageous in view of reducing the production costs in the process of synthesizing the fluorine compound.
Specifically, at least one elemental precursor selected from the group consisting of Cs, K, Li, Na, Rb, Ti, Ag(I), Ag(II), Ba, Ca, Cu, Cd, Fe, Hg(II), Hg(I), Mn(II), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi(III), Ce(III), Cr, Dy, Eu, Ga, Gd, Fe, Ho, In, La, Lu, Mn(III), Nd, VO, Pr, Sb(III), Sc, Sm, Tb, Ti(III), Tm, Y, Yb, TI, Ce(IV), Ge, Hf, Si, Sn, Ti(IV), V, Zr, Nb, Sb(V), Ta, Bi(V), Mo, Re, S and W, is first dissolved in an alcohol solvent such as methanol, ethanol, isopropanol or the like, or in an ether solvent such as ethylene glycol, butyl glycol or the like, or in distilled water, and then the formed solution is mixed with a solution containing fluorine (F) to form a powdered fluorine compound.
Here, it is preferable to use a solution of elemental precursor at a concentration of 0.1 to 3 M, and to use a solution of fluorine (F) at a concentration of 0.1 to 18 M. When a solution of elemental precursor at a concentration less than 0.1 M is used, the total amount of the elemental precursor is insufficient, and thus, precipitates are not formed even though the solution containing fluorine (F) is added, thus the production of fluorine compound being difficult. When a solution of elemental precursor at a concentration higher than 3 M is used, the concentration of the elemental precursor is too high that a fluorine compound of very large crystals may be formed instead of the desired powdered fluorine compound. This is because the rate of fluoride ions binding with the elemental precursor molecules is very high. Fluoride ion is an anion having the fastest binding ability among others.
Moreover, the reason for using a solution containing fluorine (F) at a concentration of 0.1 M to 18 M is that, when a solution of elemental precursor at a concentration of 0.1 M to 3 M is used, the valency of the cation of the elemental precursor is in the range of +1 to +6, while the fluoride anion to bind with the cation is F~, and thus, the concentration of the fluoride ion should be at least equal to the concentration of the cation of the elemental precursor (for example, in the case of producing LiF) , or should be at most 6 times the concentration of the cation of the elemental precursor (for example, in the case of producing W+6 + 6F~ → WF6) .
For the elemental precursor, alkoxides such as methoxides, ethoxides, isopropoxides and butoxides, sulfates, nitrates, acetates, chlorides or oxides can be used.
The solution containing fluorine (F) , which is added to precipitate the elemental precursor in the complex salt form, may be a solution of NH4F, HF, AHF (anhydrous HF) or the like. The solution of elemental precursor and the solution containing fluorine (F) are mixed and reacted at a temperature of 500C to 15O0C for 1 to 48 hours. According to another embodiment of the present invention, there is provided a method of producing a powdered fluorine compound, the method comprising adding a solution containing fluorine (F) to a solution of dissolved powdered elemental precursor of high dispersibility at a constant rate, and allowing the mixture to react at a temperature of 5O0C to 1500C for 1 to 48 hours, thus to form a powdered fluorine compound in a complex salt form. The reason for increasing the temperature of the co-immersion reaction is that co-immersion of the elemental precursor can result in a precipitate of high dispersibility in a complex salt form at high temperatures.
When a fluorine compound is formed by mixing an elemental precursor and fluorine (F) as described above, there may be occurrences in which the resulting fluorine compound cannot attain a powdered form of high dispersibility due to the characteristics of the elemental precursor, and rather aggregates with strong tendency to form large granules of the fluorine compound. At this time, addition of the fluorine compound to a cathode active material may lead to an effect of improving the properties of the cathode active material, which is negligible. Therefore, in such a case, it is desirable to add the solution containing fluorine (F) at a constant rate as described above, thus to control the precipitation rate and to form the fluorine compound in a powdered form of high dispersibility.
More specifically, at least one elemental precursor selected from the group consisting of Cs, K, Li, Na, Rb, Ti, Ag(I), Ag(II), Ba, Ca, Cu, Cd, Fe, Hg(II), Hg(I), Mn(II), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi(III), Ce(III), Cr, Dy, Eu, Ga, Gd, Fe, Ho, In, La, Lu, Mn(III), Nd, VO, Pr, Sb(III), Sc, Sm, Tb, Ti(III), Tm, Y, Yb, TI, Ce(IV), Ge, Hf, Si, Sn, Ti(IV), V, Zr, Nb, Sb(V), Ta, Bi(V), Mo, Re, S and W, is first dissolved in an alcohol solvent such as methanol, ethanol, isopropanol or the like, or in an ether solvent such as ethylene glycol, butyl glycol or the like, or in distilled water, and then a solution containing fluorine (F) is added thereto at a constant rate, thus to form a powdered fluorine compound of high dispersibility.
According to the present invention, the formed powdered fluorine compound is dried at 1100C for β to 24 hours, and then thermally treated at a temperature of 15O0C to 9000C for 1 to 20 hours in any of an oxidizing atmosphere, a reducing atmosphere and a vacuum. Thus produced powdered fluorine compound can be used as an additive for cathode active materials for lithium secondary battery. The process of thermal treatment allows removal of any impurities that have not been removed previously, so that a powdered fluorine compound in the desired form can be obtained.
When the synthesized powdered fluorine compound is added to a cathode active material, the effect of the acid generated in the vicinity of the cathode active material may be reduced, or the reactivity of the cathode active material with the electrolyte may be suppressed, and thereby the phenomenon that the battery capacity rapidly decreases can be improved. It is also possible to provide a cathode active material having improved charging/discharging characteristics, life span characteristics, high voltage characteristics, and high rate capability.
According to a preferred embodiment of the present invention, there is provided a cathode active material for lithium secondary battery, to which a synthesized powdered fluorine compound is added, the method comprising uniformly mixing 0.05 to 10 parts by weight of the powdered fluorine compound with 100 parts by weight of the cathode active material for lithium secondary battery. When the powdered fluorine compound is mixed in an amount of less than 0.05 parts by weight, the amount added is insufficient, and it is difficult to achieve the effect of the present invention sufficiently.
On the other hand, when the powdered fluorine compound is mixed in an amount of more than 10 parts by weight, the fluorine compound is added to the cathode active material in excess, and acts as a resistance factor, thus causing a rapid decrease in the initial capacity. As a result, a cathode active material having excellent charging/discharging characteristics, life span characteristics, high voltage characteristics, and high rate capability cannot be provided. This can be understood as an occurrence similar to a phenomenon found in an already known technology for surface treatment of cathode active materials, that when surface treatment is performed using an excess of a material, the material in excess acts as a resistance factor, and deteriorates the charging/discharging characteristics, life span characteristics and high rate capability.
Accordingly, it is extremely important to appropriately control the amounts of the additive and the extent of surface treatment. The most important reason for operating the cathode active material at high voltages is to increase the capacity, and the most important reason for increasing the capacity of the cathode active material is to provide more storage for energy in the produced batteries. From this point of view, the rapid decrease in the initial capacity is contradictory to the object of the present invention to solve the problem of improving the performance of batteries.
According to the current embodiment of the present invention, a uniform mixture of the cathode active material and the synthesized powdered fluorine compound is further thermally treated at a temperature of 1500C to 6000C for 1 to 20 hours in any of an oxidizing atmosphere, a reducing atmosphere and a vacuum to obtain a powdered fluorine compound-added cathode active material for lithium secondary battery. The process of thermal treatment allows increasing the binding power of the fluorine compound and the cathode active material. [Advantageous Effects]
According to the present invention, a fluorine compound-added cathode active material for lithium secondary battery is prepared by synthesizing a powdered fluorine compound as an additive for cathode active materials for lithium secondary battery, and adding the obtained fluorine compound to a cathode active material for lithium secondary battery. This powdered fluorine compound-added cathode active material for lithium secondary battery exhibits excellent charging/discharging characteristics, life span characteristics, high voltage characteristics and high rate capability, which characteristics are obtained by reducing the effect of acid generated in the vicinity of the cathode active material, or suppressing the reactivity of the cathode active material and the electrolyte, thereby to improve the phenomenon that the battery capacity rapidly decreases . [Description of Drawings]
Hereinafter, the present invention will be described in detail with reference to Examples, but these Examples are not intended to limit the present invention by any means. [EXAMPLE 1]
1. Production of AlF3
In a 500-ml beaker, Al (NO3) 3- 9H2O was dissolved in 100 ml of distilled water to a concentration of 0.25 M, and then 100 ml of a 0.75 M solution of NH4F was produced. After maintaining the reactor temperature at about 800C, the two solutions were mixed at a flow rate of 1 ml/min, and were subjected to a co-immersion reaction, followed by stirring for 12 hours. The average temperature of the reactor was maintained at about 8O0C. The reason for increasing the temperature of the co-immersion reaction is because co- immersion of AlF3 results in a precipitate of high dispersibility in a complex salt form at high temperatures. The fluorine compound thus obtained was washed several times with distilled water, and was dried in a constant temperature air dryer at 1100C for 12 hours. Then, the product was thermally treated at 4000C in an inert atmosphere to produce AIF3.
2. Evaluation of properties of AlF3 i) XRD (X-Ray Diffraction) An X-ray diffraction pattern of the AIF3 produced as described above was measured using an X-ray diffraction analyzer (trade name: Rint-2000, manufactured by Rigaku Corp., Japan). The resulting pattern is presented in Fig. 2. ii) SEM (Scanning Electron Microscopy)
A SEM (trade name: JSM 6400, manufactured by JEOL, Inc., Japan) photograph of the AlF3 produced by the method of Example 1 is presented in Fig. 3.
3. Production of AlF3-added LiCoO2 The AIF3 produced as described above was added to a commercially available cathode active material for lithium secondary battery, LiCoO2, in a proportion of 2 mol% based on the cathode active material, and the mixture was uniformly mixed to produce AlF3-added LiCoO2. 4. Properties evaluation of AlF3-added LiCoO2 i) XRD
An X-ray diffraction pattern of the AlF3-added LiCoO2 produced as described above was measured using an X-ray diffraction analyzer (trade name: Rint-2000, manufactured by Rigaku Corp., Japan). The resulting pattern is presented in
Fig. 4. ii) SEM
A SEM (trade name: JSM 6400, manufactured by JEOL, Inc., Japan) photograph of the AlF3-added LiCoO2 produced as described above is presented in Fig. 5. iii) EDS (Energy Dispersive Spectroscopy) An EDS (trade name: JSM 6400, manufactured by JEOL, Inc., Japan) photograph of the AlF3~added LiCoθ2 produced as described above is presented in Fig. 7. Al and F were mixed with a uniform distribution. 5. Production of cathode
In order to produce a cathode using the AlF3~added LiCoθ2 produced according to the present invention, 20 mg of the AlF3-added LiCoO2, 8 mg of Teflonized acetylene black, and 4 mg of graphite were mixed uniformly. The mixture was uniformly compressed under a pressure of 1 ton using a stainless steel Ex-met, and was dried at 13O0C to produce a cathode for lithium secondary battery. 6. Production of coin cell
Using the cathode produced as described above, a counter electrode formed from lithium foil, and a separator formed from porous polyethylene film (Celgard 2300 manufactured by Celgard LLC, thickness: 25 μm) , and using a 1 M solution of LiPF6 in a mixed solvent of ethylene carbonate and dimethyl carbonate at a volume ratio of 1:1 as liquid electrolyte, a CR-2032 coin cell was produced according to a conventional production procedure for lithium battery. To evaluate the properties of the coin cell produced as described above, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at ambient temperature (300C) in a potential region of from 3.0 to 4.5 V and at current densities of 0.2 mA/cm2 and 0.8 mA/cm2. The changes in capacity with the number of cycles are presented in Fig. 8 and Fig. 9. In the case of AlF3-added LiCoθ2, the coin cell exhibited a capacity retention of 94.4% at 0.2 mA/cm2 and a capacity retention of 89% at 0.8 mA/cm2, both at ambient temperature (300C), up to 50 cycles. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [EXAMPLE 2]
1. Production of ZrF4
In a 500-ml beaker, ZrO (NO3) 2* 2H2O was dissolved in 100 ml of distilled water to a concentration of 0.25 M, and then 100 ml of a 1 M solution of NH4F was produced. After maintaining the reactor temperature at about 800C, the two solutions were mixed at a flow rate of 1 ml/min, and were subjected to a co-immersion reaction, followed by stirring for 12 hours. The average temperature of the reactor was maintained at about 8O0C. The reason for increasing the temperature of the co- immersion reaction is because co-immersion of ZrF4 results in a precipitate of high dispersibility in a complex salt form at high temperatures. The fluorine compound thus obtained was washed several times with distilled water, and was dried in a constant temperature air dryer at HO0C for 12 hours. Then, the product was thermally treated in an inert atmosphere to produce ZrF4.
2. Production of ZrF4-added LiCoO2 The ZrF4 produced as described above was added to a commercially available cathode active material for lithium secondary battery, LiCoO2, in a proportion of 2 mol% based on the cathode active material, and the mixture was uniformly mixed to produce ZrF4-added LiCoO2. 3. Production of coin cell and properties evaluation
Using the ZrF4-added LiCoO2 produced as described above, a cathode was produced in the same manner as in Example 1, and a coin cell containing this cathode was produced.
To evaluate the properties of the coin cell produced as described above, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 30°C in a potential region of from 3.0 to 4.5 V and at a current density of 0.2 mA/cm2. The change in capacity with the number of cycles is presented in Fig. 10. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [EXAMPLE 3]
1. Production of MgF2
In a 500-ml beaker, Mg (NO3) 2- 6H2O was dissolved in 100 ml of distilled water to a concentration of 0.25 M, and then 100 ml of a 0.5 M solution of NH4F was produced. After maintaining the reactor temperature at about 8O0C, the two solutions were mixed at a flow rate of 1 ml/min, and were subjected to a co-immersion reaction, followed by stirring for 12 hours. The average temperature of the reactor was maintained at about 8O0C. The reason for increasing the temperature of the co-immersion reaction is because co- immersion of MgF2 results in a precipitate of high dispersibility in a complex salt form at high temperatures. The fluorine compound thus obtained was washed several times with distilled water, and was dried in a constant temperature air dryer at 1100C for 12 hours. Then, the product was thermally treated in an inert atmosphere to produce MgF2.
2 . Production of MgF2-added LiCoO2
The MgF2 produced as described above was added to a commercially available cathode active material for lithium secondary battery, LiCoO2, in a proportion of 2 mol% based on the cathode active material, and the mixture was uniformly mixed to produce MgF2-added LiCoO2. 3. Production of coin cell and properties evaluation
Using the MgF2-added LiCoO2 produced as described above, a cathode was produced in the same manner as in Example 1, and a coin cell containing this cathode was produced.
To evaluate the properties of the coin cell produced as described above, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 300C in a potential region of from 3.0 to 4.5 V and at a current density of 0.2 mA/cm2. The change in capacity with the number of cycles is presented in Fig. 10. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [EXAMPLE 4] 1. Production of ZnF2
In a 500-ml beaker, Zn (NO3) 2" 2H2O was dissolved in 100 ml of distilled water to a concentration of 0.25 M, and then 100 ml of a 0.5 M solution of NH4F was produced. After maintaining the reactor temperature at about 80 °C, the two solutions were mixed at a flow rate of 1 ml/min, and were subjected to a co-immersion reaction, followed by stirring for 12 hours. The average temperature of the reactor was maintained at about 800C. The reason for increasing the temperature of the co-immersion reaction is because co- immersion of ZnF2 results in a precipitate of high dispersibility in a complex salt form at high temperatures. The fluorine compound thus obtained was washed several times with distilled water, and was dried in a constant temperature air dryer at HO0C for 12 hours. Then, the product was thermally treated in an inert atmosphere to produce ZnF2.
2. Production of ZnF2-added LiCoO2
The ZnF2 produced as described above was added to a commercially available cathode active material for lithium secondary battery, LiCoO2, in a proportion of 2 mol% based on the cathode active material, and the mixture was uniformly mixed to produce ZnF2-added LiCoO2.
3. Production of coin cell and properties evaluation Using the ZnF2-added LiCoO2 produced as described above, a cathode was produced in the same manner as in Example 1, and a coin cell containing this cathode was produced.
To evaluate the properties of the coin cell produced as described above, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 30 °C in a potential region of from 3.0 to 4.5 V and at a current density of 0.2 mA/cm2. The change in capacity with the number of cycles is presented in Fig. 10. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [EXAMPLE 5] AlF3-added LiNi0-SMn0.5O2 was produced in the same manner as in Example 1, and the properties were evaluated. Then, a coin cell was produced using the AlF3-added LiNi0.5Mn0-SO2. To evaluate the properties of the produced coin cell, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 300C in a potential region of from 2.8 to 4.5 V and at current densities of 0.2 mA/cm2 and 0.8 mA/cm2. The changes in capacity with the number of cycles are presented in Fig. 12 and Fig. 13. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [EXAMPLE 6]
AlF3-added LiNii/3Cθi/3Mni/3θ2 was produced in the same manner as in Example 1, and the properties were evaluated. Then, a coin cell was produced using the AlF3- added LiNii/3Cθi/3Mni/3θ2. To evaluate the properties of the produced coin cell, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 3O0C in a potential region of from 2.8 to 4.6 V and at current densities of 0.2 mA/cm2 and 0.8 mA/cm2. The changes in capacity with the number of cycles are presented in Fig. 15 and Fig. 16. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [EXAMPLE 7]
AlF3-added LiNi0.4C00.2Mn0-4O2 was produced in the same manner as in Example 1, and the properties were evaluated. Then, a coin cell was produced using the AlF3-added LiNi0-4Co0.2Mn0-4O2. To evaluate the properties of the produced coin cell, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 3O0C in a potential region of from 2.8 to 4.6 V and at current densities of 0.2 mA/cm2 and 0.8 mA/cm2. The changes in capacity with the number of cycles are presented in Fig. 18 and Fig. 19. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [EXAMPLE 8]
AlF3-added LiNi0.8Co0.iMn0.iθ2 was produced in the same manner as in Example 1, and the properties were evaluated. Then, a coin cell was produced using the AlF3-added LiNio.8Cθo.iMn0.iC>2" To evaluate the properties of the produced coin cell, a charging/discharging experiment was performed using an electrochemical battery analyzer (Toscat 3000U manufactured by Toyo System Co., Ltd., Japan), at 3O0C in a potential region of from 3.0 to 4.5 V and at current densities of 0.2 mA/cm2 and 0.8 mA/cm2. The changes in capacity with the number of cycles are presented in Fig. 21 and Fig. 22. The coin cell showed a small decrease in capacity with the number of cycles, and thus, the coin cell exhibited excellent life span characteristics. [COMPARATIVE EXAMPLE 1]
A conventional LiCoθ2 cathode active material with no added fluorine compound was used to evaluate the properties in the same manner as in Example 1. Fig. 4 shows X-ray diffraction (XRD) patterns of the cathode active materials obtained in Example 1 and Comparative Example 1. Furthermore, a field emission scanning electron microscopic (FE-SEM) photograph of the cathode active material obtained in Comparative Example 1 is presented in Fig. 6. The cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 1 and Comparative Example 1 at 3O0C in a voltage range of from 3.0 to 4.5 V and at a constant current density of 0.2 mA/cm2, are presented in Fig. 8, while the cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 1 and Comparative Example 1 at 3O0C in a voltage range of from 3.0 to 4.5 V and at a constant current density of 0.8 mA/cm2, are presented in Fig. 9. The cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Examples 1 through 4 and Comparative Example 1 at 3O0C in a voltage range of from 3.0 to 4.5 V and at a constant current density of 0.2 mA/cm2, are presented in Fig. 10. [COMPARATIVE EXAMPLE 2]
LiNio.5Mno.5O2 cathode active material with no added AIF3 was used to evaluate the properties in the same manner as in Example 1. Fig. 11 shows XRD patterns of the cathode active materials obtained in Example 5 and Comparative Example 2. The cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 5 and Comparative Example 2 at 300C in a voltage range of from 2.8 to 4.5 V and at a constant current density of 0.2 mA/cm2, are presented in Fig. 12, while the cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 5 and Comparative Example 2 at 300C in a voltage range of from 2.8 to 4.5 V and at a constant current density of 0.8 mA/cm2, are presented in Fig. 13. [COMPARATIVE EXAMPLE 3]
LiNii/3Cθi/3Mni/3θ2 cathode active material with no added AIF3 was used to evaluate the properties in the same manner as in Example 1. Fig. 14 shows XRD patterns of the cathode active materials obtained in Example 6 and Comparative Example 3. The cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 6 and Comparative Example 3 at 3O0C in a voltage range of from 2.8 to 4.6 V and at a constant current density of 0.2 mA/cm2, are presented in Fig. 15, while the cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 6 and Comparative Example 3 at 3O0C in a voltage range of from 2.8 to 4.6 V and at a constant current density of 0.8 mA/cm2, are presented in Fig. 16. [COMPARATIVE EXAMPLE 4] LiNio.4Coo.2Mno.4O2 cathode active material with no added AlF3 was used to evaluate the properties in the same manner as in Example 1. Fig. 17 shows XRD patterns of the cathode active materials obtained in Example 7 and Comparative Example 4. The cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 7 and Comparative Example 4 at 300C in a voltage range of from 2.8 to 4.6 V and at a constant current density of 0.2 mA/cm2, are presented in Fig. 18, while the cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 7 and Comparative Example 4 at 300C in a voltage range of from 2.8 to 4.6 V and at a constant current density of 0.8 mA/cm2, are presented in Fig. 19.
[COMPARATIVE EXAMPLE 5]
LiNio.8Coo.1Mno.1O2 cathode active material with no added AlF3 was used to evaluate the properties in the same manner as in Example 1. Fig. 20 shows XRD patterns of the cathode active materials obtained in Example 8 and Comparative Example 5. The cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 8 and Comparative Example 5 at 3O0C in a voltage range of from 3.0 to 4.5 V and at a constant current density of 0.2 mA/cm2, are presented in Fig. 21, while the cycling curves of half cells, which are obtained by performing an experiment using the cathode active materials of Example 8 and Comparative Example 5 at 3O0C in a voltage range of from 3.0 to 4.5 V and at a constant current density of 0.8 mA/cm2, are presented in Fig. 22. [industrial Applicability]
According to the present invention, a fluorine compound-added cathode active material for lithium secondary battery is produced by synthesizing a powdered fluorine compound as an additive for cathode active materials for lithium secondary battery, and adding this powdered fluorine compound to a cathode active material for lithium secondary battery. This powdered fluorine compound-added cathode active material for lithium secondary battery exhibits excellent charging/discharging characteristics, life span characteristics, high voltage characteristics and high rate capability, which characteristics are obtained by reducing the effect of acid generated in the vicinity of the cathode active material, or suppressing the reactivity of the cathode active material and the electrolyte, to thereby improve the phenomenon that the battery capacity rapidly decreases . As discussed above, while the present invention has been particularly shown and described with reference to limited drawings and Examples, it will be understood by those of ordinary skill in the art that the present invention is not limited thereby, and that various corrections and modifications may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.

Claims

[CLAIMS]
[Claim l]
A cathode active material for lithium secondary battery, comprising a fluorine compound in a complex salt form added thereto. [Claim 2]
The cathode active material for lithium secondary battery according to claim 1, wherein the fluorine compound is at least one selected from the group consisting of CsF, KF, LiF, NaF, RbF, TiF, AgF, AgF2 , BaF2, CaF2, CuF2, CdF2, FeF2, HgF2, Hg2F2, MnF2, MgF2, NiF2, PbF2, SnF2, SrF2, XeF2, ZnF2, AlF3, BF3, BiF3, CeF3, CrF3, DyF3, EuF3, GaF3, GdF3, FeF3, HoF3, InF3, LaF3, LuF3, MnF3, NdF3, VOF3, PrF3, SbF3, ScF3, SmF3, TbF3, TiF3, TmF3, YF3, YbF3, TIF3, CeF4, GeF4, HfF4, SiF4, SnF4, TiF4, VF4, ZrF4, NbF5, SbF5, TaF5, BiF5, MoF6, ReF6, SF6 and WF6. [Claim 3]
The cathode active material for lithium secondary battery according to claim 1, wherein the cathode active material to which the fluorine compound is added, is any one selected from the following:
Lii+a[Cθi-xMx]θ2-bNb having a hexagonal layered rock-salt structure (0.01 ≤ a ≤ 0.2, 0.01 ≤ b ≤ 0.2, 0.01 ≤ x ≤ 0.1; M is at least one metal selected from the group consisting of Mg, Al, Ni, Mn, Zn, Fe, Cr, Ga, Mo and W; and N is F or S) , Lii+a [Nii_xMχ] 02-bNb having a hexagonal layered rock- salt structure (0.01 < a < 0.2, 0.01 < b ≤ 0.2, 0.01 < x < 0.5, M is at least one metal selected from the group consisting of Mg, Al, Co, Mn, Zn, Fe, Cr, Ga, Mo and W; and 5 N is F or S) ,
Lii+a[Nii-.x-yCoxMny]θ2-bNb having a hexagonal layered rock- salt structure (0.01 < a < 0.
2, 0.01 < b < 0.1, 0.05 < x < 0.
3, 0.1 ≤ Y ≤ 0.35, 0.15 ≤ x+y ≤ 0.6; and N is F or S),
Li [Li3 (NixCθi_2χMnx) i_a]O2-bNb having a hexagonal layered 0 rock-salt structure (0.01 ≤ a ≤ 0.2, 0.01 ≤ x ≤ 0.5, 0.01 ≤ b ≤ 0.1; and N is F or S) ,
Li [Lia(NixCoi-.2XMnx-y/2My) i-a]O2-bNb having a hexagonal layered rock-salt structure (0.01 < a < 0.2, 0.01 ≤ x ≤ 0.5,
0.01 < y < 0.1, 0.01 ≤ b ≤ 0.1; M is at least one metal 5 selected from the group consisting of Mg, Ca, Cu and Zn; and
N is F or S) ,
Li [Lia(Nii/3Co(1/3-2χ)Mn(i/3+X)Mx)i-a]02-bNb having a hexagonal layered rock-salt structure (0.01 ≤ a ≤ 0.2, 0.01 ≤ x ≤ 0.5,
0.01 < y < 0.1, 0.01 ≤ b ≤ 0.1; M is at least one metal
-0 selected from the group consisting of Mg, Ca, Cu and Zn; and
N is F or S) ,
Li [Lia (NixCoi-2x-yMnxMy) i-a] O2-bNb having a hexagonal layered rock-salt structure (0.01 < a ≤ 0.2, 0.01 ≤ x ≤ 0.5, 0.01 ≤ y ≤ 0.1, 0.01 ≤ b ≤ 0.1; M is at least one metal selected from the group consisting of B, Al, Fe and Cr; and N is F or S),
Li [Lia(NixCθi_2χ-yMnx-z/2MyNz) i-a]O2-bNb having a hexagonal layered rock-salt structure (0.01 ≤ a ≤ 0.2, 0.01 ≤ x ≤ 0.5, 0.01 < y ≤ 0.1, 0.01 ≤ b < 0.1; M is at least one metal selected from the group consisting of B, Al, Fe and Cr; and
N is Mg or Ca; N is F or S),
LiMxFei-xPθ4 having an olivine structure (0 ≤ x ≤ 1; and M is at least one metal selected from the group consisting of Co, Ni and Mn) ,
Lii+a[Mn2-χMx]O4-bNb having a cubic spinel structure (0.01 < a ≤ 0.15, 0.01 < b < 0.2, 0.01 < x < 0.1; M is at least one metal selected from the group consisting of Co, Ni, Cr, Mg, Al, Zn, Mo and W; and N is F or S) , and Lii+a[Nio.5Mni.5-χMx]θ4-bNb having a cubic spinel structure (0.01 < a < 0.15, 0.01 < b < 0.2, 0.01 < x < 0.1; M is at least one metal selected from the group consisting of Co, Ni, Cr, Mg, Al, Zn, Mo and W; and N is F or S) .
[Claim 4] The cathode active material for lithium secondary battery according to any one of claims 1 to 3, wherein the fluorine compound is added to the cathode active material in an amount of 0.05 to 10 parts by weight relative to 100 parts by weight of the cathode active material. [Claim 5]
A method of producing a cathode active material for lithium secondary battery, the method comprising the steps of: preparing a solution of a powdered elemental precursor of high dispersibility and a solution of dissolved fluorine (F); mixing and reacting the two solutions to obtain a powdered fluorine compound of high dispersibility in a complex salt form; drying the obtained powdered fluorine compound, and then thermally treating the powdered fluorine compound in any of an oxidizing atmosphere, a reducing atmosphere and a vacuum; and adding the thermally treated powdered fluorine compound to a cathode active material for lithium secondary battery in an amount of 0.05 to 10 parts by weight relative to 100 parts by weight of the cathode active material, and uniformly mixing the mixture to obtain a fluorine compound- added cathode active material for lithium secondary battery. [Claim 6]
The method of producing a cathode active material for lithium secondary battery according to claim 5, wherein the concentration of the solution of elemental precursor is 0.1 to 3 M, while the concentration of the solution of dissolved fluorine (F) is 0.1 to 18 M. [Claim 7]
The method of producing a cathode active material for lithium secondary battery according to claim 5 or 6, wherein the elemental precursor is any one compound selected from alkoxides, sulfates, nitrates, acetates, chlorides and phosphates of at least one element selected from the group consisting of Cs, K, Li, Na, Rb, Ti, Ag(I), Ag(II), Ba, Ca, Cu, Cd, Fe, Hg(II), Hg(I), Mn(II), Mg, Ni, Pb, Sn, Sr, Xe, Zn, Al, B, Bi(III), Ce(III), Cr, Dy, Eu, Ga, Gd, Fe, Ho, In, La, Lu, Mn(III), Nd, VO, Pr, Sb(III), Sc, Sm, Tb, Ti(III), Tm, Y, Yb, TI, Ce(IV), Ge, Hf, Si, Sn, Ti(IV), V, Zr, Nb, Sb(V), Ta, Bi(V), Mo, Re, S and W. [Claim 8]
The method of producing a cathode active material for lithium secondary battery according to claim 5, wherein the solution of dissolved fluorine (F) intended to precipitate the elemental precursor in a complex salt form is a solution of at least one compound selected from NH4F, HF and AHF (anhydrous HF) .
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KR101523081B1 (en) * 2013-11-28 2015-06-05 주식회사 포스코 Complex of positive electrode active material and fluorine compound, manufacturing method of the same, and rechargable lithium battery including the complex
KR101670664B1 (en) 2015-05-04 2016-10-31 한국과학기술연구원 Cathode active material coated with F-dopped lithium metal manganese oxide, lithium-ion secondary battery comprising the same and the prepration method thereof
KR101994813B1 (en) 2017-02-24 2019-07-01 정형진 Self-extinguishing adhesive tape

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020095421A (en) * 2001-06-14 2002-12-26 삼성에스디아이 주식회사 Active material for battery and a method of preparing same
KR20030091581A (en) * 2002-05-28 2003-12-03 삼성에스디아이 주식회사 A positive active material for lithium secondary battery and a method of preparing same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050026443A (en) * 2005-02-03 2005-03-15 박우락 The lighter and tobacco case

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020095421A (en) * 2001-06-14 2002-12-26 삼성에스디아이 주식회사 Active material for battery and a method of preparing same
KR20030091581A (en) * 2002-05-28 2003-12-03 삼성에스디아이 주식회사 A positive active material for lithium secondary battery and a method of preparing same

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8697288B2 (en) 2008-04-16 2014-04-15 Envia Systems, Inc. High energy lithium ion secondary batteries
US8187752B2 (en) 2008-04-16 2012-05-29 Envia Systems, Inc. High energy lithium ion secondary batteries
US8916294B2 (en) 2008-09-30 2014-12-23 Envia Systems, Inc. Fluorine doped lithium rich metal oxide positive electrode battery materials with high specific capacity and corresponding batteries
US8389160B2 (en) 2008-10-07 2013-03-05 Envia Systems, Inc. Positive electrode materials for lithium ion batteries having a high specific discharge capacity and processes for the synthesis of these materials
US9960424B2 (en) 2008-12-11 2018-05-01 Zenlabs Energy, Inc. Positive electrode materials for high discharge capacity lithium ion batteries
US8465873B2 (en) 2008-12-11 2013-06-18 Envia Systems, Inc. Positive electrode materials for high discharge capacity lithium ion batteries
US10056644B2 (en) 2009-07-24 2018-08-21 Zenlabs Energy, Inc. Lithium ion batteries with long cycling performance
US8741485B2 (en) 2009-08-27 2014-06-03 Envia Systems, Inc. Layer-layer lithium rich complex metal oxides with high specific capacity and excellent cycling
US8535832B2 (en) 2009-08-27 2013-09-17 Envia Systems, Inc. Metal oxide coated positive electrode materials for lithium-based batteries
US8475959B2 (en) 2009-08-27 2013-07-02 Envia Systems, Inc. Lithium doped cathode material
US8394534B2 (en) 2009-08-27 2013-03-12 Envia Systems, Inc. Layer-layer lithium rich complex metal oxides with high specific capacity and excellent cycling
US9843041B2 (en) 2009-11-11 2017-12-12 Zenlabs Energy, Inc. Coated positive electrode materials for lithium ion batteries
US8993177B2 (en) 2009-12-04 2015-03-31 Envia Systems, Inc. Lithium ion battery with high voltage electrolytes and additives
US8765306B2 (en) 2010-03-26 2014-07-01 Envia Systems, Inc. High voltage battery formation protocols and control of charging and discharging for desirable long term cycling performance
US8741484B2 (en) 2010-04-02 2014-06-03 Envia Systems, Inc. Doped positive electrode active materials and lithium ion secondary battery constructed therefrom
US9083062B2 (en) 2010-08-02 2015-07-14 Envia Systems, Inc. Battery packs for vehicles and high capacity pouch secondary batteries for incorporation into compact battery packs
US8928286B2 (en) 2010-09-03 2015-01-06 Envia Systems, Inc. Very long cycling of lithium ion batteries with lithium rich cathode materials
US8663849B2 (en) 2010-09-22 2014-03-04 Envia Systems, Inc. Metal halide coatings on lithium ion battery positive electrode materials and corresponding batteries
US11380883B2 (en) 2010-11-02 2022-07-05 Zenlabs Energy, Inc. Method of forming negative electrode active material, with lithium preloading
US9166222B2 (en) 2010-11-02 2015-10-20 Envia Systems, Inc. Lithium ion batteries with supplemental lithium
US9923195B2 (en) 2010-11-02 2018-03-20 Zenlabs Energy, Inc. Lithium ion batteries with supplemental lithium
US9553301B2 (en) 2011-08-19 2017-01-24 Envia Systems, Inc. High capacity lithium ion battery formation protocol and corresponding batteries
US9159990B2 (en) 2011-08-19 2015-10-13 Envia Systems, Inc. High capacity lithium ion battery formation protocol and corresponding batteries
US10170762B2 (en) 2011-12-12 2019-01-01 Zenlabs Energy, Inc. Lithium metal oxides with multiple phases and stable high energy electrochemical cycling
US9070489B2 (en) 2012-02-07 2015-06-30 Envia Systems, Inc. Mixed phase lithium metal oxide compositions with desirable battery performance
US9780358B2 (en) 2012-05-04 2017-10-03 Zenlabs Energy, Inc. Battery designs with high capacity anode materials and cathode materials
US11502299B2 (en) 2012-05-04 2022-11-15 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
US10290871B2 (en) 2012-05-04 2019-05-14 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
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US10686183B2 (en) 2012-05-04 2020-06-16 Zenlabs Energy, Inc. Battery designs with high capacity anode materials to achieve desirable cycling properties
US9552901B2 (en) 2012-08-17 2017-01-24 Envia Systems, Inc. Lithium ion batteries with high energy density, excellent cycling capability and low internal impedance
US10115962B2 (en) 2012-12-20 2018-10-30 Envia Systems, Inc. High capacity cathode material with stabilizing nanocoatings
US11476494B2 (en) 2013-08-16 2022-10-18 Zenlabs Energy, Inc. Lithium ion batteries with high capacity anode active material and good cycling for consumer electronics
US11094925B2 (en) 2017-12-22 2021-08-17 Zenlabs Energy, Inc. Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance
US11742474B2 (en) 2017-12-22 2023-08-29 Zenlabs Energy, Inc. Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance
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US11631848B2 (en) 2018-05-23 2023-04-18 Samsung Sdi Co., Ltd. Positive electrode for rechargeable lithium battery and rechargeable lithium battery including same
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CN113594435A (en) * 2021-07-21 2021-11-02 淮北夏川新能源有限公司 High specific energy lithium battery for electric tool

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