(19)
(11)EP 3 486 979 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
14.10.2020 Bulletin 2020/42

(21)Application number: 18747131.3

(22)Date of filing:  02.02.2018
(51)Int. Cl.: 
H01M 4/36  (2006.01)
H01M 4/505  (2010.01)
H01M 4/131  (2010.01)
C01G 53/00  (2006.01)
C01F 7/02  (2006.01)
H01M 4/48  (2010.01)
H01M 4/525  (2010.01)
H01M 4/485  (2010.01)
H01M 10/052  (2010.01)
C01B 35/10  (2006.01)
H01M 4/139  (2010.01)
H01M 10/0525  (2010.01)
(86)International application number:
PCT/KR2018/001470
(87)International publication number:
WO 2018/143734 (09.08.2018 Gazette  2018/32)

(54)

CATHODE ACTIVE MATERIAL FOR SECONDARY BATTERY, AND PREPARATION METHOD THEREFOR

KATHODENAKTIVMATERIAL FÜR LITHIUMSEKUNDÄRBATTERIE UND HERSTELLUNGSVERFAHREN DAFÜR

MATÉRIAU ACTIF DE CATHODE DESTINÉ À UNE BATTERIE SECONDAIRE ET SON PROCÉDÉ DE PRÉPARATION


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 02.02.2017 KR 20170015158

(43)Date of publication of application:
22.05.2019 Bulletin 2019/21

(73)Proprietor: LG Chem, Ltd.
Seoul 07336 (KR)

(72)Inventors:
  • BAEK, So Ra
    Daejeon 34122 (KR)
  • KIM, Ji Hye
    Daejeon 34122 (KR)
  • YOO, Tae Gu
    Daejeon 34122 (KR)
  • JUNG, Wang Mo
    Daejeon 34122 (KR)
  • PARK, Byung Chun
    Daejeon 34122 (KR)

(74)Representative: Hoffmann Eitle 
Patent- und Rechtsanwälte PartmbB Arabellastraße 30
81925 München
81925 München (DE)


(56)References cited: : 
WO-A1-2016/099229
JP-A- 2009 152 214
KR-A- 20040 049 811
US-A1- 2002 071 991
JP-A- 2002 164 053
JP-A- 2009 218 217
KR-A- 20160 049 995
US-A1- 2008 166 637
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention relates to a positive electrode active material for a secondary battery, in which resistance is reduced and gas generation in the secondary battery is reduced, a method of preparing the same, a positive electrode for a secondary battery, and a secondary battery.

    BACKGROUND ART



    [0002] Demand for secondary batteries as an energy source has been significantly increased as technology development and demand with respect to mobile devices have increased. Among these secondary batteries, lithium secondary batteries having high energy density, high voltage, long cycle life, and low self-discharging rate have been commercialized and widely used.

    [0003] However, lithium secondary batteries have limitations in that lifetime rapidly decreases as charge and discharge are repeated. In particular, these limitations are more serious in a long-life or high-voltage battery. The reason for this is due to a phenomenon that occurs when an electrolyte is decomposed or an active material is degraded due to moisture in the battery or other effects, and the internal resistance of the battery increases. Particularly, with respect to a positive electrode material, if degradation of the positive electrode material itself is intensified, dissolution of positive electrode active material components is increased and, as a result, the battery lifetime is rapidly degraded or it is not possible to use the battery at a high voltage.

    [0004] In order to address these limitations, methods of forming a surface treatment layer on a surface of the positive electrode active material have been proposed. Among these methods, with respect to an aluminum-based surface treatment layer in which stabilities at a high voltage and in an electrolyte solution are recognized, since the aluminum-based surface treatment layer in a crystalline state is coated on the surface of a particle, it is difficult for the entire active material to be uniformly coated with the aluminum-based surface treatment layer. Also, there is a limitation in that resistance may be increased due to crystallinity of the aluminum-based compound itself. Furthermore, with respect to a boron (B)-based coating, since the boron (B)-based coating is uniformly formed in an amorphous state, it does not interfere with the movement of lithium ions from the positive electrode material to the electrolyte solution. However, since the boron (B)-based coating reacts with moisture, there is a limitation in that it does not serve as a coating layer when the reaction with the electrolyte solution is prolonged.

    [0005] Thus, development of a positive electrode active material, which may improve lithium secondary battery performance while addressing the above limitations, is urgently required.

    [0006] US 2002/0071991 A1 describes a positive active material for a rechargeable lithium battery. The positive active material includes a core having a lithiated compound and at least two surface-treatment layers on the core, and each of the two surface-treatment layers includes at least one coating element. Alternatively, the positive active material includes at least one surface-treatment layer on the core, wherein the surface treatment at least comprises at least two coating element-included oxides.

    [0007] WO 2016/099229 A1 describes a mixed positive electrode active material, comprising a large-grain positive electrode active material with an average diameter of 10 µm or greater and a small-grain positive electrode active material with an average diameter of 5 µm or smaller, wherein the large-grain positive electrode active material and the small-grain positive electrode active material are coated with different materials between lithium triborate and a metal oxide, respectively.

    [0008] US 2008/166637 A1 relates to a nonaqueous electrolyte battery that includes a positive electrode, a negative electrode and a specific nonaqueous electrolyte. The negative electrode contains a titanium-containing oxide. In certain examples, an active material made of LiCoO2 particles coated with Al2O3 or B2O3 is used.

    DISCLOSURE OF THE INVENTION


    TECHNICAL PROBLEM



    [0009] An aspect of the present invention provides a positive electrode active material, in which output characteristics are excellent due to a decrease in resistance and gas generation in a secondary battery is reduced, a method of preparing the same, a positive electrode for a secondary battery, and a secondary battery.

    TECHNICAL SOLUTION



    [0010] According to an aspect of the present invention, there is provided a positive electrode active material for a secondary battery including: a core including a lithium composite metal oxide represented by Formula 1

            <Formula 1>     Lia(NixCoyMlz)bM2cO2

    wherein, in Formula 1,

    M1 is at least one element selected from the group consisting of manganese and aluminum , and

    M2 is at least one element selected from the group consisting of barium, calcium, zirconium, titanium, magnesium, tantalum, niobium, and molybdenum,

    wherein 1≤a≤1.5, 0.9≤b≤1, 0≤c≤0.1, 0.6≤x<1, 0<y<0.4, 0<z≤0.4, and b+c=1; and a surface treatment layer which is disposed on the core and includes an amorphous oxide containing lithium (Li), boron (B), and aluminum (Al), wherein the surface treatment layer includes the amorphous oxide in which a lithium oxide, a boron oxide, and an aluminum oxide are chemically bonded to one another, wherein the lithium oxide is Li2O, the boron oxide is B2O3, and the aluminum oxide is Al2O3; and, in the amorphous oxide in the surface treatment layer, an amount of the aluminum oxide is greater than an amount of the boron oxide, and an amount of a lithium by-product comprising at least one of LiOH or Li2CO3 present on a surface of the positive electrode active material is less than 0.55 wt% based on a total weight of the positive electrode active material.



    [0011] According to another aspect of the present invention, there is provided a method of preparing a positive electrode active material for a secondary battery as described above including: a first step of preparing a mixture by mixing a lithium composite metal oxide, a boron-containing raw material, and an aluminum-containing raw material; and a second step of forming a surface treatment layer including an amorphous oxide on a core including the lithium composite metal oxide represented by formula 1 above by performing a heat treatment on the mixture in an oxygen atmosphere, , an amount of the aluminum-containing raw material included is greater than 1 time to less than 2.5 times an amount of the boron-containing raw material included, and the heat treatment is performed in a temperature range of 500°C to 800°C.

    [0012] According to another aspect of the present invention, there is provided a positive electrode for a secondary battery and a secondary battery which include the above positive electrode active material.

    ADVANTAGEOUS EFFECTS



    [0013] Since a positive electrode active material of the present invention has excellent lithium ion conductivity even if a surface treatment layer including an amorphous oxide is disposed on a core including a lithium composite metal oxide, a resistance increase rate is low even if the number of charge and discharge cycles is increased, and thus, output characteristics may be excellent.

    [0014] The positive electrode active material of the present invention may prevent damage of the lithium composite metal oxide due to an electrolyte solution and hydrogen fluoride derived from the electrolyte solution by allowing the surface treatment layer including the amorphous oxide on the core including the lithium composite metal oxide to prevent a direct contact between the core and the lithium composite metal oxide. Also, gas generation derived from the contact may be prevented.

    [0015] In the positive electrode active material of the present invention, since LiOH and Li2CO3, which are present on the surface of the positive electrode active material during the formation of the surface treatment layer, are removed by reaction with boron- and/or aluminum-containing materials, the amount of a lithium by-product in the positive electrode active material may be reduced.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0016] 

    FIG. 1 is a graph illustrating discharge capacity retentions relative to an initial cycle of lithium secondary batteries prepared in Examples 1 and 2, and Comparative Examples 1 to 7;

    FIG. 2 is a graph illustrating direct current resistance increase rates according to the number of cycles relative to direct current resistances of the initial cycle of the lithium secondary batteries prepared in Examples 1 and 2 and Comparative Examples 1 to 7; and

    FIG. 3 is a graph illustrating gas generation amounts increased over time relative to initial gas generation amounts of the lithium secondary batteries prepared in Examples 1 and 2 and Comparative Examples 1 to 3 and 6.


    MODE FOR CARRYING OUT THE INVENTION



    [0017] Hereinafter, the present invention will be described in more detail to allow for a clearer understanding of the present invention.

    [0018] A positive electrode active material for a secondary battery according to the present invention may include a core including a lithium composite metal oxide.

    [0019] The lithium composite metal oxide is a compound capable of reversibly intercalating and deintercalating lithium (lithiated intercalation compound). For example, the lithium composite metal oxide may be a layered lithium composite metal oxide which may be used at high capacity and high voltage.

    [0020] The lithium composite metal oxide is represented by Formula 1 below.

            <Formula 1>     Lia(NixCoyM1z)bM2cO2



    [0021] In Formula 1, M1 is at least one element selected from the group consisting of manganese (Mn) and aluminum (Al), and M2 is at least one element selected from the group consisting of barium (Ba), calcium (Ca), zirconium (Zr), titanium (Ti), magnesium (Mg), tantalum (Ta), niobium (Nb), and molybdenum (Mo), wherein 1≤a≤1.5, 0.9≤b≤1, 0≤c≤0.1, 0.6≤x<1, 0<y<0.4, 0<z≤0.4, and b+c=1.

    [0022] In the lithium composite metal oxide represented by Formula 1, lithium (Li) may be included in an amount corresponding to a, that is, 1≤a≤1.5, for example, 1≤a≤1.2. When a satisfies the above-described range, an effect of improving capacity characteristics of the positive electrode active material according to the control of the amount of the Li is significant, and sinterability during the preparation of the active material may be balanced. When a is less than 1, capacity may be reduced, and, when a is greater than 1.5, since particles are sintered in a sintering process, the preparation of the active material may be difficult.

    [0023] In the lithium composite metal oxide represented by Formula 1, nickel (Ni) may be included in an amount corresponding to x, that is, 0.6≤x<1, for example, 0.7≤x<0.95. When the amount of the Ni satisfies the above range, a high-capacity positive electrode active material may be obtained.

    [0024] In the lithium composite metal oxide of Formula 1, cobalt (Co) may be included in an amount corresponding to y, that is, 0<y<0.4, particularly 0<y≤0.2, and more particularly 0.04<y≤0.15. When the amount of the Co satisfies the above-described range, the capacity characteristics may be improved. In a case in which y is 0, the capacity characteristics may be reduced. In a case in which y is greater than the above-described range, costs may be increased.

    [0025] Also, in the lithium composite metal oxide of Formula 1, M1 may be at least one selected from the group consisting of Mn and Al. In a case in which the M1 is Mn, since the M1 improves the capacity characteristics and structural stability of the positive electrode active material, a secondary battery, as a final product, may have high capacity and output characteristics may be improved. In a case in which the M1 is Al, the M1 may improve the output characteristics of the active material.

    [0026] The M1 may be included in an amount corresponding to z, that is, 0<z≤0.4, particularly 0<z≤0.2, and more particularly 0.02<z≤0.15. When z is 0, an improvement effect due to the inclusion of the M1 may not be obtained. In a case in which z is greater than the above-described range, the output characteristics and capacity characteristics of the secondary battery may be reduced.

    [0027] Furthermore, in the lithium composite metal oxide of Formula 1, M2 may be included in an amount corresponding to c, that is, 0≤c≤0.1, for example, 0≤c≤0.05. When the amount of the M2 satisfies the above-described range, the M2 may improve the structural stability of the positive electrode active material, and, as a result, the output characteristics of the secondary battery may be improved. Specifically, the M2 may include at least one element selected from the group consisting of Ba, Ca, Zr, Ti, Mg, Ta, Nb, and Mo, and, for example, may include at least one selected from the group consisting of Zr, Ti, and Mg.

    [0028] a is a mole ratio of Li in the lithium composite metal oxide, b is a mole ratio of Ni, Co, and M1 in the lithium composite metal oxide, and c is a mole ratio of M2 in the lithium composite metal oxide. In this case, b+c may be 1.

    [0029] The lithium composite metal oxide may include primary particles or a secondary particle in which the primary particles are agglomerated. In this case, the primary particles may be uniform or non-uniform. Also, the lithium composite metal oxide may further include a segregation phase of Zr oxide on a surface of the secondary particle or at an interface between the primary particles.

    [0030] Also, the positive electrode active material may have an average particle diameter (D50) of 1 µm to 20 µm. In a case in which the average particle diameter of the positive electrode active material is less than 1 µm, there is a concern that dispersibility in a positive electrode material mixture may be reduced due to the agglomeration of the positive electrode active material, and, in a case in which the average particle diameter of the positive electrode active material is greater than 20 µm, there is a concern that mechanical strength and specific surface area of the positive electrode active material may be reduced. Furthermore, the positive electrode active material may have an average particle diameter (D50) of 3 µm to 18 µm in consideration of significant improvement in rate capability and initial capacity characteristics of the battery due to the control of the particle diameter of the positive electrode active material. Also, in a case in which the positive electrode active material includes the secondary particle, an average particle diameter (D50) of the primary particles constituting the secondary particle may be in a range of 50 nm to 1,000 nm.

    [0031] In the present invention, the average particle diameters (D50) of the positive electrode active material may be defined as a particle diameter at 50% in a cumulative particle diameter distribution. In the present invention, the average particle diameters (D50) of the positive electrode active material, for example, may be measured by using a laser diffraction method. Specifically, with respect to the average particle diameter (D50) of the positive electrode active material, after particles of the positive electrode active material are dispersed in a dispersion medium, the dispersion medium is introduced into a commercial laser diffraction particle size measurement instrument (e.g., Microtrac MT 3000) and irradiated with ultrasonic waves having a frequency of about 28 kHz and an output of 60 W, and the average particle diameter (D50) at 50% in a cumulative particle diameter distribution of the measurement instrument may then be calculated.

    [0032] The positive electrode active material according to the present invention includes a surface treatment layer which is disposed on the core and includes an amorphous oxide containing lithium (Li), boron (B), and aluminum (Al).

    [0033] Since the amorphous oxide does not react with an electrolyte solution and hydrogen fluoride derived from the electrolyte solution and is disposed on the core, the amorphous oxide may prevent or minimize a direct contact between the core and the electrolyte solution and hydrogen fluoride derived from the electrolyte solution. Accordingly, since damage of the core due to the electrolyte solution and hydrogen fluoride derived from the electrolyte solution may be minimized, life characteristics of the lithium secondary battery, as the final product, may be improved.

    [0034] Also, an amount of a lithium by-product present on a surface of the positive electrode active material is less than 0.55 wt%, for example, in a range of 0.4 wt% to less than 0.55 wt% based on a total weight of the positive electrode active material. As described above, in a case in which a lithium composite metal oxide, in which the amount of the nickel is 60 mol% or more based on a total number of moles of the lithium composite metal oxide, is used as the core, high capacity characteristics may be exhibited, but it is disadvantageous in that an excessive amount of the lithium by-product may be formed on the surface of the positive electrode active material. Thus, as the surface treatment layer including the amorphous oxide is formed on the core, since the lithium by-product comprising at least one of LiOH and Li2CO3 present on a surface of the core reacts with boron- and/or aluminum-containing materials to be formed as the amorphous oxide, the amount of the lithium by-product in the positive electrode active material may be reduced. For example, in a case in which the amount of the lithium by-product present on the surface of the positive electrode active material is greater than the above range, a reaction of a lithium salt included in the electrolyte solution with the lithium by-product continuously occurs to generate oxygen, HF, H2O, and other gases, and, as a result, performance of the lithium secondary battery may be adversely affected. Specifically, the reaction may be represented by the following Reaction Formula 1.

            <Reaction Formula 1>     LiPF6 → LiF + PF5 PF5 + 2LiOH → 2LiF + H2O + POF3 PF5 + H2O → POF3 + 2HF 4PF5 + 2Li2CO3 → 3LiPF6 + 2CO2 + LiPO2F2 2HF + Li2CO3 → 2LiF + H2O + CO2



    [0035] Specifically, the surface treatment layer includes a lithium oxide, a boron oxide, and an aluminum oxide, and, in the amorphous oxide in the surface treatment layer, an amount of the aluminum oxide is greater than an amount of the boron oxide. Specifically, the surface treatment layer includes an amorphous oxide containing Li2O, B2O3, and Al2O3, and the Li2O, the B2O3, and the Al2O3 are chemically bonded to one another. The amorphous oxide is chemically bonded and may be present in the form of Li2O-B2O3-Al2O3. For example, the amorphous oxide may be present in the form of 2LiAl7B4O5, 2LiAlB2O5, or 2Li2AlB2O5, and the amorphous oxide may include B and Al in a mole ratio of greater than 1:1 to less than 1:2.5, for example, greater than 1:1 to less than 1:2. In a case in which the amorphous oxide includes B and Al within the above range as in the present invention, since an effect of reducing the lithium by-product present on the surface may be large, gas generation due to the reaction with the electrolyte solution may be improved.

    [0036] For example, in a case in which the amorphous oxide included in the surface treatment layer is present in the form of a mixture of one of Li2O, B2O3, and Al2O3, or two thereof are chemically bonded to each other and the remaining one exists alone, specifically, the amorphous oxide is present in the form of Al2O3, Li2O-Al2O3, Li2O-B2O3, or Li2O-B4O5, since the effect of reducing the lithium by-product present on the surface may be small, a large amount of gas may be generated during the reaction with the electrolyte solution.

    [0037] The Li2O may improve meltability or moldability by reducing high-temperature viscosity of the amorphous oxide. Li2O has excellent lithium ion conductivity and does not react with the electrolyte solution and hydrogen fluoride derived from the electrolyte solution during charging/discharging. Accordingly, the Li2O may improve life characteristics and cycle characteristics of the positive electrode active material by effectively protecting the core. The Li2O may be derived from LiOH and Li2CO3, as the lithium by-products present on the surface of the core.

    [0038] The B2O3 is a main component constituting a glass composition, wherein it plays a role in increasing thermal and chemical stability by forming a three-dimensional network in glass. However, since the B2O3 reacts with moisture, it may reduce chemical stability of the surface treatment layer when a large amount of the B2O3 is included in the amorphous oxide.

    [0039] The Al2O3 is a material having high lithium ion conductivity and may act as a network former in the amorphous oxide. The Al2O3 may affect a thermal expansion coefficient and high-temperature viscosity of the amorphous oxide.

    [0040] In a case in which the surface treatment layer including the amorphous oxide is formed on the core, since the reaction with the electrolyte solution and hydrogen fluoride derived from the electrolyte solution may be suppressed during charging/discharging due to the excellent lithium ion conductivity, the life characteristics may be improved and a positive electrode active material having improved thermal stability may be provided.

    [0041] Also, the above-described surface treatment layer including the amorphous oxide may be uniformly formed on the entire surface of the core.

    [0042] The surface treatment layer may be uniformly formed to an appropriate thickness in consideration of a particle diameter of the core which determines capacity of the positive electrode active material. Specifically, based on a radius of the core, the surface treatment layer may have an average thickness of 20 nm to 100 nm, for example, 50 nm to 100 nm. When the average thickness of the surface treatment layer is less than the above range, an improvement effect resulting from the formation of the surface treatment layer may be insignificant, and, when the average thickness of the surface treatment layer is greater than the above range, resistance of the positive electrode active material may be increased.

    [0043] In the present invention, the particle diameter of the core and the thickness of the surface treatment layer may be measured by cross-sectional analysis of the particle using a focused ion beam (FIB).

    [0044] A method of preparing a positive electrode active material according to the present invention includes a first step of preparing a mixture by mixing a lithium composite metal oxide, a boron-containing raw material, and an aluminum-containing raw material; and a second step of forming a surface treatment layer including an amorphous oxide on a core including the lithium composite metal oxide represented by the above formula 1 by performing a heat treatment on the mixture in an oxygen atmosphere, wherein an amount of the aluminum-containing raw material included is greater than 1 time to less than 2.5 times an amount of the boron-containing raw material included, and the heat treatment is performed in a temperature range of 500°C to 800°C.

    [0045] The lithium composite metal oxide may be prepared by a general method used in the art, or a commercially available lithium composite metal oxide may be purchased and used.

    [0046] In a case in which the amount of the nickel is 60 mol% or more base on the total number of moles of the lithium composite metal oxide, the positive electrode active material may exhibit high capacity characteristics, but an excessive amount of the lithium by-product may be formed on the surface of the positive electrode active material due to low reactivity between a lithium source and a precursor during sintering. As described above, in a case in which the excessive amount of the lithium by-product is present on the surface of the positive electrode active material, the reaction of the lithium salt included in the electrolyte solution with the lithium by-product occurs to generate gas, and, as a result, the performance of the secondary battery may be adversely affected.

    [0047] Thus, since the lithium composite metal oxide, the boron-containing raw material, and the aluminum-containing raw material are mixed and heat-treated, the lithium by-product present on the surface of the lithium composite metal oxide reacts with the boron-containing raw material and the aluminum-containing raw material. Accordingly, the present inventors found that the amount of the lithium by-product present on the surface of the lithium composite metal oxide may not only be reduced, but a positive electrode active material having excellent output characteristics may also be prepared through the formation of an amorphous oxide having excellent lithium ion conductivity, thereby leading to the completion of the present invention.

    [0048] The boron-containing raw material may include at least one selected from the group consisting of H3BO3, HBPO4, B2O3, B2O5, Li2B4O7, and (NH4)2B4O7, and may specifically be H3BO3.

    [0049] The aluminum-containing raw material may include at least one selected from the group consisting of Al(OH)3, Al2(SO4)3, AlCl3, and Al(NO3)3, and may specifically be Al(OH)3.

    [0050] In the first step, based on 100 parts by weight of the lithium composite metal oxide, the boron-containing raw material may be mixed in an amount of 0.1 parts by weight to 0.8 parts by weight, particularly 0.1 parts by weight to 0.5 parts by weight, and more particularly 0.1 parts by weight to 0.2 parts by weight, and the aluminum-containing raw material may be mixed in an amount of 0.1 parts by weight to 1 parts by weight, particularly 0.1 parts by weight to 0.5 parts by weight, and more particularly 0.3 parts by weight to 0.5 parts by weight. In this case, the amount of the aluminum-containing raw material included may be greater than 1 time to less than 2.5 times, for example, 1.1 times to twice the amount of the boron-containing raw material included.

    [0051] As described above, in a case in which the amount of the aluminum-containing raw material is greater than the amount of the boron-containing raw material, Li2O, B2O3, and Al2O3 may exist in a state in which they are chemically bonded to one another. In contrast, in a case in which the amount of the aluminum-containing raw material is the same as the amount of the boron-containing raw material, the amount of the boron-containing raw material is greater, or the amount of the aluminum-containing raw material is greater than the amount of the boron-containing raw material in a range exceeding the above range, the amorphous oxide may be present in the form of a mixture of one of Li2O, B2O3, and Al2O3, or two thereof may be chemically bonded to each other and the remaining one may exist alone.

    [0052] Also, during the mixing in the first step, the amount of the aluminum-containing raw material included may be greater than 1 time to less than 2.5 times, for example, 1.1 times to twice the amount of the boron-containing raw material included.

    [0053] As described above, in a case in which the amount of the aluminum-containing raw material is greater than the amount of the boron-containing raw material, since the formation of a lithium boron aluminum oxide, in which Li2O, B2O3, and Al2O3 are chemically bonded to one another, is favorable and the probability that the Li2O, B2O3, and Al2O3 each exist alone in the surface treatment layer is low, the lithium by-product may be effectively reduced and output and resistance characteristics may be improved. In contrast, in the case that the amount of the aluminum-containing raw material is the same as the amount of the boron-containing raw material, the amount of the boron-containing raw material is greater, or the amount of the aluminum-containing raw material is greater than the amount of the boron-containing raw material in a range exceeding the above range, since Li2O, B2O3, and Al2O3 each exist alone in the surface treatment layer, the lithium by-product reducing effect is insignificant, and thus, gas may be generated. Also, in a case in which Li2O, B2O3, and Al2O3 each exist alone in the surface treatment layer, since the surface treatment layer may act as a resistance layer, resistance may be increased.

    [0054] It is desirable that the mixing is solid-phase mixing. The reason for this is that, in a case in which a solid-phase mixing method is used, there is no concern about the formation of a side reaction product by a solvent used during liquid-phase mixing, and it is possible to form a more uniform surface treatment layer.

    [0055] To be suitable for the solid-phase mixing, the boron-containing raw material may have an average particle diameter of greater than 5 µm to 50 µm or less. To be suitable for the solid-phase mixing, the aluminum-containing raw material may have an average particle diameter of greater than 0 µm to 1 µm or less. When the average particle diameters respectively satisfy the above-described ranges, the raw materials may be uniformly coated on the core, and an agglomeration phenomenon between the raw materials may be prevented.

    [0056] Since the aluminum-containing raw material has lower reactivity than the boron-containing raw material, it is desirable that the average particle diameter of the aluminum-containing raw material is smaller than that of the boron-containing raw material.

    [0057] A separate milling process may be performed on the boron and aluminum-containing raw materials to have the above-described average particle diameters. The milling may be a conventional milling process such as ball milling.

    [0058] Next, the heat treatment in the second step may be performed in a temperature range of 500°C to 800°C, for example, 500°C to 700°C. If the above-described temperature range is satisfied, Li2O, B2O3, and Al2O3 in the amorphous oxide may be present in a state in which they are chemically bonded to one another. If the temperature is less than the above-described temperature range, one of Li2O, B2O3, and Al2O3 in the amorphous oxide is present in the form of a mixture, or two thereof are physically or chemically bonded to each other and the remaining one exists alone. Specifically, since Al2O3, Li2O-Al2O3, Li2O-B2O3, or Li20-B4O5 is present in the form of a mixture in the amorphous oxide, the effect due to the surface treatment layer of the present invention may not be obtained. If the temperature is greater than the above-described temperature range, the positive electrode active material may be modified.

    [0059] The heat treatment process may be performed for 3 hours to 40 hours, for example, 5 hours to 10 hours under the above-described conditions.

    [0060] Also, the heat treatment process may be performed in multiple stages within the above-described temperature range, and, in this case, the heat treatment process may be performed while changing the temperature variously as each stage progresses.

    [0061] Furthermore, according to another embodiment of the present invention, a positive electrode including the above-described positive electrode active material may be provided.

    [0062] Specifically, the positive electrode includes a positive electrode collector and a positive electrode active material layer formed on the positive electrode collector and including the positive electrode active material according to the present invention.

    [0063] The positive electrode collector is not particularly limited as long as it has conductivity without causing adverse chemical changes in the battery, and, for example, stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel that is surface-treated with one of carbon, nickel, titanium, silver, or the like may be used. Also, the positive electrode collector may typically have a thickness of 3 µm to 500 µm, and microscopic irregularities may be formed on the surface of the collector to improve the adhesion of the positive electrode active material. The positive electrode collector, for example, may be used in various shapes such as that of a film, a sheet, a foil, a net, a porous body, a foam body, a non-woven fabric body, and the like.

    [0064] Also, the positive electrode active material layer may include a conductive agent and a binder in addition to the above-described positive electrode active material.

    [0065] In this case, the conductive agent is used to provide conductivity to the electrode, wherein any conductive agent may be used without particular limitation as long as it has suitable electron conductivity without causing adverse chemical changes in the battery. Specific examples of the conductive agent may be graphite such as natural graphite or artificial graphite; carbon based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, and carbon fibers; powder or fibers of metal such as copper, nickel, aluminum, and silver; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and any one thereof or a mixture of two or more thereof may be used. The conductive agent may be typically included in an amount of 1 wt% to 30 wt% based on a total weight of the positive electrode active material layer.

    [0066] Furthermore, the binder improves the adhesion between the positive electrode active material particles and the adhesion between the positive electrode active material and the current collector. Specific examples of the binder may be polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, an ethylene-propylene-diene monomer (EPDM), a sulfonated EPDM, a styrene-butadiene rubber (SBR), a fluorine rubber, or various copolymers thereof, and any one thereof or a mixture of two or more thereof may be used. The binder may be included in an amount of 1 wt% to 30 wt% based on the total weight of the positive electrode active material layer.

    [0067] The positive electrode may be prepared according to a typical method of preparing a positive electrode except that the above-described positive electrode active material is used. For example, the above-described positive electrode active material as well as selectively the binder and the conductive agent is dissolved or dispersed in a solvent to form a slurry for forming a positive electrode active material layer, the slurry is coated on the positive electrode collector, and the positive electrode may then be prepared by drying and rolling the coated positive electrode collector. In this case, types and amounts of the positive electrode active material, the binder, and the conductive are the same as those previously described.

    [0068] The solvent may be a solvent normally used in the art, and, for example, the solvent may include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, or water, but the present invention is not limited thereto. Any one thereof or a mixture of two or more thereof may be used as the solvent. An amount of the solvent used may be sufficient if the solvent may dissolve or disperse the positive electrode active material, the conductive agent, and the binder in consideration of a coating thickness of the slurry and manufacturing yield, and may allow to have a viscosity that may provide excellent thickness uniformity during the subsequent coating for the preparation of the positive electrode.

    [0069] Also, as another method, the positive electrode may be prepared by casting the slurry for forming a positive electrode active material layer on a separate support and then laminating a film separated from the support on the positive electrode collector.

    [0070] According to another embodiment of the present invention, an electrochemical device including the positive electrode is provided. The electrochemical device may specifically be a battery or a capacitor, and, for example, may be a lithium secondary battery.

    [0071] The lithium secondary battery specifically includes a positive electrode, a negative electrode disposed to face the positive electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the positive electrode is as described above. Also, the lithium secondary battery may further selectively include a battery container accommodating an electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member sealing the battery container.

    [0072] In the lithium secondary battery, the negative electrode includes a negative electrode collector and a negative electrode active material layer disposed on the negative electrode collector.

    [0073] The negative electrode collector is not particularly limited as long as it has high conductivity without causing adverse chemical changes in the battery, and, for example, copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel that is surface-treated with one of carbon, nickel, titanium, silver, or the like, and an aluminum-cadmium alloy may be used. Also, the negative electrode collector may typically have a thickness of 3 µm to 500 µm, and, similar to the positive electrode collector, microscopic irregularities may be formed on the surface of the collector to improve the adhesion of a negative electrode active material. The negative electrode collector, for example, may be used in various shapes such as that of a film, a sheet, a foil, a net, a porous body, a foam body, a non-woven fabric body, and the like.

    [0074] The negative electrode active material layer selectively includes a binder and a conductive agent in addition to the negative electrode active material. The negative electrode active material layer, for example, may be prepared by dissolving or dispersing the negative electrode active material as well as selectively the binder and the conductive agent in a solvent to form a slurry for forming a negative electrode, coating the slurry on the negative electrode collector and drying the coated negative electrode collector, or may be prepared by casting the slurry for forming a negative electrode on a separate support and then laminating a film separated from the support on the negative electrode collector.

    [0075] A compound capable of reversibly intercalating and deintercalating lithium may be used as the negative electrode active material. Specific examples of the negative electrode active material may be a carbonaceous material such as artificial graphite, natural graphite, graphitized carbon fibers, and amorphous carbon; a metallic compound alloyable with lithium such as silicon (Si), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), bismuth (Bi), indium (In), magnesium (Mg), gallium (Ga), cadmium (Cd), a Si alloy, a Sn alloy, or an Al alloy; a metal oxide which may be doped and undoped with lithium such as SiOx(0 < x < 2), SnO2, vanadium oxide, and lithium vanadium oxide; or a composite including the metallic compound and the carbonaceous material such as a SiC composite or a Sn-C composite, and any one thereof or a mixture of two or more thereof may be used. Also, a metallic lithium thin film may be used as the negative electrode active material. Furthermore, both low crystalline carbon and high crystalline carbon may be used as the carbon material. Typical examples of the low crystalline carbon may be soft carbon and hard carbon, and typical examples of the high crystalline carbon may be irregular, planar, flaky, spherical, or fibrous natural graphite or artificial graphite, Kish graphite, pyrolytic carbon, mesophase pitch-based carbon fibers, meso-carbon microbeads, mesophase pitches, and high-temperature sintered carbon such as petroleum or coal tar pitch derived cokes.

    [0076] Also, the binder, the conductive agent and solvent may be the same as those previously described in the positive electrode.

    [0077] In the lithium secondary battery, the separator separates the negative electrode and the positive electrode and provides a movement path of lithium ions, wherein any separator may be used as the separator without particular limitation as long as it is typically used in a lithium secondary battery, and particularly, a separator having high moisture-retention ability for an electrolyte as well as low resistance to the transfer of electrolyte ions may be used. Specifically, a porous polymer film, for example, a porous polymer film prepared from a polyolefin-based polymer, such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, or a laminated structure having two or more layers thereof may be used. Also, a typical porous nonwoven fabric, for example, a nonwoven fabric formed of high melting point glass fibers or polyethylene terephthalate fibers may be used. Furthermore, a coated separator including a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and the separator having a single layer or multilayer structure may be selectively used.

    [0078] Also, the electrolyte used in the present invention may include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, or a molten-type inorganic electrolyte which may be used in the preparation of the lithium secondary battery, but the present invention is not limited thereto.

    [0079] Specifically, the electrolyte may include an organic solvent and a lithium salt.

    [0080] Any organic solvent may be used as the organic solvent without particular limitation so long as it may function as a medium through which ions involved in an electrochemical reaction of the battery may move. Specifically, an ester-based solvent such as methyl acetate, ethyl acetate, γ-butyrolactone, and ε-caprolactone; an ether-based solvent such as dibutyl ether or tetrahydrofuran; a ketone-based solvent such as cyclohexanone; an aromatic hydrocarbon-based solvent such as benzene and fluorobenzene; or a carbonate-based solvent such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methylethyl carbonate (MEC), ethylmethyl carbonate (EMC), ethylene carbonate (EC), and propylene carbonate (PC); an alcohol-based solvent such as ethyl alcohol and isopropyl alcohol; nitriles such as R-CN (where R is a linear, branched, or cyclic C2-C20 hydrocarbon group and may include a double-bond aromatic ring or ether bond); amides such as dimethylformamide; dioxolanes such as 1,3-dioxolane; or sulfolanes may be used as the organic solvent. Among these solvents, the carbonate-based solvent may be used, and, for example, a mixture of a cyclic carbonate (e.g., ethylene carbonate or propylene carbonate) having high ionic conductivity and high dielectric constant, which may increase charge/discharge performance of the battery, and a low-viscosity linear carbonate-based compound (e.g., ethylmethyl carbonate, dimethyl carbonate, or diethyl carbonate) may be used. In this case, the performance of the electrolyte solution may be excellent when the cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1:1 to about 1:9.

    [0081] The lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in the lithium secondary battery. Specifically, LiPF6, LiClO4, LiAsF6, LiBF4, LiSbF6, LiAlO4, LiAlCl4, LiCF3SO3, LiC4F9SO3, LiN(C2F5SO3)2, LiN(C2F5SO2)2, LiN(CF3SO2)2, LiCl, LiI, or LiB(C2O4)2 may be used as the lithium salt. The lithium salt may be used in a concentration range of 0.1 M to 2.0 M. In a case in which the concentration of the lithium salt is included within the above range, since the electrolyte may have appropriate conductivity and viscosity, excellent performance of the electrolyte may be obtained and lithium ions may effectively move.

    [0082] In order to improve lifetime characteristics of the battery, suppress the reduction in battery capacity, and improve discharge capacity of the battery, at least one additive, for example, a halo-alkylene carbonate-based compound such as difluoroethylene carbonate, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexaphosphoric triamide, a nitrobenzene derivative, sulfur, a quinone imine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, an ammonium salt, pyrrole, 2-methoxy ethanol, or aluminum trichloride, may be further added to the electrolyte in addition to the electrolyte components. In this case, the additive may be included in an amount of 0.1 wt% to 5 wt% based on a total weight of the electrolyte.

    [0083] As described above, since the lithium secondary battery including the positive electrode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention, the lithium secondary battery is suitable for portable devices, such as mobile phones, notebook computers, and digital cameras, and electric cars such as hybrid electric vehicles (HEVs).

    [0084] Thus, according to another embodiment of the present invention, a battery module including the lithium secondary battery as a unit cell and a battery pack including the battery module are provided.

    [0085] The battery module or the battery pack may be used as a power source of at least one medium and large sized device of a power tool; electric cars including an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); or a power storage system.

    [0086] Hereinafter, examples of the present invention will be described in detail in such a manner that it may easily be carried out by a person with ordinary skill in the art to which the present invention pertains. The invention may, however, be embodied in many different forms and should not be construed as being limited to the examples set forth herein.

    Example 1


    (Preparation of Positive Electrode Active Material)



    [0087] H3BO3 and Al(OH)3 were mixed in amounts as listed in Table 1 with 100 parts by weight of a lithium composite metal oxide (Li(Ni0.83Co0.11Mn0.06)0.97Zr0.03O2) using a dry mixer (CYCLOMIX, HOSOKAWA Micron Corporation), and a heat treatment was then performed at a temperature listed in Table 1 for 5 hours in an oxygen atmosphere to prepare a positive electrode active material on which a surface treatment layer including an amorphous oxide listed in Table 1 was formed.

    (Preparation of Positive Electrode)



    [0088] The above-prepared positive electrode active material, carbon black as a conductive agent, and PVDF as a binder, at a weight ratio of 95:2.5:2.5 were mixed in N-methylpyrrolidone as a solvent, to prepare a composition for forming a positive electrode (viscosity: 5,000 mPa·s). An aluminum current collector was coated with the composition for forming a positive electrode, dried at 130°C, and then rolled to prepare a positive electrode.

    (Preparation of Negative Electrode)



    [0089] Natural graphite as a negative electrode active material, carbon black as a conductive agent, and polyvinylidene fluoride (PVDF) as a binder, at a weight ratio of 85:10:5 were mixed in N-methylpyrrolidone, as a solvent, to prepare a composition for forming a negative electrode, and a copper current collector was coated with the composition to prepare a negative electrode.

    (Preparation of Lithium Secondary Battery)



    [0090] An electrode assembly was prepared by disposing porous polyethylene, as a separator, between the positive electrode and the negative electrode, and a lithium secondary battery was prepared by disposing the electrode assembly in a case, and then injecting an electrolyte solution into the case. In this case, the electrolyte solution was prepared by dissolving 1.0 M lithium hexafluorophosphate (LiPF6) in an organic solvent composed of ethylene carbonate/dimethyl carbonate/ethylmethyl carbonate (mixing volume ratio of EC/DMC/EMC=3/4/3) .

    Example 2



    [0091] H3BO3 and Al(OH)3 were mixed in amounts as listed in Table 1 with 100 parts by weight of a lithium composite metal oxide (Li(Ni0.83Co0.11Mn0.06)0.97Zr0.03O2) using a dry mixer, and a heat treatment was then performed at 500°C to prepare a positive electrode active material on which a surface treatment layer including an amorphous oxide having a composition as listed in Table 1 was formed. A positive electrode and a lithium secondary battery were prepared in the same manner as in Example 1 except that the above positive electrode active material was used.

    Comparative Example 1



    [0092] A positive electrode and a lithium secondary battery were prepared in the same manner as in Example 1 except that a lithium composite metal oxide (Li (Ni0.83CO0.11Mn0.06)0.97Zr0.03O2), on which a surface treatment layer was not formed, was used as a positive electrode active material.

    Comparative Example 2



    [0093] H3BO3 was mixed in an amount as listed in Table 1 with 100 parts by weight of a lithium composite metal oxide (Li (Ni0.83Co0.11Mn0.06)0.97Zr0.03O2) using a dry mixer, and a heat treatment was then performed at 300°C to prepare a positive electrode active material on which a surface treatment layer including an amorphous oxide having a composition as listed in Table 1 was formed. A positive electrode and a lithium secondary battery were prepared in the same manner as in Example 1 except that the above positive electrode active material was used.

    Comparative Example 3



    [0094] Al(OH)3 was mixed in an amount as listed in Table 1 with 100 parts by weight of a lithium composite metal oxide (Li(Ni0.83Co0.11Mn0.06)0.97Zr0.03O2) using a dry mixer, and a heat treatment was then performed at 300°C to prepare a positive electrode active material on which a surface treatment layer including an amorphous oxide having a composition as listed in Table 1 was formed. A positive electrode and a lithium secondary battery were prepared in the same manner as in Example 1 except that the above positive electrode active material was used.

    Comparative Example 4



    [0095] H3BO3 and Al(OH)3 were mixed in amounts as listed in Table 1 with 100 parts by weight of a lithium composite metal oxide (Li (Ni0.83Co0.11Mn0.06)0.97Zr0.03O2) using a dry mixer, and a heat treatment was then performed at 700°C to prepare a positive electrode active material on which a surface treatment layer including an amorphous oxide having a composition as listed in Table 1 was formed. A positive electrode and a lithium secondary battery were prepared in the same manner as in Example 1 except that the above positive electrode active material was used.

    Comparative Example 5



    [0096] H3BO3 and Al(OH)3 were mixed in amounts as listed in Table 1 with 100 parts by weight of a lithium composite metal oxide (Li (Ni0.83Co0.11Mn0.06)0.97Zr0.03O2) using a dry mixer, and a heat treatment was then performed at 700°C to prepare a positive electrode active material on which a surface treatment layer including an amorphous oxide having a composition as listed in Table 1 was formed. A positive electrode and a lithium secondary battery were prepared in the same manner as in Example 1 except that the above positive electrode active material was used.

    Comparative Example 6



    [0097] H3BO3 and Al(OH)3 were mixed in amounts as listed in Table 1 with 100 parts by weight of a lithium composite metal oxide (Li (Ni0.83Co0.11Mn0.06)0.97Zr0.03O2) using a dry mixer, and a heat treatment was then performed at 300°C to prepare a positive electrode active material on which a surface treatment layer including an amorphous oxide having a composition as listed in Table 1 was formed. A positive electrode and a lithium secondary battery were prepared in the same manner as in Example 1 except that the above positive electrode active material was used.

    Comparative Example 7



    [0098] H3BO3 and Al(OH)3 were mixed in amounts as listed in Table 1 with 100 parts by weight of a lithium composite metal oxide (Li (Ni0.83Co0.11Mn0.06)0.97Zr0.03O2) using a dry mixer, and a heat treatment was then performed at 700°C to prepare a positive electrode active material on which a surface treatment layer including an amorphous oxide having a composition as listed in Table 1 was formed. A positive electrode and a lithium secondary battery were prepared in the same manner as in Example 1 except that the above positive electrode active material was used.
    [Table 1]
    CategoryH3BO3 (parts by weight)Al(OH)3 (parts by weight)Heat treatment temperature (°C)Amorphous oxide
    CompositionAverage thickness (nm)
    Example 1 0.2 0.3 700 Li2O-B2O3-Al2O3 70
    Example 2 0.2 0.3 500 Li2O-B2O3-Al2O3 70
    Comparative Example 1 0 0 0 - -
    Comparative Example 2 0.2 0 300 Li2O-B2O3 70
    Comparative Example 3 0 0.3 300 Li2O-Al2O3 70
    Comparative Example 4 0.2 0.2 700 Li2O-B2O3-Al2O3 70
    Comparative Example 5 0.3 0.2 700 Li2O-B2O3-Al2O3 70
    Comparative Example 6 0.2 0.3 300 Li2O-B2O3-Al2O3 70
    Comparative Example 7 0.2 0.5 700 Li2O-B2O3-Al2O3 70

    Experimental Example 1: Characterization of Positive Electrode Active Material



    [0099] An amount of a lithium by-product remaining on a surface of each of the positive electrode active materials prepared in Examples 1 and 2 and Comparative Examples 1 to 7 was measured by pH titration. In the pH titration, after distilled water was poured into 10 g of the positive electrode active material to dissolve the lithium by-product remaining on the surface of the positive electrode active material, the solution thus obtained was filtered and titrated by adding 0.1 M HCl at a rate of 0.3 mL/min to 0.5 mL/min. In this case, an amount of the residual lithium by-product was calculated from an amount of the HCl added to pH 5. Equipment by Metrohm AG was used for the pH titration. The results thereof are presented in the following Table 2. In the following Table 2, amounts of LIOH and Li2CO3 listed were weight % based on a total weight of the positive electrode active material.
    [Table 2]
    CategoryLiOH (wt%)Li2CO3 (wt%)Sum (wt%)
    Example 1 0.424 0.057 0.481
    Example 2 0.428 0.115 0.543
    Comparative Example 1 0.480 0.730 1.210
    Comparative Example 2 0.422 0.135 0.557
    Comparative Example 3 0.465 0.564 1.029
    Comparative Example 4 0.433 0.125 0.558
    Comparative Example 5 0.438 0.127 0.565
    Comparative Example 6 0.452 0.157 0.609
    Comparative Example 7 0.44 0.131 0.571


    [0100] Referring to Table 2, with respect to each of the positive electrode active materials prepared in Examples 1 and 2, the amount of the lithium by-product was less than about 0.55 wt% based on the total weight of the positive electrode active material, wherein it may be confirmed that the amount of the lithium by-product was smaller than those of the positive electrode active materials prepared in Comparative Examples 1 to 7.

    Experimental Example 2: Characterization of Lithium Secondary Battery (1)



    [0101] The lithium secondary batteries prepared in Examples 1 and 2 and Comparative Examples 1 to 7 were charged and discharged 30 times at a temperature of 45°C under conditions of 0.3 C/0.3 C within a driving voltage range of 2.5 V to 4.25 V. Then, a discharge capacity retention, as a ratio of discharge capacity according to the number of cycles to discharge capacity in the first cycle, was measured. The results thereof are presented in FIG. 1.

    [0102] Referring to FIG. 1, the lithium secondary batteries of Examples 1 and 2 had a smaller change in capacity retention than Comparative Examples 1 to 7 even if the number of cycles was increased. Particularly, with respect to the lithium secondary battery of Example 1, there was almost no change in discharge capacity according to the number of cycles to discharge capacity in the first cycle.

    Experimental Example 3: Characterization of Lithium Secondary Battery (2)



    [0103] When evaluating life characteristics of each lithium secondary battery at 45°C, an initial discharge voltage drop was measured every 5 cycles for 0 second to 60 seconds and resistance was calculated by dividing the voltage drop by the current (0.3 C). As a result, direct current internal resistance (DCIR) at 45°C in Example 1 was 10.6 mΩ.

    [0104] Referring to FIG. 2, since the lithium secondary batteries of Examples 1 and 2 had a lower direct current resistance increase rate than the lithium secondary batteries prepared in Comparative Examples 1 to 7, it may be expected that the lithium secondary batteries of Examples 1 and 2 may exhibit excellent power density.

    Experimental Example 4: Characterization of Lithium Secondary Battery (3)



    [0105] Each of the lithium secondary batteries prepared in Examples 1 and 2 and Comparative Examples 1 to 3 and 6 was charged at a constant current of 0.3 C to a voltage of 4.25 V and then stored at 60°C for 6 weeks. An amount of gas generated in each lithium secondary battery over time was measured and illustrated in FIG. 3. The amount of gas generated in the lithium secondary battery was measured by a change in volume of the lithium secondary battery.

    [0106] Referring to FIG. 3, it may be confirmed that the amount of the gas generated in each of the lithium secondary batteries prepared in Examples 1 and 2 was significantly lower than those generated in the lithium secondary batteries prepared in Comparative Examples 1 to 3 and 6.


    Claims

    1. A positive electrode active material for a secondary battery, the positive electrode active material comprising:

    a core including a lithium composite metal oxide represented by Formula 1

            <Formula 1>     Lia(NixCoyM1z)bM2cO2

    wherein, in Formula 1,

    M1 is at least one element selected from the group consisting of manganese and aluminum , and

    M2 is at least one element selected from the group consisting of barium, calcium, zirconium, titanium, magnesium, tantalum, niobium, and molybdenum,

    wherein 1≤a≤1.5, 0.9≤b≤1, 0≤c≤0.1, 0.6≤x<1, 0<y<0.4, 0<z≤0.4, and b+c=1; and

    a surface treatment layer which is disposed on the core and includes an amorphous oxide containing a lithium oxide, a boron oxide, and an aluminum oxide,

    wherein the lithium oxide, the boron oxide, and the aluminum oxide are chemically bonded to one another and wherein the lithium oxide is Li2O, the boron oxide is B2O3, and the aluminum oxide is Al2O3; and

    in the amorphous oxide in the surface treatment layer, an amount of the aluminum oxide is greater than an amount of the boron oxide, and an amount of a lithium by-product comprising at least one of LiOH or Li2CO3 present on a surface of the positive electrode active material is less than 0.55 wt% based on a total weight of the positive electrode active material.


     
    2. The positive electrode active material for a secondary battery of claim 1, wherein a mole ratio of the boron oxide to the aluminum oxide is in a range of greater than 1:1 to less than 1:2.5.
     
    3. The positive electrode active material for a secondary battery of claim 1, wherein the Li2O, the B2O3, and the Al2O3 are chemically bonded to one another in a form selected from the group consisting of 2LiAl7B4O5, 2LiAlB2O5, and 2Li2AlB2O5.
     
    4. The positive electrode active material for a secondary battery of claim 1, wherein the surface treatment layer has an average thickness of 20 nm to 100 nm.
     
    5. The positive electrode active material for a secondary battery of claim 1, wherein the positive electrode active material has an average particle diameter (D50) of 1 µm to 20 µm.
     
    6. The positive electrode active material for a secondary battery of claim 1, wherein the lithium composite metal oxide is a secondary particle formed by agglomeration of primary particles, and
    further comprises a segregation phase of Zr oxide on a surface of the secondary particle or at an interface between the primary particles.
     
    7. A method of preparing a positive electrode active material for a secondary battery in accordance with claims 1 to 6, the method comprising:

    preparing a mixture by mixing a lithium composite metal oxide, a boron-containing raw material, and an aluminum-containing raw material; and

    forming a surface treatment layer including an amorphous oxide on a core including the lithium composite metal oxide represented by formula 1 of claim 1 by performing a heat treatment on the mixture in an oxygen atmosphere,

    wherein an amount of the aluminum-containing raw material included is greater than 1 time to less than 2.5 times an amount of the boron-containing raw material included, and the heat treatment is performed in a temperature range of 500°C to 800°C.


     
    8. The method of claim 7, wherein the boron-containing raw material is mixed in an amount of 0.1 parts by weight to 0.8 parts by weight and the aluminum-containing raw material is mixed in an amount of 0.1 parts by weight to 1 parts by weight, based on 100 parts by weight of the lithium composite metal oxide.
     
    9. The method of claim 7, wherein the boron-containing raw material comprises at least one of H3BO3, HBPO4, B2O3, B2O5, Li2B4O7, or (NH4)2B4O7.
     
    10. The method of claim 7, wherein the aluminum-containing raw material comprises at least one of Al(OH)3, Al2(SO4)3, AlCl3, or Al(NO3)3.
    +
     
    11. A positive electrode for a secondary battery, the positive electrode comprising the positive electrode active material of claim 1, a binder, a conductive agent, and a positive electrode collector.
     
    12. A secondary battery comprising the positive electrode of claim 11, a negative electrode disposed to face the positive electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte.
     


    Ansprüche

    1. Aktivmaterial für eine positive Elektrode einer Sekundärbatterie, wobei das Aktivmaterial für eine positive Elektrode umfasst:

    einen Kern, enthaltend ein Lithium-Kompositmetalloxid,

    dargestellt durch die Formel 1:

            <Formula 1>     Lia(NixCoyM1z)bM2cO2

    wobei in Formel 1,

    M1 mindestens ein Element ist, ausgewählt aus der Gruppe bestehend aus Mangan und Aluminium, und

    M2 mindestens ein Element ist, ausgewählt aus der Gruppe bestehend aus Barium, Kalzium, Zirkonium, Titan, Magnesium, Tantal, Niob und Molybdän,

    worin 1≤a≤1.5, 0.9≤b≤1, 0≤c≤0.1, 0.6≤x<1, 0<y<0.4, 0<z≤0.4 und b+c=1; und

    eine Oberflächenbehandlungsschicht, die auf dem Kern angeordnet ist und ein amorphes Oxid enthält, das ein Lithiumoxid, ein Boroxid und ein Aluminiumoxid enthält,

    wobei das Lithiumoxid, das Boroxid und das Aluminiumoxid chemisch aneinander gebunden sind und wobei das Lithiumoxid Li2O, das Boroxid B2O3 und das Aluminiumoxid Al2O3 ist; und

    in dem amorphen Oxid in der Oberflächenbehandlungsschicht eine Menge des Aluminiumoxids größer als eine Menge des Boroxids ist und eine Menge eines Lithium-Nebenprodukts, das mindestens eines von LiOH oder Li2CO3 umfasst, das auf einer Oberfläche des Aktivmaterials für eine positive Elektrode vorliegt, weniger als 0,55 Gew.-% beträgt, bezogen auf das Gesamtgewicht des Aktivmaterials für eine positive Elektrode.


     
    2. Aktivmaterial für eine positive Elektrode einer Sekundärbatterie gemäß Anspruch 1, wobei das Molverhältnis des Boroxids zu dem Aluminiumoxid in einem Bereich von mehr als 1:1 bis weniger als 1:2,5 liegt.
     
    3. Aktivmaterial für eine positive Elektrode einer Sekundärbatterie gemäß Anspruch 1, worin das Li2O, das B2O3 und das Al2O3 in einer Form chemisch aneinander gebunden sind, die aus der Gruppe bestehend aus 2LiAl7B4O5, 2LiAlB2O5, und 2Li2AlB2O5 ausgewählt ist.
     
    4. Aktivmaterial für eine positive Elektrode einer Sekundärbatterie gemäß Anspruch 1, wobei die Oberflächenbehandlungsschicht eine mittlere Dicke von 20 nm bis 100 nm aufweist.
     
    5. Aktivmaterial für eine positive Elektrode einer Sekundärbatterie gemäß Anspruch 1, wobei das aktive Material der positiven Elektrode einen mittleren Partikeldurchmesser (D50) von 1 µm bis 20 µm aufweist.
     
    6. Aktivmaterial für eine positive Elektrode einer Sekundärbatterie gemäß Anspruch 1, wobei das Lithium-Kompositmetalloxid ein Sekundärteilchen ist, das durch Agglomeration von Primärteilchen gebildet ist, und ferner eine Entmischungsphase aus Zr-Oxid auf einer Oberfläche des Sekundärteilchens oder an einer Grenzfläche zwischen den Primärteilchen umfasst.
     
    7. Verfahren zur Herstellung eines Aktivmaterial für eine positive Elektrode einer Sekundärbatterie gemäß einem der Ansprüch 1 bis 6, wobei das Verfahren umfasst:

    Herstellen einer Mischung durch Mischen eines Lithium-Kompositmetalloxids, eines borhaltigen Ausgangsmaterials und eines aluminiumhaltigen Ausgangsmaterials; und

    Ausbilden einer ein amorphes Oxid enthaltenden Oberflächenbehandlungsschicht auf einem Kern, der das Lithium-Kompositmetalloxid der Formel 1 von Anspruch 1 enthält, durch Durchführen einer Wärmebehandlung an der Mischung in einer Sauerstoffatmosphäre,

    wobei eine Menge des enthaltenen aluminiumhaltigen Ausgangsmaterials mehr als das 1fache bis weniger als das 2,5-fache einer Menge des enthaltenen borhaltigen Ausgangsmaterials beträgt und die Wärmebehandlung in einem Temperaturbereich von 500°C bis 800°C durchgeführt wird.


     
    8. Verfahren gemäß Anspruch 7, wobei das borhaltige Ausgangsmaterial in einer Menge von 0,1 Gew.-Teilen bis 0,8 Gew.-Teilen und das aluminiumhaltige Ausgangsmaterial in einer Menge von 0,1 Gew.-Teilen bis 1 Gew.-Teilen, bezogen auf 100 Gew.-Teile des Lithium-Komposit metalloxids, gemischt werden.
     
    9. Verfahren gemäß Anspruch 7, wobei das borhaltige Ausgangsmaterial mindestens eines von H3BO3, HBPO4, B2O3, B2O5, Li2B4O7, oder (NH4)2B4O7 umfasst.
     
    10. Verfahren gemäß Anspruch 7, wobei das aluminiumhaltige Ausgangsmaterial mindestens eines von Al(OH)3, Al2(SO4)3, AlCl3, oder Al(NO3)3 umfasst.
    +
     
    11. Positive Elektrode für eine Sekundärbatterie, wobei die positive Elektrode das Aktivmaterial für eine positive Elektrode gemäß Anspruch 1, ein Bindemittel, ein leitfähiges Mittel und einen positiven Elektrodenkollektor enthält.
     
    12. Sekundärbatterie, umfassend die positive Elektrode gemäß Anspruch 11, eine negativen Elektrode, die gegenüber zur positiven Elektrode angeordnet ist, einen Separator, der zwischen der positiven Elektrode und der negativen Elektrode angeordnet ist, und einen Elektrolyten.
     


    Revendications

    1. Matériau actif d'électrode positive pour une batterie secondaire, le matériau actif d'électrode positive comprenant :

    un noyau incluant un oxyde métallique composite de lithium représenté par la Formule 1

            < Formule 1 >     Lia(NixCoyM1z)bM2cO2

    dans lequel, dans la Formule 1,

    M1 est au moins un élément sélectionné à partir du groupe constitué par le manganèse et l'aluminium, et

    M2 est au moins un élément sélectionné à partir du groupe constitué par le baryum, le calcium, le zirconium, le titane, le magnésium, le tantale, le niobium et le molybdène,

    dans lequel 1 ≤ a ≤ 1,5, 0,9 ≤ b ≤ 1, 0 ≤ c ≤ 0,1, 0,6 ≤ x < 1, 0 < y < 0,4, 0 < z ≤ 0,4, et b + c = 1 ; et

    une couche de traitement de surface qui est disposée sur le noyau et inclut un oxyde amorphe contenant un oxyde de lithium, un oxyde de bore et un oxyde d'aluminium,

    dans lequel l'oxyde de lithium, l'oxyde de bore et l'oxyde d'aluminium sont chimiquement liés les uns aux autres et dans lequel l'oxyde de lithium est Li2O, l'oxyde de bore est B2O3 et l'oxyde d'aluminium est Al2O3 ; et

    dans l'oxyde amorphe dans la couche de traitement de surface, une quantité de l'oxyde d'aluminium est supérieure à une quantité de l'oxyde de bore, et une quantité d'un sous-produit de lithium comprenant au moins un parmi LiOH ou Li2CO3 présent sur une surface du matériau actif d'électrode positive est inférieure à 0,55 % en poids sur la base d'un poids total du matériau actif d'électrode positive.


     
    2. Matériau actif d'électrode positive pour une batterie secondaire selon la revendication 1, dans lequel un rapport molaire entre l'oxyde de bore et l'oxyde d'aluminium est dans une plage de supérieur à 1:1 à inférieur à 1:2,5.
     
    3. Matériau actif d'électrode positive pour une batterie secondaire selon la revendication 1, dans lequel le Li2O, le B2O3 et le Al2O3 sont chimiquement liés les uns aux autres sous une forme sélectionnée à partir du groupe constitué par 2LiAl7B4O5, 2LiAlB2O5, et 2Li2AlB2O5.
     
    4. Matériau actif d'électrode positive pour une batterie secondaire selon la revendication 1, dans lequel la couche de traitement de surface présente une épaisseur moyenne de 20 nm à 100 nm.
     
    5. Matériau actif d'électrode positive pour une batterie secondaire selon la revendication 1, dans lequel le matériau actif d'électrode positive présente un diamètre de particule moyen (D50) de 1 µm à 20 µm.
     
    6. Matériau actif d'électrode positive pour une batterie secondaire selon la revendication 1, dans lequel l'oxyde métallique composite de lithium est une particule secondaire formée par agglomération de particules primaires, et
    comprend en outre une phase de ségrégation d'oxyde de Zr sur une surface de la particule secondaire ou au niveau d'une interface entre les particules primaires.
     
    7. Procédé de préparation d'un matériau actif d'électrode positive pour une batterie secondaire selon l'une quelconque des revendications 1 à 6, le procédé comprenant les étapes consistant à :

    préparer un mélange en mélangeant un oxyde métallique composite de lithium, une matière première contenant du bore, et une matière première contenant de l'aluminium ; et

    former une couche de traitement de surface incluant un oxyde amorphe sur un noyau incluant l'oxyde métallique composite de lithium représenté par la formule 1 selon la revendication 1 en effectuant un traitement thermique sur le mélange dans une atmosphère d'oxygène,

    dans lequel une quantité de la matière première contenant de l'aluminium incluse est supérieure à 1 fois à inférieure à 2,5 fois une quantité de la matière première contenant du bore incluse, et le traitement thermique est effectué dans une plage de températures de 500 °C à 800 °C.


     
    8. Procédé selon la revendication 7, dans lequel la matière première contenant du bore est mélangée dans une quantité de 0,1 partie en poids à 0,8 partie en poids et la matière première contenant de l'aluminium est mélangée dans une quantité de 0,1 partie en poids à 1 partie en poids, sur la base de 100 parties en poids de l'oxyde métallique composite de lithium.
     
    9. Procédé selon la revendication 7, dans lequel la matière première contenant du bore comprend au moins un parmi H3BO3, HBPO4, B2O3, B2O5, Li2B4O7, ou (NH4)2B4O7.
     
    10. Procédé selon la revendication 7, dans lequel la matière première contenant de l'aluminium comprend au moins un parmi Al(OH)3, Al2(SO4)3, AlCl3, ou Al(NO3)3.
     
    11. Électrode positive pour une batterie secondaire, l'électrode positive comprenant le matériau actif d'électrode positive selon la revendication 1, un liant, un agent conducteur, et un collecteur d'électrode positive.
     
    12. Batterie secondaire comprenant l'électrode positive selon la revendication 11, une électrode négative disposée pour faire face à l'électrode positive, un séparateur disposé entre l'électrode positive et l'électrode négative, et un électrolyte.
     




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    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description