KR100542195B1 - Negative active material for lithium secondary battery and lithium secondary battery comprising same - Google Patents

Abstract

The present invention relates to a negative electrode active material for a lithium secondary battery and a lithium secondary battery including the same, wherein the negative electrode active material includes: a matrix metal capable of forming an alloy with lithium; And a material forming an intermetallic bond with the matrix metal selected from the group consisting of Mg, K, Li, B, Na, Ca and H.

The negative electrode active material for a lithium secondary battery of the present invention reduces the irreversible capacity by adding an additive to a structurally unstable reaction site in which lithium ions can be trapped in a metal capable of forming an alloy with lithium during charge and discharge, thereby reducing the irreversible capacity. This improves the initial efficiency and capacity characteristics of the battery.

Lithium secondary battery, intermetallic compound, cathode, matrix metal

Description

Negative active material for lithium secondary battery and lithium secondary battery comprising same TECHNICAL FIELD

1 is a perspective view showing an example of a lithium secondary battery.

2 is a view showing the charge and discharge characteristics of Example 1 and Comparative Example 1 according to the present invention.

* Description of the symbols for the main parts of the drawings *

1: lithium secondary battery 2: negative electrode

3: anode 4: separator

5: battery container 6: sealing member

[Industrial use]

The present invention relates to a negative electrode active material for a lithium secondary battery and a lithium secondary battery including the same, and more particularly, to a negative electrode active material for a lithium secondary battery having excellent initial charge and discharge efficiency and capacity characteristics, and a lithium secondary battery including the same.

[Prior art]

Lithium secondary batteries, which are in the spotlight as power sources of recent portable small electronic devices, exhibit high energy density by showing a discharge voltage that is twice as high as that of a battery using an alkaline aqueous solution using an organic electrolyte solution.

As a cathode active material of a lithium secondary battery, an oxide composed of lithium and a transition metal having a structure capable of intercalating lithium, such as LiCoO ₂ , LiMn ₂ O ₄ , and LiNi _1-x Co _x O ₂ (0 <X <1) Was mainly used.

Lithium metal was initially used as a negative electrode active material. However, due to a problem of dendrites occurring and a very short lifespan, various types of carbon-based carbonaceous materials including artificial graphite, natural graphite, and hard carbon, which can be inserted / desorbed of lithium, have recently been used. The material is being used. However, the carbon-based anode active material can solve the problem of dendrites and has excellent voltage flatness and good life characteristics at low potential, but due to high reactivity with the organic electrolyte and low diffusion rate of lithium in the material, power ( There are problems such as power characteristics, initial irreversible control, and electrode swelling during charging and discharging.

Accordingly, researches for using lithium alloy as a negative electrode active material to solve the problem of dendrites have a long life. U. S. Patent No. 6,051, 340 describes a negative electrode comprising a metal that is not alloyed with lithium and a metal that is alloyed with lithium. In this patent, the metal that is not alloyed with lithium serves as a current collector, and the metal that is alloyed with lithium forms an alloy with lithium ions that are released from the positive electrode during charging, and the alloy serves as a negative electrode active material, The negative electrode contains lithium during charging.

However, even with the lithium alloy described above, it was difficult to obtain satisfactory battery characteristics. Particularly, in the case of forming an alloy with lithium ions, lithium ions enter the alloy during charging to form an intermetallic compound, and during discharging, the compound phase changes as lithium ions escape. However, even after the discharge is completed, there is a case in which lithium does not completely escape from the alloy, and the remaining lithium forms an intermetallic compound and does not return to the metal state and remains in the final discharge state. As such, lithium trapped in structurally unstable sites in the alloy increases the irreversible capacity. This increase in irreversible capacity has a problem of lowering the initial charge and discharge efficiency of the lithium alloy to about 80%. When the initial charge and discharge efficiency is low, the excessive use of the positive electrode is caused, thereby lowering the battery capacity.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a negative electrode active material for a lithium secondary battery excellent in initial charge and discharge efficiency and capacity characteristics, and a lithium secondary battery comprising the same.

In order to achieve the above object, the present invention is a matrix metal capable of forming an alloy with lithium; And a material forming an intermetallic bond with the matrix metal selected from the group consisting of Mg, K, Li, B, Na, Ca, and H.

The invention also provides a matrix metal capable of forming an alloy with lithium; And a negative electrode active material including a material forming a metal-to-metal bond with the matrix metal selected from the group consisting of Mg, K, Li, B, Na, Ca, and H; intercalation and deintercalation of lithium ions A positive electrode comprising a cathode active material; And it provides a lithium secondary battery comprising an electrolyte.

Hereinafter, the present invention will be described in more detail.

The negative electrode active material for a lithium secondary battery of the present invention is an intermetallic compound capable of reducing the irreversible capacity of a matrix metal prepared by reacting a matrix metal capable of forming an alloy with lithium and a specific additive to the reaction site of the matrix metal and lithium. to be.

As the matrix metal, a metal capable of forming an alloy with lithium may be used. Specifically, a metal selected from the group consisting of Sn, Sb, Si, Zn, Pb, Cd, Ag, and Al may be used. Metals selected from the group consisting of Si, Zn, Pb, and Al are preferred, of which Al is most preferred. The additive is preferably selected from the group consisting of Mg, K, Li, B, Na, Ca and H.

The matrix metal is used in an amount of 60 to 99.95% by weight, preferably 60 to 99% by weight, more preferably 80 to 98% by weight, based on the total anode active material, and the additive material is 0.05 to 40% by weight, preferably It is used in an amount of 1 to 40% by weight, more preferably 2 to 20% by weight. Since the additive material is inserted into the reaction site with lithium in the matrix metal to form a bond between the matrix metal and the metal, the smaller the particle size, the more preferable. Preferably it has an average particle diameter of 0.1 micrometers-30 micrometers, More preferably, it has an average particle diameter of 0.5 micrometers-30 micrometers.

The negative electrode active material of the present invention may be manufactured through mechanical milling to form an alloy by causing mechanical collision and friction by mixing a matrix metal and an additive material and then using a ball mill type stirrer. In this case, the matrix metal and the additive material may be prepared in an inert atmosphere such as argon or nitrogen, and alcohols or benzenes may be used as a solvent to help the mixing and efficient grinding of the two materials. In addition, a method of vaporizing an additive material on the matrix metal to adhere to the surface of the matrix metal and then diffusing it to form an alloy may be used. However, it is not necessarily limited to these methods.

The metal-based negative electrode active material is coated on a current collector to prepare a negative electrode. The coating process of the metal-based negative electrode active material can be performed by any method. As a representative example thereof, a method of mixing a negative electrode active material with a polymer binder and coating the same may be used. In addition, sputtering, electron beam evaporation, vacuum thermal evaporation, laser ablation, chemical vapor deposition, thermal evaporation, plasma chemical vapor deposition, laser chemistry A vapor deposition method, a jet vapor deposition method, a plating method such as an electroplating or electroless plating method, a rolling method, and the like. The deposition process is carried out by heating in a high vacuum of 10 ^-6 Torr or more, the deposition atmosphere is carried out in a dry room with little moisture.

The current collector may be selected from the group consisting of Ni, Ti, Cu, Ag, At, Pt, Fe, Co, Cr, W and Mo. In addition, the current collector may be coated with a current collector material on one side or both sides of a polymer substrate such as a film form. The polymer may be a polymer selected from the group consisting of polyethylene terephthalate, polyimide, polyethylene naphthalate, polypropylene, polyethylene, and polyester.

Coating the current collector material on the polymer substrate may be carried out by any method. Representative examples include sputtering, electron beam evaporation, vacuum thermal evaporation, laser ablation, chemical vapor deposition, thermal evaporation, and plasma chemical vapor deposition. , A plating method such as a laser chemical vapor deposition method and a jet vapor deposition method, an electroplating method or an electroless plating method, and a rolling method. The deposition process is carried out by heating in a high vacuum of 10 ^-6 Torr or more, the deposition atmosphere is carried out in a dry room with little moisture.

The metal-based negative electrode active material of the present invention is used as a negative electrode active material of a lithium secondary battery. EMBODIMENT OF THE INVENTION Hereinafter, the lithium secondary battery which is one Embodiment of this invention is demonstrated with reference to drawings. The lithium secondary battery of the present invention is not limited to the form shown in the following figures.

1 is a perspective view of a lithium secondary battery 1 which is an embodiment of the present invention. The lithium secondary battery 1 is cylindrical and has a negative electrode 2, a positive electrode 3, a separator 4 disposed between the negative electrode 2 and the positive electrode 3, a negative electrode 2, a positive electrode 3, and The main part consists of the sealing member 6 which encloses the electrolyte, the cylindrical battery container 5, and the battery container 5 impregnated with the separator 4 as a main part. The lithium secondary battery 1 is configured by stacking the negative electrode 2, the positive electrode 3, and the separator 4 in order, and then storing the lithium secondary battery 1 in the battery container 5 in a state of being wound in a spiral shape.

The lithium secondary battery includes a cathode including a cathode active material capable of reversibly intercalating and deintercalating lithium ions. Representative examples of the positive electrode active material may be selected from the group consisting of the following formula (1) to (12).

[Formula 1]
Li _x Mn _1-y M _y A ₂ (0.90≤x≤1.1, 0 <y≤0.5)
[Formula 1a]

Li _x MnA ₂ (0.90≤x≤1.1)

[Formula 2]
Li _x Mn _1-y M _y O _2-z X _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5)
[Formula 2a]
Li _x MnO _2-z X _z (0.90≤x≤1.1, 0 <z≤0.5)
[Formula 2b]
Li _x Mn _1-y M _y O ₂ (0.90≤ x≤1.1, 0 <y≤0.5)
[Formula 2c]

Li _x MnO ₂ (0.90≤x≤1.1)

[Formula 3]
Li _x Mn ₂ O _4-z X _z (0.90≤x≤1.1, 0 <z≤0.5)
[Formula 3a]

Li _x Mn ₂ O ₄ (0.90≤x≤1.1)

[Formula 4]
Li _x Co _1-y M _y A ₂ (0.90≤x≤1.1, 0 <y≤0.5)
[Formula 4a]

Li _x CoA ₂ (0.90≤x≤1.1)

[Formula 5]
Li _x Co _1-y M _y O _2-z X _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5)
[Formula 5a]
Li _x CoO _2-z X _z (0.90≤x≤1.1, 0 <z≤0.5)
[Formula 5b]
Li _x Co _1-y M _y O ₂ (0.90≤x≤1.1, 0 <y≤0.5)
[Formula 5c]

Li _x CoO ₂ (0.90≤x≤1.1)

[Formula 6]
Li _x Ni _1-y M _y A ₂ (0.90≤x≤1.1, 0 <y≤0.5)
[Formula 6a]

Li _x NiA ₂ (0.90≤x≤1.1)

[Formula 7]
Li _x Ni _1-y M _y O _2-z X _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5)
[Formula 7a]
Li _x NiO _2-z X _z (0.90≤x≤1.1, 0 <z ≤0.5)
[Formula 7b]
Li _x Ni _1-y M _y O ₂ (0.90≤x≤1.1, 0 <y ≤0.5)
[Formula 7c]

Li _x NiO ₂ (0.90≤x≤1.1)

[Formula 8]
Li _x Ni _1-y Co _y O _2-z X _z (0.90≤x≤1.1, 0 <y ≤0.5, 0 <z ≤0.5)
[Formula 8a]
Li _x NiO _2-z X _z (0.90≤x≤1.1, 0 <z≤0.5)
[Formula 8b]
Li _x Ni _1-y Co _y O ₂ (0.90≤x≤1.1, 0 <y≤0.5)
[Formula 8c]

Li _x NiO ₂ (0.90≤x≤1.1)

[Formula 9]
Li _x Ni _1-yz Co _y M _z A _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5, 0 <α≤2)
[Formula 9a]
Li _x Ni _1-z M _z A _α (0.90≤x≤1.1, 0 <z≤0.5, 0 <α≤2)
[Formula 9b]
Li _x Ni _1-y Co _y A _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <α≤2)
[Formula 9c]
Li _x Ni _1-yz Co _y M _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5)
[Formula 9d]
Li _x NiA _α (0.90≤x≤1.1, 0 <α≤2)
[Formula 9e]
Li _x Ni _1-y Co _y (0.90≤x≤1.1, 0 <y≤0.5)
[Formula 9f]
Li _x Ni _1-z M _z (0.90≤x≤1.1, 0 <z≤0.5)
[Formula 9g]

Li _x Ni (0.90≤x≤1.1)

[Formula 10]
Li _x Ni _1-yz Co _y M _z O _2-α X _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5, 0 <α≤2)
[Formula 10a]
Li _x Ni _1-z M _z O _2-α X _α (0.90≤x≤1.1, 0 <z≤0.5, 0 <α≤2)
[Formula 10b]
Li _x Ni _1-y Co _y O _2-α X _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <α≤2)
[Formula 10c]
Li _x Ni _1-yz Co _y M _z O ₂ (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5)
[Formula 10d]
Li _x NiO _2-α X _α (0.90≤x≤1.1, 0 <α≤2)
[Formula 10e]
Li _x Ni _1-z M _z O ₂ (0.90≤x≤1.1, 0 <z≤0.5)
[Formula 10f]
Li _x Ni _1-y Co _y O ₂ (0.90≤x≤1.1, 0 <y≤0.5)
[Formula 10g]

Li _x NiO ₂ (0.90≤x≤1.1)

[Formula 11]
Li _x Ni _1-yz Mn _y M _z A _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5, 0 <α≤2)
[Formula 11a]
Li _x Ni _1-z M _z A _α (0.90≤x≤1.1, 0 <z≤0.5, 0 <α≤2)
[Formula 11b]
Li _x Ni _1-y Mn _y A _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <α≤2)
[Formula 11c]
Li _x Ni _1-yz Mn _y M _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5)
Formula 11d]
Li _x NiA _α (0.90≤x≤1.1, 0 <α≤2)
[Formula 11e]
Li _x Ni _1-z M _z (0.90≤x≤1.1, 0 <z≤0.5)
[Formula 11f]
Li _x Ni _1-y Mn _y (0.90≤x≤1.1, 0 <y≤0.5)
[Formula 11g]

Li _x Ni (0.90≤x≤1.1)

[Formula 12]
Li _x Ni _1-yz Mn _y M _z O _2-α X _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5, 0 <α≤2)
[Formula 12a]
Li _x Ni _1-z M _z O _2-α X _α (0.90≤x≤1.1, 0 <z≤0.5, 0 <α≤2)
[Formula 12b]
Li _x Ni _1-y Mn _y O _2-α X _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <α≤2)
[Formula 12c]
Li _x Ni _1-yz Mn _y M _z O ₂ (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5)
[Formula 12d]
Li _x NiO _2-α X _α (0.90≤x≤1.1, 0 <α≤2)
[Formula 12e]
Li _x Ni _1-z M _z O ₂ (0.90≤x≤1.1, 0 <z≤0.5)
[Formula 12f]
Li _x Ni _1-y Mn _y O ₂ (0.90≤x≤1.1, 0 <y≤0.5)
[Formula 12g]

Li _x NiO ₂ (0.90≤x≤1.1)

(In the above formula, M is at least one element selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V and rare earth elements, A is composed of O, F, S and P) Is an element selected from the group, X is F, S or P.)

As the electrolyte filled in the positive electrode and the negative electrode, an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like may be used, but are not limited thereto.

The organic liquid electrolyte includes an organic solvent and a lithium salt. The organic solvent is propylene carbonate, ethylene carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ν-butyrolactone, dioxolane, 4-methyldioxolane, N, N -Dimethylformamide, dimethylacetoamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate , Aprotic solvents such as methyl isopropyl carbonate, ethyl butyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diethylene glycol, dimethyl ether, or a mixed solvent in which two or more of these solvents are mixed. One or more selected from the group may be used. The mixing ratio in the case of mixing more than one can be appropriately adjusted according to the desired battery performance, which can be widely understood by those skilled in the art.

Examples of the lithium salt include LiPF ₆ , LIBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ At least one salt selected from the group consisting of, LiN (C _× F _{2x + 1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ) (where x and y are natural numbers), LiCl, and LiI may be used. They are dissolved in organic solvents and act as a source of lithium ions in the cell to enable operation of the basic lithium ion secondary battery and to promote the movement of lithium ions between the positive and negative electrodes.

The lithium secondary battery of the present invention may or may not include a separator depending on the electrolyte. For example, in the case of a solid electrolyte, since the electrolyte may also play a role of a separator, a separator may not be used. As the separator, polyethylene, polypropylene, polyvinylidene fluoride or two or more multilayer films thereof may be used, and polyethylene / polypropylene two-layer separator, polyethylene / polypropylene / polyethylene three-layer separator, polypropylene / polyethylene / poly It goes without saying that a mixed multilayer film such as a propylene three-layer separator can be used.

Hereinafter, examples and comparative examples of the present invention are described. However, the following examples are only one preferred embodiment of the present invention and the present invention is not limited to the following examples.

(Comparative Example 1)

Sn was deposited on a copper current collector as a negative electrode active material to prepare a negative electrode plate. A positive electrode active material slurry was prepared by mixing a LiCoO ₂ positive electrode active material, a polyvinylidene fluoride binder, and a super-P conductive material in an N-methylpyrrolidone mixed solvent at a 94/3/3 weight ratio. The slurry was coated on an aluminum current collector, dried, and rolled using a rolling mill to prepare a positive electrode plate.

The battery was assembled using the positive plate and the negative plate. The battery produced had a specification of 4.9 cm high, 3.4 cm wide and 0.4 cm thick and had a capacity of 850 mAh. In this case, a mixed solution of ethylene carbonate / dimethyl carbonate and ethylmethyl carbonate (3/3/4 volume ratio) in which 1.0 M LiPF ₆ was dissolved was used.

(Example 1)

Intermetallic compounds were prepared by reacting Sn and Li in a 1: 1 ratio. Copper was deposited on both sides of a polyethylene terephthalate film having a thickness of 5 μm. The intermetallic compound was deposited on both sides of a copper-deposited polyethylene terephthalate film to prepare a negative electrode plate. Using the negative electrode, a battery was manufactured in the same manner as in Comparative Example 1. The battery measures 4.9cm high, 3.4cm wide and 0.4cm thick and has a capacity of 850mAh.

(Example 2)

Intermetallic compounds were prepared by reacting Sn and B in a 1: 1 ratio. Copper was deposited on both sides of a polyethylene terephthalate film having a thickness of 5 μm. The intermetallic compound was deposited on both sides of a copper-deposited polyethylene terephthalate film to prepare a negative electrode plate. Using the negative electrode, a battery was manufactured in the same manner as in Comparative Example 1. The battery measures 4.9cm high, 3.4cm wide and 0.4cm thick and has a capacity of 850mAh.

The batteries of Examples 1, 2 and Comparative Example 1 were charged and discharged at a cut-off voltage of 2.75-4.2V. The charge and discharge curves of Example 1 and Comparative Example 1 are shown in FIG. 2. As shown in Figure 2 it can be seen that the discharge capacity of Example 1 is significantly superior to Comparative Example 1.

The negative electrode active material for a lithium secondary battery of the present invention reduces the irreversible capacity by adding an additive to a structurally unstable reaction site in which lithium ions can be trapped in a metal capable of forming an alloy with lithium during charge and discharge, thereby reducing the irreversible capacity. This improves the initial efficiency and capacity characteristics of the battery.

Claims (19)

Matrix metals capable of forming alloys with lithium; And A material for forming an intermetallic bond with the matrix metal selected from the group consisting of Mg, K, Li, B, Na, Ca and H A negative electrode active material for a lithium secondary battery comprising a. The negative active material of claim 1, wherein the matrix metal is selected from the group consisting of Sn, Sb, Si, Zn, Pb, Cd, Ag, and Al. The negative active material of claim 1, wherein the matrix metal is used in an amount of 60 to 99 wt% based on the total anode active material and the additive material is used in an amount of 1 to 40 wt%. The negative active material of claim 3, wherein the matrix metal is used in an amount of 80 to 98 wt% with respect to the entire negative active material, and the additive material is used in an amount of 2 to 20 wt%. The negative active material of claim 1, wherein the additive material has an average particle diameter of about 0.1 micrometers to about 30 micrometers. A negative electrode active material including a matrix metal capable of forming an alloy with lithium and a material forming an intermetallic bond with the matrix metal selected from the group consisting of Mg, K, Li, B, Na, Ca and H Cathode; A positive electrode comprising a positive electrode active material capable of intercalation and deintercalation of lithium ions; And Lithium secondary battery comprising an electrolyte. The lithium secondary battery of claim 6, wherein the matrix metal is used in an amount of 60 to 99 wt% based on the total anode active material, and the additive material is used in an amount of 1 to 40 wt%. The lithium secondary battery of claim 7, wherein the matrix metal is used in an amount of 80 to 98 wt% based on the total negative active material, and the additive material is used in an amount of 2 to 20 wt%. The lithium secondary battery of claim 6, wherein the additive has an average particle diameter of about 0.1 micrometers to about 30 micrometers. The lithium secondary battery of claim 6, wherein the negative electrode is manufactured by coating a negative electrode active material on a current collector. The lithium secondary battery of claim 10, wherein the current collector is made of at least one metal selected from the group consisting of Ni, Ti, Cu, Ag, At, Pt, Fe, Co, Cr, W, and Mo. The method of claim 10, wherein the current collector is prepared by coating at least one metal selected from the group consisting of Ni, Ti, Cu, Ag, At, Pt, Fe, Co, Cr, W and Mo on a polymer substrate Phosphorus Lithium Secondary Battery. The lithium secondary battery of claim 12, wherein the polymer substrate is selected from the group consisting of polyethylene terephthalate, polyimide, polyethylene naphthalate, polypropylene, polyethylene, and polyester. The lithium secondary battery of claim 6, wherein the cathode active material is a compound selected from the group consisting of Chemical Formulas 1 to 12: [Formula 1] Li _x Mn _1-y M _y A ₂ (0.90≤x≤1.1, 0 <y≤0.5) [Formula 1a] Li _x MnA ₂ (0.90≤x≤1.1) [Formula 2] Li _x Mn _1-y M _y O _2-z X _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5) [Formula 2a] Li _x MnO _2-z X _z (0.90≤x≤1.1, 0 <z≤0.5) [Formula 2b] Li _x Mn _1-y M _y O ₂ (0.90≤ x≤1.1, 0 <y≤0.5) [Formula 2c] Li _x MnO ₂ (0.90≤x≤1.1) [Formula 3] Li _x Mn ₂ O _4-z X _z (0.90≤x≤1.1, 0 <z≤0.5) [Formula 3a] Li _x Mn ₂ O ₄ (0.90≤x≤1.1) [Formula 4] Li _x Co _1-y M _y A ₂ (0.90≤x≤1.1, 0 <y≤0.5) [Formula 4a] Li _x CoA ₂ (0.90≤x≤1.1) [Formula 5] Li _x Co _1-y M _y O _2-z X _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5) [Formula 5a] Li _x CoO _2-z X _z (0.90≤x≤1.1, 0 <z≤0.5) [Formula 5b] Li _x Co _1-y M _y O ₂ (0.90≤x≤1.1, 0 <y≤0.5) [Formula 5c] Li _x CoO ₂ (0.90≤x≤1.1) [Formula 6] Li _x Ni _1-y M _y A ₂ (0.90≤x≤1.1, 0 <y≤0.5) [Formula 6a] Li _x NiA ₂ (0.90≤x≤1.1) [Formula 7] Li _x Ni _1-y M _y O _2-z X _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5) [Formula 7a] Li _x NiO _2-z X _z (0.90≤x≤1.1, 0 <z≤0.5) [Formula 7b] Li _x Ni _1-y M _y O ₂ (0.90≤x≤1.1, 0 <y ≤0.5) [Formula 7c] Li _x NiO ₂ (0.90≤x≤1.1) [Formula 8] Li _x Ni _1-y Co _y O _2-z X _z (0.90≤x≤1.1, 0 <y ≤0.5, 0 <z ≤0.5) [Formula 8a] Li _x NiO _2-z X _z (0.90≤x≤1.1, 0 <z≤0.5) [Formula 8b] Li _x Ni _1-y Co _y O ₂ (0.90≤x≤1.1, 0 <y≤0.5) [Formula 8c] Li _x NiO ₂ (0.90≤x≤1.1) [Formula 9] Li _x Ni _1-yz Co _y M _z A _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5, 0 <α≤2) [Formula 9a] Li _x Ni _1-z M _z A _α (0.90≤x≤1.1, 0 <z≤0.5, 0 <α≤2) [Formula 9b] Li _x Ni _1-y Co _y A _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <α≤2) [Formula 9c] Li _x Ni _1-yz Co _y M _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5) [Formula 9d] Li _x NiA _α (0.90≤x≤1.1, 0 <α≤2) [Formula 9e] Li _x Ni _1-y Co _y (0.90≤x≤1.1, 0 <y≤0.5) [Formula 9f] Li _x Ni _1-z M _z (0.90≤x≤1.1, 0 <z≤0.5,) [Formula 9g] Li _x Ni (0.90≤x≤1.1) [Formula 10] Li _x Ni _1-yz Co _y M _z O _2-α X _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5, 0 <α≤2) [Formula 10a] Li _x Ni _1-z M _z O _2-α X _α (0.90≤x≤1.1, 0 <z≤0.5, 0 <α≤2) [Formula 10b] Li _x Ni _1-y Co _y O _2-α X _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <α≤2) [Formula 10c] Li _x Ni _1-yz Co _y M _z O ₂ (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5) [Formula 10d] Li _x NiO _2-α X _α (0.90≤x≤1.1, 0 <α≤2) [Formula 10e] Li _x Ni _1-z M _z O ₂ (0.90≤x≤1.1, 0 <z≤0.5) [Formula 10f] Li _x Ni _1-y Co _y O ₂ (0.90≤x≤1.1, 0 <y≤0.5) [Formula 10g] Li _x NiO ₂ (0.90≤x≤1.1) [Formula 11] Li _x Ni _1-yz Mn _y M _z A _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5, 0 <α≤2) [Formula 11a] Li _x Ni _1-z M _z A _α (0.90≤x≤1.1, 0 <z≤0.5, 0 <α≤2) [Formula 11b] Li _x Ni _1-y Mn _y A _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <α≤2) [Formula 11c] Li _x Ni _1-yz Mn _y M _z (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5) Formula 11d] Li _x NiA _α (0.90≤x≤1.1, 0 <α≤2) [Formula 11e] Li _x Ni _1-z M _z (0.90≤x≤1.1, 0 <z≤0.5) [Formula 11f] Li _x Ni _1-y Mn _y (0.90≤x≤1.1, 0 <y≤0.5) [Formula 11g] Li _x Ni (0.90≤x≤1.1) [Formula 12] Li _x Ni _1-yz Mn _y M _z O _2-α X _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5, 0 <α≤2) [Formula 12a] Li _x Ni _1-z M _z O _2-α X _α (0.90≤x≤1.1, 0 <z≤0.5, 0 <α≤2) [Formula 12b] Li _x Ni _1-y Mn _y O _2-α X _α (0.90≤x≤1.1, 0 <y≤0.5, 0 <α≤2) [Formula 12c] Li _x Ni _1-yz Mn _y M _z O ₂ (0.90≤x≤1.1, 0 <y≤0.5, 0 <z≤0.5) [Formula 12d] Li _x NiO _2-α X _α (0.90≤x≤1.1, 0 <α≤2) [Formula 12e] Li _x Ni _1-z M _z O ₂ (0.90≤x≤1.1, 0 <z≤0.5) [Formula 12f] Li _x Ni _1-y Mn _y O ₂ (0.90≤x≤1.1, 0 <y≤0.5) [Formula 12g] Li _x NiO ₂ (0.90≤x≤1.1) (In the above formula, M is at least one element selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V and rare earth elements, A is composed of O, F, S and P) Is an element selected from the group, X is F, S or P.) The lithium secondary battery of claim 6, wherein the electrolyte is selected from the group consisting of an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte. The method of claim 15, wherein the organic liquid electrolyte is propylene carbonate, ethylene carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, v-butyrolactone, dioxolane, 4-methyl Dioxolane, N, N-dimethylformamide, dimethylacetoamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl ethyl carbonate, di At least one organic solvent selected from the group consisting of ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl butyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diethylene glycol, and dimethyl ether The lithium secondary battery. The method of claim 15, wherein the organic liquid electrolyte is LiPF ₆ , LIBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ) (where x and y are natural numbers), LiCl, and LiI A lithium secondary battery comprising a. The lithium secondary battery of claim 6, wherein the lithium secondary battery further comprises a separator. 19. The separator according to claim 18, wherein the separator is polyethylene, polypropylene, polyvinylidene fluoride, polyethylene / polypropylene bilayer separator, polyethylene / polypropylene / polyethylene three layer separator, and polypropylene / polyethylene / polypropylene three layer separator. A lithium secondary battery selected from the group consisting of.

Images