WO2019132080A1 - Cathode active material for lithium secondary battery, and lithium secondary battery comprising same - Google Patents

Abstract

The present invention relates to a cathode active material for a lithium secondary battery, a preparation method thereof, and a lithium secondary battery comprising the same. A cathode active material for a lithium secondary battery, according to one embodiment, may comprise a compound represented by the following chemical formula 1. [Chemical formula 1] Li1+k[M11-α M2α]O2-βQβ In chemical formula 1, M1 is NixCoyMnz, M2 is TiaZrbMgcM3d, M3 comprises at least one of alkaline-earth metal, alkali metal, a metal element of groups 3 to 12, and an element of groups 13 to 15, and Q comprises at least one of P and S, wherein -0.1 ≤ k ≤ 0.1, 0.0007≤ α ≤ 0.05, 0 ≤ β ≤ 0.1, 0.800 ≤ x ≤ 0.880, 0.01 ≤ y ≤ 0.15, 0.01 ≤ z ≤ 0.199, 1.6 ≤ (a+b)/c ≤ 10, and 0 ≤ d ≤ 0.01.

Description

Cathode active material for lithium secondary battery and lithium secondary battery comprising same

The present invention relates to a cathode active material for a lithium secondary battery and a lithium secondary battery comprising the same.

2. Description of the Related Art [0002] Recently, there has been an active research into the capacity of lithium secondary batteries of lithium secondary batteries, which are used as a power source for these devices, as they are expanded to middle and large device industries such as electric vehicles and hybrid vehicles as well as portable electronic devices.

Therefore, studies on the improvement of the performance of the cathode active material, which is a core material of the lithium secondary battery, have been actively conducted to increase the capacity of the lithium secondary battery.

At present, LiCoO ₂ and LiMn ₂ O ₄ And so on. However, LiCoO ₂ has a limitation in realizing a high capacity battery, LiMn ₂ O ₄ has a low energy density, and has a short life characteristic due to a problem of Mn ion elution.

Accordingly, there is a high interest in nickel-based cathode active materials capable of realizing high capacity batteries in recent years. However, the nickel-based cathode active material can realize a high capacity characteristic, but has poor thermal stability and low life characteristics at high temperature.

Therefore, it is urgent to develop a cathode active material for a lithium secondary battery that can realize a high capacity lithium secondary battery and has excellent thermal stability and life characteristics at a high temperature as well as at room temperature.

The present embodiments provide a cathode active material for a lithium secondary battery having excellent lifetime characteristics and thermal stability while securing a high capacity characteristic of the lithium secondary battery and a lithium ion battery including the same.

The cathode active material for a secondary battery according to one embodiment may include a compound represented by the following general formula (1).

[Chemical Formula 1]

Li _{1 + k} [M1 _{1 -?} M2 _? ] O2 _-? Q _?

M3 is at least one element selected from the group consisting of alkaline earth metal, alkali metal, Group 3 to Group 12 metal elements and Group 13 to Group 15 elements, M1 is Ni _x Co _y Mn _{z ,} M2 is Ti _a Zr _b Mg _c M3 _{d ,} Wherein Q comprises at least one of P and S, wherein -0.1? K? 0.1, 0.0007??? 0.05, 0??? 0.1, 0.800? X? 0.880, 0.01? Y? 0.15, 0.01? Z ? 0.199, 1.6? (A + b) / c? 10, 0? D? 0.01.

The lithium secondary battery according to one embodiment may include a cathode, a cathode, and an electrolyte including a cathode active material for a lithium secondary battery according to one embodiment.

The positive electrode active material for a secondary battery according to an embodiment of the present invention can be used in a lithium secondary battery by combining appropriate doping elements under specific conditions so that the capacity of the battery can be increased while maintaining excellent thermal stability, The lithium secondary battery having excellent lifetime characteristics can be realized.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

Also, throughout the specification, when an element is referred to as "including" an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

Hereinafter, a cathode active material for a lithium secondary battery according to an embodiment, a method of manufacturing the same, and a lithium secondary battery including the same will be described in detail.

Cathode active material for lithium secondary battery

The cathode active material for a lithium secondary battery according to one embodiment may include a compound represented by the following general formula (1).

[Chemical Formula 1]

Li _{1 + k} [M1 _{1 -?} M2 _? ] O2 _-? Q _?

M3 is at least one element selected from the group consisting of alkaline earth metal, alkali metal, Group 3 to Group 12 metal elements and Group 13 to Group 15 elements, M1 is Ni _x Co _y Mn _{z ,} M2 is Ti _a Zr _b Mg _c M3 _{d ,} Wherein Q comprises at least one of P and S, wherein -0.1? K? 0.1, 0.0007??? 0.05, 0??? 0.1, 0.800? X? 0.880, 0.01? Y? 0.15, 0.01? Z ? 0.199, 1.6? (A + b) / c? 10, 0? D? 0.01.

In the above formula (1), k may be -0.1 or more and 0.1 or less. Accordingly, the molar ratio of Li can be 0.9 or more and 1.1 or less. When the molar ratio of Li is less than 0.9, Ni is liable to be incorporated into the Li phase and the occupancy rate of the metal sites of the lithium site becomes large, and it is difficult to obtain a Li-Ni composite oxide capable of realizing a high capacity battery. When the molar ratio of Li is larger than 1.1, the incorporation of Li into the metal site increases, so that Ni separated from the metal site is mixed into the Li phase and the metal occupation ratio of the lithium site becomes large. Therefore, k is preferably in the above range, more specifically, 0? K? 0.05.

In the formula (1), M1 may be a nickel-based lithium metal oxide having a layered structure, that is, Ni _x Co _y Mn _z . The nickel-based lithium metal oxide of this embodiment has a high molar ratio of nickel. That is, in M1 of Formula 1, the molar ratio x of nickel may be in the range of 0.800? X? 0.880, more specifically, 0.820? X? 0.860. When the molar ratio of nickel satisfies the above range, a high capacity lithium secondary battery can be realized.

Further, the nickel-based lithium metal oxide includes Co and Mn, and y and z, which are contents of Co and Mn, may be in the range of 0.01? Y? 0.15 and 0.01? Z? 0.199, respectively. More specifically, y and z may be in the range of 0.05? Y? 0.15 and 0.03? Z? 0.1, respectively. When the molar ratio of Co and Mn in the nickel-based lithium metal oxide satisfies the above range, the structural stability of the cathode active material capable of realizing a high capacity can be improved.

Then, M2 dopant is shown.

First, M2 may include at least three kinds of dopants, and may further include M3 as needed. That is, M2 can be expressed as Ti _a Zr _b Mg _c M _d . The total molar ratio alpha of M2, that is, a + b + c + d, may be in the range of 0.0007??? 0.05, more specifically 0.005?? 0.03 or 0.008?? 0.04. Further, a, b and c, which represent the molar ratios of the respective doping elements in M2, may be 1.6? (A + b) / c? 10, more specifically 1.9? (A + b) / c? 8 or 2.6 ? (A + b) / c? 5. In addition, the molar ratio of M3, which is an additional doping element, may be in the range of 0? D? 0.01, more specifically, 0? D? 0.009 as necessary.

When the three kinds of dopants represented by M2 as the dopant in the cathode active material according to this embodiment, that is, Ti, Zr and Mg, are contained in the above ratio, the structural stability and surface stabilization of the cathode active material can be improved.

Specifically, Ti may be included in a ratio of 0.0005? A? 0.02, or 0.001? A? 0.01. When Ti is included in the above ratio, it is possible to control the phase transition of the nickel-based lithium metal oxide to the irreversible region when the lithium is desorbed and inserted in the charge-discharge process. In addition, the structural stability of the cathode active material can be improved by controlling the expansion of the c-axis in the nickel metal-oxide having a layered crystal structure.

Further, Zr may be contained in a ratio of 0.0001? B? 0.01, or 0.0005? B? 0.005. When Zr is contained in the above ratio, Zr is partially substituted with the transition metal located on the surface of the nickel-based lithium metal oxide particle, and an oxide containing Zr is formed on the surface of the nickel-based lithium metal oxide particle, So that stabilization of the surface can be improved.

On the other hand, Mg may be contained in a ratio in the range of 0.0001? C? 0.01, or 0.001? C? 0.005. When Mg is contained in the above ratio, cation mixing between lithium and nickel in the lithium layer of the nickel-based lithium metal oxide having the layered crystal structure can be suppressed. Accordingly, by improving the structural stability of the cathode active material, a lithium secondary battery having improved capacity and life characteristics at the same time can be realized.

In the above Formula 1 of the present embodiment, M3 is a dopant other than M1 and M2 described above and may include at least one of an alkaline earth metal, an alkali metal, a Group 3 to Group 12 metal element, and a Group 13 to Group 15 element. For example, M3 may be Al, B, P, S, Mo, V, W, Ca, Na, Zn, Cr, Fe, Cu, Ru, Sr, Be, Si, Ge, Ba, , Ta, Ga, Os, As, and Sb. More specifically, the C may include at least one of Al and B. Alternatively, M3 may include both Al and B.

In this case, in the above formula (1), the molar ratio of Al may be in a range of 0.001? Al? 0.01, more specifically 0.002? Al? 0.01. The molar ratio of B may be in the range of 0.0001? B? 0.001, more specifically, 0.0005? B? 0.001.

When Al is contained in the above ratio, thermal stability and structure stabilization of the cathode active material according to this embodiment are possible.

B is confirmed to be related to the densification of the positive electrode active material particles. When B is contained in the above-mentioned ratio, the inter-primary-particle bonding of the above-mentioned nickel-based lithium oxide is made robust, And the ion conductivity can be improved.

Next, the compound represented by Formula 1 may have I (003/104) of 1.8 or more, more specifically 1.8 or more and 2 or less, as measured by X-ray diffraction analysis using a CuK? Ray.

Generally, when the positive electrode active material has a layered crystal structure containing no lithium excess phase, when the substitution of lithium contained in the transition metal, that is, cation mixing, between the transition metal contained in the transition metal layer and the lithium layer occurs, .

As one of such cationic mixed indexes, the peak intensity ratio I (003/104) of the XRD measurement results can be used, and generally, the larger the I (003/104), the less the cationic mixing is.

In this embodiment, the intensity I003 of the diffraction peak of the (003) plane and the intensity I003 of the diffraction peak of the (104) plane measured by the X-ray diffraction analysis using the CuKa ray as the parameter indicating the crystallinity of the nickel- The intensity ratio I (003/104) to the intensity I104 was measured.

The diffraction peak of the (003) plane is inherent to the layered crystal structure, and the diffraction peak of the (104) plane is measured not only in the layered crystal structure but also in the cubic crystal structure. Therefore, the larger the I (003/104), the closer to the single phase of the layered crystal structure. That is, the crystallinity of the nickel-based lithium metal oxide is improved.

In the present embodiment, the I (003/104) range of the compound represented by Formula 1 is as described above. I (003/104) satisfies the above range, the lithium secondary battery using the cathode active material of this embodiment has an excellent initial capacity and can improve lifetime characteristics at room temperature and high temperature environment.

Lithium secondary battery

The cathode active material for a lithium secondary battery according to one embodiment described above can be usefully used for the anode of a lithium secondary battery. That is, the lithium secondary battery according to an embodiment of the present invention includes a cathode and an anode including the above-described cathode active material and an electrolyte.

Specifically, the lithium secondary battery according to an embodiment of the present invention may include an electrode assembly including a cathode, a cathode, and a separator disposed between the anode and the cathode.

The negative electrode may be prepared by preparing a composition for forming a negative electrode active material layer by mixing a negative electrode active material, a binder and a conductive material, and then applying the composition to an anode current collector such as copper.

As the negative electrode active material, a material capable of intercalating / deintercalating lithium is used. Examples of the negative active material include lithium metal, lithium alloy, coke, artificial graphite, natural graphite, Lt; / RTI >

Examples of the binder include polyvinyl alcohol, carboxymethylcellulose / styrene-butadiene rubber, hydroxypropylene cellulose, diacetylene cellulose, polyvinyl chloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene Polypropylene and the like can be used, but the present invention is not limited thereto. The binder may be mixed in an amount of 1 to 30% by weight based on the total amount of the composition for forming the negative electrode active material layer.

The conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and specifically includes graphite such as natural graphite and artificial graphite; Carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used. The conductive material may be mixed in an amount of 0.1 to 30% by weight based on the total amount of the composition for forming the anode active material layer.

The anode includes the cathode active material for a lithium secondary battery according to an embodiment. That is, the cathode active material, the binder and optionally the conductive material may be mixed to prepare a composition for forming a cathode active material layer, and then the composition may be applied to a cathode current collector such as aluminum. Further, the conductive material, binder and solvent are used in the same manner as in the case of the above-mentioned anode.

As the electrolyte to be filled in the lithium secondary battery, a non-aqueous electrolyte or a known solid electrolyte may be used, and a lithium salt dissolved therein may be used.

The lithium salt may be, for example, 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 , LiCl, and LiI may be used.

Examples of the solvent of the non-aqueous electrolyte include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate; Chain carbonates such as dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; Esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and? -Butyrolactone; Ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane and 2-methyltetrahydrofuran; Nitriles such as acetonitrile; Amides such as dimethylformamide, and the like can be used, but the present invention is not limited thereto. These may be used singly or in combination. Particularly, a mixed solvent of cyclic carbonate and chain carbonate can be preferably used.

As the electrolyte, a gelated polymer electrolyte in which an electrolyte solution is impregnated with a polymer electrolyte such as polyethylene oxide or polyacrylonitrile, or an inorganic solid electrolyte such as LiI or Li ₃ N can be used.

The separator may be an olefin-based polymer such as polypropylene, which is chemically resistant and hydrophobic; A sheet or a nonwoven fabric made of glass fiber, polyethylene or the like can be used. When a solid electrolyte such as a polymer is used as the electrolytic solution, the solid electrolytic solution may also serve as a separation membrane.

Examples of the present invention, comparative examples thereof, and evaluation examples thereof will be described below. The following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention.

Example 1

(1) Preparation of cathode active material

The desired Li _{1 . 025} Ni _{0 . 82812} Co _{0 . 09859} Mn _{0 . 05915} Ti _{0 . 00877} Zr _{0. 00153} Mg _{0 . To} be a stoichiometric molar ratio of O ₂ , Ni _{0 . 84} Co _{0 .} The 1Mn _{0 .06} (OH) _2, the lithium source material LiOH, Ti raw material is TiO _2, Zr source material is ZrO _2, and Mg raw material of Mg (OH) _2, were mixed in a dry process.

4.0 kg of the dry mixture was filled in a mullite saggar and fired in a box-type sintering furnace in an air atmosphere at a firing temperature of 785 캜 for a total of 30 hours. Thereafter, it was naturally cooled to room temperature.

The material thus obtained was pulverized and classified to prepare a cathode active material of Example 1 having an average particle diameter of 10 mu m.

(2) Production of secondary battery

90 wt% of the positive electrode active material for a lithium secondary battery, 5 wt% of a conductive material (Super-P), and 5 wt% of a binder (PVDF) And uniformly mixed to prepare a slurry.

The slurry was uniformly applied to an aluminum (Al) current collector, and then NMP was evaporated through hot air drying. The slurry was compressed by a roll press and then vacuum dried in a vacuum oven at 100 ° C to 200 ° C for 12 hours to prepare a positive electrode.

Lithium metal (Li-metal) was used as a counter electrode, and 1.2 mol of LiPF 6 (LiPF 6) was added to a mixed solvent having a volume ratio of ethylene carbonate (EC: ethylene carbonate: DMC: Dimethyl Carbonate) ₄ solution was used.

Using each of the above components, a CR2032 half-cell was fabricated according to a conventional manufacturing method.

Examples 2 to 7 and Comparative Examples 1 to 3

The stoichiometric molar ratio of Ni, Co, Mn, Ti, Zr, Mg, Al, and B and the value of I (003/104) in the target cathode active material were as shown in Table 1 below. 1), a lithium secondary battery was prepared in the same manner as in (2) of Example 1.

division	Ni	Co	Mn	Ti	Zr	Mg	Al	B	(a + b) / c	I (003/104)
Example 1	0.82812	0.09859	0.05915	0.00877	0.00153	0.00384	-	-	2.682	1.8358
Example 2	0.82855	0.09864	0.05918	0.00877	0.00102	0.00384	-	-	2.549	1.8229
Example 3	0.82893	0.09868	0.05921	0.00877	0.00153	0.00288	-	-	3.576	1.8168
Example 4	0.82304	0.09798	0.05879	0.00877	0.00153	0.00384	0.00519	0.00086	2.682	1.8621
Example 5	0.83055	0.09888	0.05933	0.00586	0.00154	0.00384	-	-	1.922	1.8168
Example 6	0.82376	0.09807	0.05884	0.00877	0.00153	0.00384	0.00519	-	2.682	1.8638
Example 7	0.82740	0.09850	0.05910	0.00877	0.00153	0.00384	-	0.00086	2.682	1.8345
Comparative Example 1	0.83183	0.09903	0.05942	0.00587	-	0.00385	-	-	1.521	1.7897
Comparative Example 2	0.82737	0.09850	0.05910	0.00584	0.00153	0.00766	-	-	0.961	1.8172
Comparative Example 3	0.83114	0.09895	0.05937	0.00293	0.00154	-	0.00521	0.00086	-	1.7588

Experimental Example 1 - Measurement of Initial Discharge Capacity

The lithium secondary batteries produced according to Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated for forming efficiency.

Specifically, the formation efficiency between 3.0 V and 4.3 V was measured under conditions of 0.1 / 0.1C for Li + / Li at 25 캜 and 45 캜, and the results are shown in Table 2 below.

Experimental Example 2 - Measurement of Capacity Retention Rate

The capacity retention ratios of the lithium secondary batteries produced according to Examples 1 to 5 and Comparative Examples 1 to 3 were measured.

Specifically, when charging and discharging were repeated at a temperature of 3.0 V to 4.3 V at room temperature (25 캜) under 1.0 C of charge and discharge of 1.0 C, the capacity retention rate (30 ^th / 1 ^{th at} 30 cycles, ) Are shown in Table 2 below.

Separately, the lithium secondary batteries produced according to Examples 1 to 5 and Comparative Examples 1 to 3 were repeatedly charged and discharged at a high temperature (45 ° C) of 3.0 V to 4.3 V and a charging of 1.0 C and a discharge of 1.0 C 30 ^th / 1 ^th capacity retention rate (30th cycle capacity with respect to the first cycle capacity) was calculated and shown in Table 2 below.

Experimental Example 3 - Measurement of thermal stability

For the cathode active materials prepared according to Examples 1 to 5 and Comparative Examples 1 to 3, the thermal stability of a differential scanning calorimeter (DSC) was measured. DSC evaluation was carried out using Mettler Toledo's Au-plated HP cell (15 MPa), and the results are shown in Table 2.

Specifically, the electrolytic solution (mass ratio of the cathode active material and the electrolytic solution = 1: 1) was added to the cathode active materials prepared in Examples 1 to 5 and Comparative Examples 1 to 3, followed by DSC evaluation. The measurement range was 30 占 폚 to 400 占 폚.

division	Initial capacity (mAh / g)	Room temperature 30th / 1th (%)	High temperature 30th / 1th (%)	DSC (main peak, ° C)
Example 1	213.95	94.69	90.31	223.5
Example 2	213.07	92.01	87.75	-
Example 3	212.59	93.86	89.53	-
Example 4	213.95	93.69	91.31	226.82
Example 5	215.43	92.64	89.93	-
Example 6	214.12	93.72	90.28	225.17
Example 7	213.23	92.15	90.15	224.37
Comparative Example 1	216.33	91.30	87.57	-
Comparative Example 2	207.24	91.11	87.5	-
Comparative Example 3	211.62	91.47	82.93	-

Referring to Table 2, the lithium secondary battery employing the cathode active materials of Examples 1 to 7, in which Ti, Zr, and Mg were selectively doped with Al and B in a specific molar ratio, was superior in initial capacity and at the same time, It can be confirmed that the retention ratio is very excellent.

On the other hand, in the case of a lithium secondary battery employing the cathode active materials of Comparative Examples 1 to 3 prepared by doping with at least one element of Ti, Zr and Mg, at least one of the initial capacity, the room temperature, Which is lower than that of the conventional method.

In addition, the cathode active materials prepared according to Examples 1, 4, and 6 to 7 are also excellent in thermal stability.

Therefore, when a cathode active material doped to contain Ti, Zr and Mg at a specific molar ratio is employed as in the present embodiment, a high capacity characteristic can be secured, and at the same time, lithium having excellent lifetime characteristics and thermal stability at room temperature and high temperature A secondary battery can be realized.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (15)

1. 1. A cathode active material for a lithium secondary battery comprising a compound represented by the following formula (1).

   [Chemical Formula 1]

   Li _{1 + k} [M1 _{1 -?} M2 _? ] O2 _-? Q _?

   (In the formula 1,

   M1 is Ni _x Co _y Mn _z,

   M2 is Ti _a Zr _b Mg _c M3 _d,

   M3 comprises at least one of an alkaline earth metal, an alkali metal, a Group 3 to 12 metal element and a Group 13 to Group 15 element,

   Q comprises at least one of P and S,

   X? 0.10, 0.0007??? 0.1, 0.800? X? 0.880, 0.01? Y? 0.15, 0.01? Z? 0.199, 1.6? A + b / c? ? D? 0.01)
2. The method according to claim 1,

   1.9 < / = (a + b) / c? 8 in the above formula (1).
3. The method according to claim 1,

   2.6? (A + b) / c? 5 in the above formula (1).
4. The method according to claim 1,

   0.820? X? 0.860 in the above formula (1).
5. The method according to claim 1,

   The compound represented by Formula 1 has I (003/104) of 1.8 or more as determined by X-ray diffraction analysis using CuK? Ray.
6. The method according to claim 1,

   Wherein the compound represented by Formula 1 has I (003/104) of 1.8 or more and 2 or less as measured by X-ray diffraction analysis using a CuK? Ray.
7. The method according to claim 1,

   0.0005? A? 0.02 in the above formula (1).
8. The method according to claim 1,

   0.0001? B? 0.01 in the above formula (1).
9. The method according to claim 1,

   0.0001? C? 0.01 in the above formula (1).
10. The method according to claim 1,

    In the above formula 1, M3 is at least one element selected from the group consisting of Al, B, P, S, Mo, V, W, Ca, Na, Zn, Cr, Fe, Cu, Ru, Sr, Be, Si, Ge, , Ta, Ga, Os, As, and Sb.
11. The method according to claim 1,

    Wherein M3 is at least one of Al and B. In the formula,
12. 12. The method of claim 11,

    In the formula (1), the Al is 0.001? Al? 0.01.
13. 12. The method of claim 11,

    In the formula (1), B is 0.0001? B? 0.001.
14. 12. The method of claim 11,

    In the formula (1), M3 is Al and B, and the positive electrode active material for a lithium secondary battery is M3.
15. anode;

    cathode; And

    Comprising an electrolytic solution,

    The lithium secondary battery according to any one of claims 1 to 14, wherein the positive electrode comprises the positive electrode active material for a lithium secondary battery.