KR101190226B1 - Cathode active material for a lithium secondary battery, preparation thereof, and a lithium secondary battery containing the same - Google Patents

Abstract

The present invention relates to a positive electrode active material for a lithium secondary battery, and more particularly, Li _x [Li _y (Ni _{(1- (a + b))} Co _a Mn _b ) _{(1- (z + w)))} M ¹ _z A cathode active material for a lithium secondary battery represented by M ² _w ] O ₂ , and a method of manufacturing the same.

By using the cathode active material of the present invention, it is possible to manufacture an electrochemical cell, particularly a lithium secondary battery, which has excellent life characteristics and thermal stability.

Lithium secondary battery, positive electrode active material, lithium transition metal oxide, high temperature life characteristics, thermal stability

Description

Cathode active material for lithium secondary battery, manufacturing method thereof and lithium secondary battery including the same {CATHODE ACTIVE MATERIAL FOR A LITHIUM SECONDARY BATTERY, PREPARATION THEREOF, AND A LITHIUM SECONDARY BATTERY CONTAINING THE SAME}

The present invention relates to a cathode active material for a lithium secondary battery and a manufacturing method thereof, and more particularly, to a cathode active material for a lithium secondary battery excellent in high temperature life characteristics and thermal stability, and a lithium secondary battery including the same, among electrochemical characteristics of a secondary battery. It is about.

In recent years, portable electronic devices (PDAs, mobile phones, laptops, etc.) for personal electronic devices have been rapidly developed and wirelessized, and the demand for small, light, and high energy density lithium secondary batteries in charge of these driving power sources has increased. have. The characteristics required for the lithium secondary battery are charge / discharge characteristics, life characteristics, rate characteristics, and thermal stability. As these characteristics are improved, the field of application becomes wider.

Lithium secondary batteries that are currently commercialized mostly use LiCoO ₂ as a cathode active material. LiCoO ₂ is a material with excellent thermal stability due to stable charge and discharge characteristics and high electron conductivity. Recently, however, there is a need for a cathode active material for a lithium secondary battery having a high voltage and a large capacity. When LiCoO ₂ is continuously charged and discharged at 4.3 V or higher, the cathode active material reacts with the electrolyte due to lattice deformation or destruction of crystal structure. By doing so, life characteristics and safety are lowered. In addition, Co, which is a starting material of cathode active material, has a tendency to increase in price due to its small reserves, and further development of alternative cathode active material is needed due to toxicity and environmental pollution problem to human body.

Accordingly, LiNiO ₂ , LiMn ₂ O ₄ , LiFePO ₄ , and Li (Ni _x Co _y Mn _z ) O ₂ may be used as positive electrode active materials for lithium secondary batteries that are currently actively researched and developed. However, in the case of LiNiO ₂ , not only is it difficult to synthesize, but it is also difficult to commercialize due to problems of thermal stability. In the case of LiMn ₂ O ₄ , some commercialization is made in low-cost products, but structural deformation due to Mn ³⁺ (Jahn-Teller distortion) Due to the poor lifespan. In addition, LiFePO ₄ has a low price and excellent safety and is currently being studied for HEV, but due to low conductivity it is difficult to apply to other fields.

Therefore, Li (Ni _x Co _y Mn _z ) O ₂ is the most recently attracting attention as an alternative cathode active material for LiCoO ₂ . This material is cheaper than LiCoO ₂ and has the advantage of being able to be used for high capacity and high voltage, but has disadvantages of poor rate characteristics and long life at high temperatures. In order to overcome this disadvantage, a method of coating a highly conductive metal on the surface of the positive electrode active material, or doping the material such as Al, Mg, Ti, Zr, Sn, Ca, Ag and Zn in the interior Many researches have been conducted by methods, and the coating method uses a wet method, but has a large problem in that the price is actually increased in mass production. Currently, reports of increasing the characteristics of the metal through dry doping have been increasing. It is a trend.

In particular, in recent years, attempts have been made to improve the electrochemical properties of lithium secondary batteries through Ti doping. However, in order to dope inside the cathode active material using TiO ₂ , which is widely used to date, high plasticity of 1000 ° C. or higher is required. There is a disadvantage that a temperature and a large amount of firing time are required.

Therefore, in manufacturing a lithium secondary battery, lithium can be distributed evenly in the positive electrode active material and maximize the doping effect to improve the structural stability and electrochemical properties to prevent degradation of the battery performance as described above There is a need for research on cathode active materials for secondary batteries.

The present invention is to provide a positive electrode active material for a lithium secondary battery excellent in structural stability and electrochemical properties by maximizing the doping effect of the additive element and a method of manufacturing the same.

In addition, the present invention is to provide a lithium secondary battery including the positive electrode active material for the lithium secondary battery.

The present invention provides a cathode active material for a lithium secondary battery represented by Formula 1 below,

[Formula 1]

Li _x (Li _y (Ni _{(1- (a + b))} Co _a Mn _b ) _{(1- (z + w)))} M ¹ _z M ² _w ] O ₂

Wherein,

M ¹ is at least one selected from the group consisting of Al, Mg, Ti, Zr, Sn, Ca, Ag, and Zn,

M ² is at least one selected from the group consisting of Al, Ti, Zr, Ag, and Sn,

x, y, z, w, a, b are 0.8 <x <1, 0.01 ≤ y ≤ 0.1, 0.001 ≤ z ≤ 0.1, 0.001 ≤ w ≤ 0.1, 0.002 ≤ z + w ≤ 0.2, 0.1 ≤ a <0.9 , 0.1 ≦ b <0.9, 0.2 ≦ a + b <1.

In addition, the present invention comprises the steps of a) preparing a transition metal composite precursor represented by the following Chemical Formula 2 using a mixed solution containing a metal compound containing nickel, cobalt, manganese, b) the transition prepared in step a) Coating a metal composite precursor with a metal oxide represented by Formula 3, c) mixing a transition metal composite precursor coated in step b) with a lithium salt and a lithium transition metal oxide represented by Formula 3, And d) provides a method for producing a cathode active material for a lithium secondary battery represented by the formula (1) comprising the step of heat-treating the metal oxide mixed in step c),

[Formula 2]

(Ni _{(1- (a + b))} Co _a Mn _b ) (OH) ₂

(3)

M ¹ _c O _d

[Formula 4]

Li _e M ² _f O _g

Wherein,

M ¹ is at least one selected from the group consisting of Al, Mg, Ti, Zr, Sn, Ca, Ag, and Zn,

M ² is at least one selected from the group consisting of Al, Ti, Zr, Ag, and Sn,

a and b are each 0.1 ≦ a <0.9, 0.1 ≦ b <0.9, 0.2 ≦ a + b <1,

c and d are each an integer of 1 to 30 depending on the number of oxidation of M ¹ ,

e, f, g are each an integer from 1 to 30 wherein M ² according to the oxidation number of.

In addition, the present invention provides a lithium secondary battery including the cathode active material.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by producing a positive electrode active material for lithium secondary batteries excellent in structural stability and electrochemical properties by effectively and evenly distribute various transition metal particles inside the positive electrode active material for lithium secondary batteries.

In particular, in the present invention, unlike the doping of the positive electrode active material using a conventional TiO _2, etc., by performing a coating process using a transition metal oxide and a process of mixing and baking a lithium transition metal oxide, to the inside of the particles of the positive electrode active material It is characterized by distributing the additive elements evenly to achieve an excellent doping effect and thus expressing good structural stability and electrochemical properties.

The degree of improvement of the structural stability and electrochemical properties according to the doping effect of the positive electrode active material for a lithium secondary battery represented by Chemical Formula 1 of the present invention may be evaluated by XRD measurement results before and after high temperature cycling.

XRD measurement before and after high temperature cycling refers to XRD before and after 50 times or more after about 50 times to 1000 times of current density between 0.1C and 10C at a high temperature of 50 to 80 ° C, respectively. To say that to measure. Through the XRD measurement before and after the cycling, it is a method of comparing and evaluating the deterioration of the structure of the positive electrode active material by comparing the crystallinity of the initially prepared positive electrode active material and the crystallinity of the positive electrode active material after charge and discharge. In particular, at high temperatures, the resistance tends to be faster due to a decrease in resistance, leading to an increase in initial capacity, whereas the lifetime characteristics tend to be poor because the structure of the surface collapses more easily. Therefore, the structural stability at high temperature can be evaluated by analyzing XRD together with the life characteristics at high temperature.

In particular, the positive electrode active material for a lithium secondary battery represented by Chemical Formula 1 of the present invention may have a difference of 2θ (2 theta) values of 0.05 or less, preferably 0 to 0.03, according to XRD measurement results before and after the high temperature cycling. Significant differences in 2θ (2theta) values before and after cycling of the positive electrode active material, especially at high temperatures, indicate a structural degradation or collapse of the positive electrode active material during continuous charging and discharging. The smaller the difference between the values of 2θ (2 theta) in terms of lifespan characteristics and thermal stability, the better.

In addition, the cathode active material for a lithium secondary battery of the present invention may have an average particle size of preferably 1 to 20 ㎛, more preferably 3 to 12 ㎛. If the average particle diameter of the positive electrode active material is less than 1 µm, the density of the active material is low, so that the capacity of the battery using the same decreases, and if it exceeds 20 µm, the high load characteristics of the battery are reduced.

The cathode active material for a lithium secondary battery represented by Chemical Formula 1 may be coated or doped with a metal oxide including M ¹ on a transition metal composite including nickel, manganese, and cobalt, and a lithium metal oxide including M ² together with a lithium salt. In addition, Li and the additive elements M ¹ and M ² are uniformly distributed in the transition metal composite.

Nickel, manganese, and cobalt in the formula 1 is a transition metal composite is generally used in combination in the composition range that can be used in the positive electrode active material for lithium secondary batteries, but in formula 1 0.1 ≤ a <0.9, 0.1 ≤ b <0.9, 0.2 <a + b <1 can be used in the composition.

In addition, in Chemical Formula 1, M ¹ and M ² may generally use a metal element that may be used in a cathode active material for a lithium secondary battery, and M ¹ may be Al, Mg, Ti, Zr, Sn, Ca, Ag, and Zn. One or more selected from the group consisting of may be used, and M ² may use one or more selected from the group consisting of Al, Ti, Zr, Ag, and Sn. Is more preferably, in the above M ¹ used may be one or more such as Ti, Zr, Al or Mg, M ² roneun can be used at least one kind such as Ti, Zr, Al or Mg. M ¹ and M ² are preferably included in the general formula (1) as 0.001 ≤ z ≤ 0.1, 0.001 ≤ w ≤ 0.1, 0.002 ≤ z + w ≤ 0.2.

When z and w are respectively added in a small amount of less than 0.001 with respect to M ¹ and M ² in Formula 1, even doping of the material, that is, M ¹ and M ² is difficult, and also exhibits effects such as structural stability. it's difficult. In addition, when z and w are each doped more than 0.1, structurally stable, but may cause a problem that the initial capacity per gram can be significantly reduced.

In the general formula (1), the Li content is preferably adjusted to be 0.8 <x <1, and 0.01 <y <0.1. Particularly, when Li is in an excessive amount, Li remains on the surface of the particles, which increases the reactivity with the electrolyte, leading to deterioration in battery safety and oxygen deficiency, resulting in structural instability. Therefore, it is preferable to maintain 0.8 <x <1, 0.01 <y <0.1, more preferably 1.0 <x + y <1.06 in the general formula (1).

In particular, the positive electrode active material for a lithium secondary battery of the present invention M ¹ is coated on a transition metal complex in which nickel, manganese, and cobalt are combined, and the coated transition metal complex is combined with lithium and M ^2, and is represented by Chemical Formula 1 It is characterized by having a structure.

On the other hand, the cathode active material for a lithium secondary battery of the present invention can be prepared through a process comprising the following steps:

a) preparing a transition metal composite precursor represented by the following Chemical Formula 2 using a mixed solution containing a metal compound containing nickel, cobalt and manganese,

b) coating the transition metal composite precursor prepared in step a) with a metal oxide represented by Formula 3 below;

c) mixing the transition metal composite precursor coated in step b) with a lithium salt and a lithium transition metal oxide represented by the following Formula 3, and

d) heat treating the metal oxide mixed in step c);

 [Formula 2]

Ni _{(1- (a + b))} Co _a Mn _b (OH) ₂

(3)

M ¹ _c O _d

[Formula 4]

Li _e M ² _f O _g

Wherein,

M ¹ is at least one selected from the group consisting of Al, Mg, Ti, Zr, Sn, Ca, Ag, and Zn,

M ² is at least one selected from the group consisting of Al, Ti, Zr, Ag, and Sn,

a and b are each 0.1 ≦ a <0.9, 0.1 ≦ b <0.9, 0.2 ≦ a + b <1,

c and d are each an integer of 1 to 30 depending on the number of oxidation of M ¹ ,

e, f, g are each an integer from 1 to 30 wherein M ² according to the oxidation number of.

In the method for manufacturing a cathode active material for a lithium secondary battery of the present invention, the transition metal composite precursor represented by Chemical Formula 2 is a composite of nickel, cobalt, and manganese, and is prepared by using a mixed solution containing a metal compound containing each metal. It can manufacture. As the metal compound containing nickel, cobalt, and manganese, any metal compound conventionally used in the preparation of the composite precursor may be used. Preferably, the metal-containing sulfate, hydrochloride, acetate, carbonate, phosphate, or the like may be used. Can be.

In addition, the metal compound containing nickel, cobalt, and manganese may be prepared using a conventionally used organic solvent, or a mixed solution in the form of an aqueous solution.

The mixed solution may be adjusted to pH 7.0 to 11.5, preferably 7.0 to 10.0 using alkali such as sodium hydroxide or ammonia.

In preparing the transition metal complex precursor represented by Formula 2, the mixed solution is maintained in the reactor for 5 to 30 hours, preferably 10 to 20 hours while maintaining the reaction temperature at 40 ℃ to 80 ℃ to react Can be. The reason why the reaction temperature of the mixed solution is high is that it is difficult to obtain a high density composite hydroxide because cobalt hydroxide precipitates in a complex salt form at a low temperature.

When the transition metal complex precursor is produced through the precipitation reaction of the mixed solution, filtration and washing are performed, and drying or vacuum drying at 80 to 200 ° C. for 10 to 30 hours or heat treatment at 200 to 800 ° C. for 5 to 20 hours is performed. desirable.

In addition, the transition metal precursor obtained by the above method is a coating process using a metal oxide represented by the formula (3), the coating process may be carried out by a dry method or a wet method.

The metal oxide used in the coating process may include one or more metals selected from the group consisting of Al, Mg, Ti, Zr, Sn, Ca, Ag, and Zn, and particularly include Ti, Zr, Al, Mg, and the like. It is desirable to improve the structural stability and electrochemical properties.

In the present invention, the coating amount of the metal oxide may be adjusted in consideration of the lithium transition metal oxide content of Formula 4, which is further mixed in the next step, and preferably 0.1 to 10 mol% based on the total amount of the transition metal complex precursor. More preferably 0.1 to 5 mol%. When a small amount of less than 0.1 mol% is added, even doping of the material is difficult, and it is difficult to exhibit effects such as structural stability. Doping in excess of 10 mol% may be structurally stable, but there is a problem that a large decrease in the initial dose per gram occurs.

In addition, the transition metal composite precursor coated as described above may be mixed with a lithium salt and a lithium transition metal oxide represented by Chemical Formula 3 to distribute the additional elements evenly inside the cathode active material and to secure structural stability and electrochemical excellence. Make sure

In the manufacturing method of the present invention, the lithium transition metal oxide includes one or more transition metals selected from the group consisting of Al, Ti, Zr, Ag, and Sn together with lithium, and particularly includes Ti, Zr, Al, Mg, and the like. It is desirable to improve structural stability and electrochemical properties. At this time, the lithium transition metal oxide may be used to include the same metal element or different metal elements as the metal element used in the coating step.

In addition, the lithium salt may be used as one or more of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, lithium hydroxide hydrate or lithium oxide, in particular, easy to handle, stable in the air and has the advantages of low price It is preferable to use lithium carbonate.

In the present invention, the process of mixing the transition metal composite precursor, the lithium salt and the lithium transition metal oxide may be performed by a dry method or a wet method.

The ratio of 1- (a + b): a: b of the transition metal composite precursor is in a content ratio of 0.5: 0.2: 0.3 to 0.4: 0.2: 0.4 or 0.33: 0.33: 0.33, more preferably 0.5: 0.2: 0.3 It can be reacted in the content ratio of, and it is preferable to prepare in the content ratio in terms of electrochemical aspects such as capacity and life characteristics.

In addition, the content of the lithium transition metal oxide may be adjusted in consideration of the coating amount of the metal oxide used in the coating step, preferably 0.1 to 10 mol%, more preferably 0.1 based on the total amount of the transition metal composite precursor. To 5 mol%. When the lithium transition metal oxide is added in a small amount of less than 0.1 mol%, even doping of the lithium transition metal oxide is difficult, and it is difficult to exhibit effects such as structural stability. On the other hand, when doped in excess of 10 mol% may be structurally stable, but has a problem that a large decrease in the initial capacity per gram occurs.

In the method for preparing a cathode active material of the present invention, a heat treatment is performed after mixing a transition metal composite precursor, a lithium salt, and a lithium transition metal oxide represented by Formula 3, preferably 750 to 990 ° C., more preferably. The heat treatment may be performed at 800 to 950 ° C. At this time, the heat treatment temperature is preferably 700 ℃ or more in order to have a crystallinity, and at 990 ℃ or more it is preferable to heat treatment at 990 ℃ or less in terms of minimizing the damage and aging of the particle size control and equipment.

On the other hand, the present invention provides a lithium secondary battery comprising a cathode active material for a lithium secondary battery represented by the formula (1) prepared by the above method. Such a lithium secondary battery of the present invention and a method of manufacturing the same will be described below in more detail through a preferred example.

The electrode of the lithium secondary battery of the present invention is prepared using the cathode active material for lithium secondary battery of the formula (1). In addition to the active material, the preparation of the electrode requires a conductive material for providing electrical conductivity and a binder that enables adhesion between the material and the current collector. The paste was prepared by stirring the conductive material at a content ratio of 1 to 30 wt% and the binder at a content ratio of 1 to 10 wt% with respect to the positive electrode active material prepared by the above method, and then applying it to a current collector of a metal material. It is compressed and then dried to prepare a laminate electrode.

The conductive material generally adds carbon black in an amount of 1 to 30% by weight based on the total weight. Products currently available as conductive materials include acetylene black series (Chevron Chemical Company or Gulf Oil Company), Ketjen Black EC series (Armak Company, Armak) Company), Vulcan XC-72 (manufactured by Cabot Company, Cabot Company), and Super P (MM Company, MMM).

Representative examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF) and / or copolymers thereof, cellulose, and the like, and representative examples of the dispersant are isopropyl alcohol and N-methylpy. Ralidone (NMP), acetone and the like.

The current collector of the metal material may be any metal that has high conductivity and is a metal that can easily adhere the paste of the material and does not have reactivity in the voltage range of the battery. Representative examples include meshes such as aluminum or stainless steel, foils, and the like.

The method of apply | coating the paste of an electrode material to a metal material can be selected from a well-known method in consideration of the characteristic of a material, or can be performed by a new suitable method. Such an example is to distribute the paste onto the current collector, and then to uniformly disperse it using a doctor blade or the like. In some cases, a method of distributing and dispersing in one process may be used. In addition, die casting, comma coating, screen printing, or the like may be selected. Alternatively, after molding on a separate substrate, it can be bonded to the current collector by pressing or lamination method.

As a method of drying the applied paste, for example, it may be dried for 1 to 3 days in a vacuum oven at 50 to 200 ℃.

In the method of constructing a lithium secondary battery using the electrode manufactured by the above method, for example, the electrode is used as an anode, a metal lithium or an alloy-based material is used as a cathode, and a separator is inserted therebetween. The membrane blocks the internal short circuit of the two electrodes and impregnates the electrolyte, and materials that can be used include polymer, glass fiber mat, kraft paper, etc.Cellgard 2400, 2300 ( Hoechest Celanese Corp.), polypropylene membrane (manufactured by Ube Industries Ltd. or Pall RAI).

The electrolyte is a system in which a lithium salt is dissolved in an organic solvent, and the lithium salt is LiClO ₄ , LiCF ₃ SO ₃ , LiAsF ₆ , LiBF ₄ , LiN (CF ₃ SO ₂ ) ₂ , LiPF ₆ , LiSCN, and LiC (CF ₃ SO _{2 3,} etc., and the organic solvent is ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), 1,2-dime 1,2-dimethoxyethane, 1,2-diethoxyethane, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran (1,2-dimethoxyethane) 2-methyltetrahydrofuran), 1,3-dioxolane (1,3-dioxolane), 4-methyl-1,3-dioxolane (4-methyl-1,3-dioxolane), diethylether, Sulfolane etc. can be used 1 type or in mixture of 2 or more types.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

The cathode active material for a lithium secondary battery of the present invention solves the problem of locally segregation or remaining on the surface when substituted with other elements (Al, Mg, Ti, Zr, Sn, Ca, Ag, Si and Zn) in the active material, Overall, it is distributed evenly inside the active material to improve the stability of the crystal lattice, that is, structural stability, thereby improving the thermal stability, and thus the effect of improving the rate characteristic, lifetime characteristic, and thermal stability at high temperature is obtained. Can be.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Example  One: TiO ₂  On the coated precursor Li ₄ Ti ₅ O ₁₂ Added Cathode active material  Produce

A metal solution of 3 M concentration, in which nickel sulfate, manganese sulfate, and cobalt sulfate were mixed in a molar ratio of 0.5: 0.3: 0.2, was charged into a reactor containing 4 L of distilled water. The temperature of the reactor was maintained at 60 ° C and the impeller speed was maintained at 700 rpm. Sodium hydroxide solution was supplied to maintain the pH at about 8, and nitrogen gas was flowed at 500 mL / min per minute to prevent oxidation while supplying ammonia solution for smooth reaction. After maintaining the residence time of 4 hours or more in the reactor was filtered and washed. The washing was carried out with ultrapure water, and the conductivity of the washed ultrapure water became less than 70 mW / m. After holding for 12 hours in a vacuum dryer 100 ℃, transition metal composite oxide in the form of bare (Bare) precursor were obtained _{(Ni 0 .5 Co 0 .2 Mn} 0 .3) (OH) 2. Figure 1a is a FE-SEM picture of the precursor obtained by the above method.

The precursor obtained by the above method was dry-coated with a spray mixer with 1 mol% TiO ₂ having an average particle diameter of 21 nm. Figure 1b is a FE-SEM picture of the precursor so coated.

1 mol% of TiO ₂ coated precursor obtained by the above method, and Li ₄ Ti ₅ O ₁₂ together with a metal oxide containing Li ₂ CO ₃ and lithium as a lithium salt dry mixed 20-30 minutes, wherein Ti The total amount of doping was set at 5 mol%.

After mixing as described above, a heat treatment was performed while baking at 900 ° C. for 10 hours or more. During firing, the temperature was raised to within 10 ℃ / min and the lower temperature was carried out by natural cooling. Li _0.97 [Li _0.03 (Ni _0.5 Co _0.2 Mn _0.3 ) _0.95 Ti _0.05 ] O ₂ was produced by Ti doping in the same manner as described above. FE-SEM photographs and XRD results of the obtained cathode active material are shown in FIGS. 2A and 3, respectively. In addition, the Ti distribution is shown in Fig. 4 through SEM-EDX analysis of the cross section of the particles prepared to determine whether Ti is evenly distributed in the cathode active material prepared according to the above method.

Example  2: TiO ₂  On the coated precursor Li ₄ Ti ₅ O ₁₂ Added Cathode active material  Produce

Using a precursor obtained in the same manner as in Example 1, dry mixing Li ₄ Ti ₅ O ₁₂ with a metal oxide containing Li ₂ CO ₃ and lithium as the precursor and a lithium salt, Ni: Co: Li _0.97 [Li _0.03 (Ni _0.33 Co _0.33 Mn _0.33 ) _0.95 Ti _0.05 ] O ₂ was obtained in the same manner as in Example 1, except that the content ratio of Mn was changed to 0.33: 0.33: 0.33. XRD results of the obtained cathode active material are shown in FIG. 3.

Example  3: TiO ₂  On the coated precursor Li ₄ Ti ₅ O ₁₂ Added Cathode active material  Produce

Li _0.97 [Li _0.03 (Ni _0.5 Co _0.2 Mn _0.3 ) _0.95 Ti in the same manner as in Example 1, except that TiO ₂ was subjected to a wet coating process using the precursor obtained in the same manner as in Example 1. _0.05 ] O ₂ was obtained. XRD results of the obtained cathode active material are shown in FIG. 3.

Example 4: TiO ₂  On the coated precursor Li ₄ Ti ₅ O ₁₂ Added Cathode active material  Produce

As in Example 1 and a lithium salt by using the precursor obtained in the same manner as the step of mixing a Li ₄ Ti ₅ O ₁₂ was performed, except that the wet-mixing process, the same method as in Example 1 Li _{0 .97 [Li 0 .03 (Ni 0 .5} Co 0 .2 Mn 0 .3) 0.95 Ti 0 .05] was obtained.

XRD results of the obtained cathode active material are shown in FIG. 3.

Example  5: TiO ₂  On the coated precursor Li ₄ Ti ₅ O ₁₂ Added Cathode active material  Produce

Li _0.97 [Li _{0.03 (} Ni _0.5 Co _0.2 Mn _0.3 )] in the same manner as in Example 1, except that the firing process was performed at 800 ° C. for 15 hours using the precursor obtained in the same manner as in Example 1. _0.95 Ti _0.05 ] O ₂ was obtained. FE-SEM photographs and XRD results of the obtained cathode active material are shown in FIGS. 2B and 3, respectively.

Example  6: ZrO ₂  On the coated precursor Li ₄ Ti ₅ O ₁₂ Added Cathode active material  Produce

A dry coating process of 1 mol% ZrO ₂ was performed on the precursor obtained by the same method as in Example 1, and the precursor coated with 1 mol% ZrO ₂ obtained by the above method, Li ₂ CO ₃ and Li _0.97 [Li _0.03 (Ni _0.5 Co _0.2 Mn _0.3 ) _0.95 Zr _0.01 Ti _0.04 ] O in the same manner as in Example 1, except that Li ₄ Ti ₅ O ₁₂ was dry mixed together with a metal oxide containing lithium. Could get ₂

Comparative example  One: TiO ₂  On the coated precursor Li ₄ Ti ₅ O ₁₂ Unadded Cathode active material  Produce

The coating process of TiO ₂ 5 mol% was applied to the precursor obtained in the same manner as in Example 1, and instead of adding Li ₄ Ti ₅ O ₁₂ in the mixing process, for accurate comparison, the lithium salt and the coated precursor the mixture the molar ratio Li / were mixed according to _{[(Ni 0 .5 Co 0 .2} Mn 0 .3) 0.95 Ti 0 .05] = 1. After mixing as above, Li [(Ni _0.5 Co _0.2 Mn _0.3 ) _0.95 Ti _0.05 ] O ₂ was obtained through a calcining process at 900 ° C. for 10 hours. FE-SEM photographs and XRD patterns of the powders obtained by the above method are shown in FIGS. 2C and 3, respectively. In addition, the Ti distribution is shown in Fig. 4 through SEM-EDX analysis of the cross section of the particles prepared to determine whether Ti is evenly distributed in the cathode active material prepared according to the above method.

Comparative Example 2: Bare Precursor Li ₄ Ti ₅ O ₁₂ Added Cathode active material  Produce

Li ₄ Ti ₅ O ₁₂ was added to the precursor obtained in the same manner as in Example 1 without performing a dry TiO ₂ coating process, and for accurate comparison, the mixing molar ratio of the lithium salt and the coated precursor was Li / They were mixed according to _{[(Ni 0 .5 Co 0 .2} Mn 0 .3) 0.95 Ti 0 .05] = 1. After mixing as described above, Li _0.96 [Li _0.04 (Ni _0.5 Co _0.2 Mn _0.3 ) _0.95 Ti _0.05 ] O ₂ was obtained through a calcination process at 900 ° C. for 10 hours. The XRD pattern of the powder obtained by the said method is shown in FIG. In addition, the Ti distribution is shown in FIG. 4 through SEM-EDX analysis of the cross-section of the particles prepared in order to confirm whether Ti is evenly distributed in the cathode active material prepared according to the above method.

Comparative example  3: bear Bare ) Precursors Li ₄ Ti ₅ O ₁₂ Without Cathode active material  Produce

Mixing molar ratio of the lithium salt and the coated precursor for accurate comparison, instead of performing a dry TiO ₂ coating process to the precursor obtained in the same manner as in Example 1, without adding Li ₄ Ti ₅ O ₁₂ in the mixing process were mixed according to a _{= 1 Li / [Ni 0 .5} Co 0 .2 Mn 0 .3]. After the mixing as described above, Li (Ni _0.5 Co _0.2 Mn _0.3 ) O ₂ was obtained through a calcination process at 900 ° C. for 10 hours. The XRD pattern of the powder obtained by the said method is shown in FIG.

Battery performance evaluation

Using a positive electrode active material for lithium secondary batteries prepared in Examples 1-6 and Comparative Examples 1 to 3 as described below to prepare a coin-type battery, and evaluated the battery characteristics.

91 wt% of the positive electrode active material for a lithium secondary battery, 6 wt% graphite as a conductive agent, 3 wt% polyvinylidene fluoride (hereinafter referred to as PVdF) as a binder, and N-methyl-2-pyrroli A positive electrode mixed slurry was prepared by dispersing in pig (N-methyl-2-pyrrolidone: hereinafter referred to as NMP). The slurry was uniformly coated and dried on aluminum foil, and then compressed into a press machine to prepare a positive electrode.

A coin-type secondary battery for a test was manufactured using the positive electrode prepared as described above, a negative electrode of lithium metal, a separator, and an electrolyte. As the non-aqueous electrolyte, a solution prepared by dissolving LiPF ₆ in a concentration of 1 mol / L in a mixed solution having a volume mixing ratio of 1: 1 of ethylene carbonate and methyl ethyl carbonate was used.

The charge-discharge characteristics, lifetime characteristics and thermal safety characteristics of the experimental lithium secondary battery manufactured as described above were measured at room temperature / high temperature, and the cut-off voltages of the charge-discharge characteristics and the lifetime characteristics were 4.3-. The charge and discharge current was set to 3.0 V, and the charge and discharge currents were measured by the constant current method under the conditions of 0.1C once, 0.2C twice, 0.5C twice, and 1C 50 times. The thermal safety evaluation was performed by vacuum-drying the active material after washing the active material in the third charge state after 0.1C twice with a cut-off voltage of 4.5-3.0 V and measuring thermal safety using TGA (Thermogravimetric Analysis). The difference of 2θ (2theta) values according to XRD measurement results before and after 1C 50 cycles of charging and discharging at high temperature was measured. At this time, the current density of charging and discharging was flowed at 1C. Each measurement result is shown in Table 1 and FIGS. 4, 5, 6 and 7.

division Doping substance Electrochemical Characteristics (room temperature 25 ℃) Electrochemical Characteristics (High Temperature 60 ℃) High temperature
cycling
order
2θ difference TiO ₂ Li ₄ Ti ₅ O ₁₂ 0.1C
Volume
(mAh / g) 1C / 0.1C
Properties
(%) 1C 50 times
life span
characteristic
(%) 0.1C
Volume
(mAh / g) 1C / 0.1C
Properties
(%) 1C 50 times
life span
characteristic
(%) Example 1 o o 168.14 90.88 99.50 186.14 93.93 97.37 0.01 Example 2 o o 159.20 90.70 98.40 168.21 93.49 97.22 0.01 Example 3 o o 167.99 91.12 99.85 185.54 94.19 96.93 0.01 Example 4 o o 168.31 91.09 99.81 184.49 93.82 97.54 0.01 Example 5 o o 166.18 90.04 97.88 183.78 92.42 92.18 0.03 Example 6 ZrO ₂ o 167.84 90.25 97.72 184.82 94.10 91.88 0.02 Comparative Example 1 o x 168.51 89.25 95.32 184.72 91.92 86.11 0.19 Comparative Example 2 x o 167.25 89.08 94.12 184.31 90.78 84.25 0.22 Comparative Example 3 x x 169.66 88.53 92.91 182.06 88.25 79.24 0.43

First, as shown in Figure 4, through the cross-sectional analysis (SEM-EDX analysis) results of the positive electrode active material of Example 1 and Comparative Examples 1 and 2 prepared according to the present invention, the positive electrode active material of Example 1 It can be seen that the Ti is evenly distributed from the inside of the particle. That is, according to the present invention, when the initial Ti-coated precursor and the Ti oxide including Li are mixed with the lithium salt and fired, it means that the Ti is evenly doped to the inside. Only segregation was observed and evenly doped (doping) to the inside was confirmed.

In addition, as can be seen from Table 1 and the results of FIGS. 5 to 7, as a result of the evaluation of the battery performance as described above, the initial capacity and the rate characteristics at room temperature are about 167 to 169 mAh / g, a large difference of about 90%. Although not shown, in Example 1, which is prepared by coating TiO ₂ on the precursor and adding Li ₄ Ti ₅ O ₁₂ to the precursor, the capacity retention ability of 99% or more is excellent.

In the case of Example 2, Ni: Co: Mn of the precursor is the most widely commercialized composition at the ratio of 1: 1: 1 (0.33: 0.33: 0.33), but there is a disadvantage in that the price of Co and the capacity are low recently. Other than this, research on other compositions is being actively conducted. However, in the case of Example 2 according to the present invention, when doping Ti in the above method, it was confirmed that the rate characteristic at high temperature is excellent, which can be estimated that the structural stability is improved.

In particular, in the case of Example 1 in which the coating process of the metal oxide was carried out by the dry method, the initial capacity and the rate characteristics and the life characteristics at the high temperature which are equivalent to those of Examples 3 and 4 which performed the coating process of the wet method were shown. Therefore, it can be seen that an excellent effect can be obtained even by the coating of the dry method without applying a wet method, which requires a high process cost.

In addition, the bare precursors prepared in Examples 1, 3 and 6 and Comparative Examples 1 to 3 have an advantage of increasing capacity as Ni content increases with Ni: Co: Mn = 5: 2: 3. However, Li is replaced with Ni sites during charge and discharge of the excessive Ni properties, and the desorption phenomenon of oxygen easily occurs due to structural instability. For this reason, as the charge / discharge of excess lithium is inserted / desorbed, the reactivity with the electrolyte increases on the surface of the positive electrode active material, the structure on the surface collapses more easily, and the resistance of charge transfer increases, thereby improving the life characteristics. It will be lowered.

However, when Ti is evenly doped inside, as in the present invention, since Ti is 4+, the bond with more oxygen is strengthened, and in particular, Li prevents the substitution of Ni sites to prevent oxygen deficiency. It is structurally very stable, such that the resistance does not increase even if the continuous insertion / desorption reaction of Li is found to improve the life characteristics.

In particular, the electrochemical properties at high temperatures show better doping effect of Ti. The initial capacity increases at high temperatures because the decrease in resistance facilitates the movement of Li ions. However, such a decrease in resistance further increases the reactivity between the positive electrode active material and the electrolyte, and thus the initial capacity is increased, but the rate characteristics, particularly the life characteristics, are significantly reduced. As described above, in order to improve the life characteristics at high temperatures, it is essential that structurally more stable materials be developed.

In the case of Example 1 according to the present invention, the initial capacity of 186 mAh / g or more shows a large difference compared to Comparative Example 3, which is about 94% at 1C, in particular, at least 97% of the lifespan characteristics, at 0.1C or more. In addition, Comparative Examples 1 and 2 show the doping effect of Ti, but it can be seen that the performance of the battery is reduced compared with Example 1. As shown in FIG. 4, as a result of the cross-sectional EDX of the particles, in contrast to Example 1 of the present invention, in Comparative Examples 1 and 2, Ti may not be evenly substituted therein and may remain in local doping or surface, according to the present invention. As in Example 1, when Ti is evenly doped inside, it is structurally stable, and it can be seen that the rate characteristics and the life characteristics, particularly at high temperatures, are greatly improved.

In order to compare the above-mentioned structural stability, XRD measurement results before and after high temperature cycling of the cathode active materials of Example 1 and Comparative Example 3 are shown in FIG. 8. This confirmed that the peak 2 theta value of about 1C 50 times at a high temperature was very constant in the case of Example 1 in which Ti was uniformly doped into the interior.

As a result of comparing the exact figures, in Example 1, the value of 2θ (2 theta) was 0.01 ° and the value of 2θ (2 theta) was very constant. On the contrary, in the case of Comparative Example 3, it was confirmed that the peak 2θ (peak 2 theta) value moved at a high angle as a result of XRD before and after the high temperature life, and also the width of the peak was increased. Increasing the width of the peak indicates a decrease in crystallinity during charging and discharging, and shifting the value of 2θ (2 theta) means that the internal structure has changed, i.e. during charging and discharging at high temperatures. It was confirmed that the internal structure changed poorly in crystallinity. In the case of Comparative Example 3, it was confirmed that the value of 2θ (2 theta) changed by 0.43 °.

In addition, in order to confirm thermal safety, the positive electrode active material was washed in 4.5 V state and dried in vacuo to measure the TGA at 600 ° C. at 10 ° C./min.

When comparing the case of Comparative Example 3 with Example 1, it was confirmed that the comparative example 3 is larger in the change in weight according to the temperature from a lower temperature. That is, it was confirmed that the weight loss is large due to the structural change such as oxygen desorption as the temperature increases, and in the case of Comparative Example 3, about 3% more weight loss occurred than in Example 1 even near the final 600 ° C. It was. That is, it shows a large difference depending on the doping method and Example 1 according to the present invention can be seen that the electrochemical properties at high temperature is improved based on the structural safety by maximizing the doping effect.

The cathode active material for lithium secondary batteries according to the present invention is electrochemically stable at high temperatures when used in lithium secondary batteries to improve the cycle life of the battery, provide a battery of high capacity, and obtain significantly improved thermal safety characteristics.

Figure 1 is a FE-SEM (ｘ5,000) photograph of the precursor prepared according to Example 1 of the present invention (Fig. 1a before TiO ₂ coating, Figure 1b after TiO ₂ coating).

2A, 2B, and 2C are FE-SEM (ｘ5,000) photographs of the positive electrode active material for a lithium secondary battery prepared according to Example 1, Example 5, and Comparative Example 1 of the present invention.

3 is an XRD pattern of a cathode active material for a lithium secondary battery manufactured according to Examples 1 to 6 and Comparative Examples 1 to 3 of the present invention.

Figure 4 is a cross-sectional FE-SEM (ｘ5,000) photograph of the positive electrode active material for lithium secondary batteries prepared according to Examples 1 and Comparative Examples 1 and 2 of the present invention and 10 Ti component EDX analysis results along the line.

Figure 5 is a graph showing the charge / discharge capacity of the C-Rate at a high temperature (60 ℃) of a lithium secondary battery including a cathode active material for a lithium secondary battery prepared according to Example 1 of the present invention.

6 is a graph showing the charge / discharge capacity of C-Rate at high temperature (60 ° C.) of a lithium secondary battery including a cathode active material for a lithium secondary battery prepared according to Comparative Example 3 of the present invention.

7 is a graph showing the life characteristics at a high temperature (60 ℃) of a lithium secondary battery including a cathode active material for a lithium secondary battery prepared according to Example 1 and Comparative Example 3 of the present invention.

8 is an XRD pattern before and after evaluating life characteristics at high temperature (60 ° C.) of a cathode active material for a lithium secondary battery manufactured according to Example 1 and Comparative Example 3 of the present invention.

FIG. 9 is a graph illustrating thermal safety of a lithium secondary battery including a cathode active material for a lithium secondary battery prepared according to Example 1 and Comparative Example 3 of the present invention.

Claims (14)

To be represented by the formula (1), nickel, manganese, and cobalt is in M ¹ to be coated on the combined transition metal complexes, the transition metal complex of the coating will, combined with the lithium and M ² cathode active material for a lithium secondary battery: [Formula 1] Li _x (Li _y (Ni _{(1- (a + b))} Co _a Mn _b ) _{(1- (z + w)))} M ¹ _z M ² _w ] O ₂ Wherein, M ¹ is at least one selected from the group consisting of Ti, and Zr, M ² is at least one selected from the group consisting of Ti, and Zr, x, y, z, w, a, b are 0.8 <x <1, 0.01 ≤ y ≤ 0.1, 0.001 ≤ z ≤ 0.1, 0.001 ≤ w ≤ 0.1, 0.002 ≤ z + w ≤ 0.2, 0.1 ≤ a <0.9 , 0.1 ≦ b <0.9, 0.2 ≦ a + b <1. The method of claim 1, A cathode active material for a lithium secondary battery having an average particle size of 1 to 20 ㎛. delete The method of claim 1, The positive electrode active material is charged and discharged at least 50 times at a current density of 0.1 C to 10 C at 50 to 80 ° C., before and after performing the charging and discharging, respectively, XRD measurement is performed, and each XRD measurement The positive electrode active material for a lithium secondary battery having a difference of 2θ (2 theta) values of 0.05 or less. A lithium secondary battery comprising the cathode active material for lithium secondary battery according to claim 1, 2 or 4. a) preparing a transition metal composite precursor represented by the following Chemical Formula 2 using a mixed solution containing a metal compound containing nickel, cobalt and manganese, b) coating the transition metal composite precursor prepared in step a) with a metal oxide represented by the following Formula 3, c) mixing the transition metal composite precursor coated in step b) with a lithium salt and a lithium transition metal oxide represented by the following Formula 4, and d) heat-treating the metal oxide mixed in step c) Method for producing a cathode active material for a lithium secondary battery according to claim 1 comprising:  [Formula 2] Ni _{(1- (a + b))} Co _a Mn _b (OH) ₂ (3) M ¹ _c O _d [Formula 4] Li _e M ² _f O _g Wherein, M ¹ is at least one selected from the group consisting of Ti, and Zr, M ² is at least one selected from the group consisting of Ti, and Zr, a and b are each 0.1 ≦ a <0.9, 0.1 ≦ b <0.9, 0.2 ≦ a + b <1, c and d are each an integer of 1 to 30 depending on the number of oxidation of M ¹ , e, f, g are each an integer of 1 to 30 depending on the oxidation number of the M ² . The method of claim 6, The mixed solution of step a) is a method of producing a positive electrode active material for lithium secondary batteries having a pH of 7.0 to 11.5. The method of claim 6, Reaction time of the mixed solution in the step a) is a method for producing a positive electrode active material for lithium secondary batteries. The method of claim 6, Lithium further comprises a drying or vacuum drying process for 10 to 30 hours at 80 to 200 ℃, or a heat treatment process for 5 to 20 hours at 200 to 800 ℃ after preparing the transition metal composite precursor in step a) Method for producing a cathode active material for secondary batteries. The method of claim 6, The coating process of step b) is a method for producing a cathode active material for a lithium secondary battery that is carried out by a dry method or a wet method. The method of claim 6, The lithium salt of step c) is at least one selected from the group consisting of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, lithium hydroxide hydrate, and lithium oxide. The method of claim 6, The mixing process of step c) is a method for producing a cathode active material for a lithium secondary battery that is carried out by a dry method or a wet method. The method of claim 6, The step d) is a method of manufacturing a cathode active material for a lithium secondary battery consisting of heat treatment at 700 to 990 ℃. A lithium secondary battery comprising a cathode active material for a lithium secondary battery produced by the method according to any one of claims 6 to 13.

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