JP6191351B2 - Positive electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same - Google Patents

Description

  The present invention relates to a positive electrode active material for a non-aqueous electrolyte secondary battery. In particular, the present invention relates to a positive electrode active material having a significantly improved charge / discharge capacity and improved cycle characteristics.

  In recent years, with the widespread use of portable electronic devices such as mobile phones and notebook computers, development of small and lightweight secondary batteries having high energy density is strongly desired. In addition, development of a high output secondary battery is strongly desired as a battery for electric vehicles including hybrid vehicles.

  As a secondary battery satisfying such a requirement, there is a non-aqueous electrolyte secondary battery represented by a lithium ion secondary battery. A lithium ion secondary battery is composed of a negative electrode, a positive electrode, an electrolyte, and the like, and a material capable of desorbing and inserting lithium is used as an active material of the negative electrode and the positive electrode.

As a positive electrode active material of a lithium ion secondary battery, a lithium cobalt composite oxide (LiCoO ₂ ) having a layered structure that is relatively easy to synthesize is mainly put into practical use. In addition, a layered lithium nickel composite oxide (LiNiO ₂ ) using nickel, which is cheaper than cobalt, and a spinel lithium manganese composite oxide (LiMn ₂ O ₄ ) using manganese have been put into practical use. . In the lithium transition metal composite oxide having a layered structure, a lithium nickel cobalt manganese composite oxide (for example, LiNi _0.333 Co _0.333 Mn _0.333 O ₂ ) using a plurality of transition metals has been put into practical use. . When these lithium transition metal composite oxides are used as the positive electrode active material, a 4V class non-aqueous electrolyte secondary battery can be realized.

  With respect to lithium transition metal composite oxides, techniques for increasing the ratio of lithium to transition metal elements according to the purpose have been proposed.

  In paragraph 0030 of Patent Document 1, it is considered that the lithium ratio is slightly higher than the stoichiometric ratio, thereby suppressing the disorder of the crystal structure, smoothing the diffusion of lithium ions, and improving the rate characteristics and output characteristics. Has been. On the other hand, if the lithium ratio is too high, there is a possibility that a heterogeneous phase may be generated or battery performance may be lowered.

Patent Document 2 discloses that in Li [Li _x (Ni _1/2 Mn _1/2 ) _1-x ] O ₂ , when lithium becomes excessive (x is larger than 0), the heat of the active material in an overcharged state is disclosed. On the other hand, it is described that the electrical stability of the active material is lowered when x is too large (x> 0.3).

  Further, among so-called lithium transition metal composite oxides having an increased lithium ratio, what is called a so-called solid solution system has attracted attention.

In paragraph 0005 of Patent Document 3, it is disclosed that a solid solution of LiMO ₂ (M is a metal element) and Li ₂ MnO ₃ can exhibit a discharge capacity of 200 mAh / g.

In Patent Document 4, a potential region of 4.3 V or less is obtained by dissolving three components of Li [Li _1/3 Mn _2/3 ] O ₂ , LiCoO ₂ and LiNi _1/2 Mn _1/2 O _{2 in} a specific range ratio. Techniques for increasing the discharge capacity in the field have been proposed.

  On the other hand, with respect to the lithium transition metal composite oxide, a technique for further containing tungsten or the like according to the purpose has been proposed.

  Patent Document 5 proposes a technique in which a part of nickel in lithium nickelate is replaced with tungsten or the like to improve capacity and cycle characteristics and to improve reproducibility in synthesis. However, there is no description about substitution with cobalt or manganese.

  Patent Document 6 proposes a technique in which a part of manganese of lithium-excess lithium nickel manganate is replaced with tungsten or the like to increase the energy density. According to paragraph 0017, substitution of manganese with a tetravalent or higher element facilitates a change in the valence of manganese in an excess lithium state, prevents a decrease in conductivity, and results in an increase in energy density.

  Patent Document 7 proposes to use nickel cobalt lithium manganate containing tungsten as a positive electrode active material as one of means for reducing battery resistance and improving output characteristics. The amount of lithium in claim 1 is in a wide range including a state in which lithium is excessive, but what is specifically disclosed is a range in which lithium is up to 1.05 times the molar ratio of all transition metals. Moreover, there is no description about making lithium excessive.

JP 2007-214138 A International Publication No. 02/0708105 Pamphlet JP 2011-204563 A JP 2008-146392 A Japanese Patent Laid-Open No. 06-283174 JP 2005-235628 A JP 2008-243448 A

  The lithium transition metal composite oxide having a layer structure with an excess of lithium has a high charge / discharge capacity, but tends to have slightly poor cycle characteristics. In addition, since lithium is present in the transition metal layer, the influence of the ratio of the transition metal is often different from that of a normal lithium transition metal composite oxide. For this reason, in the prior art, it has been impossible to achieve both charge / discharge capacity and cycle characteristics that are high enough to be used for an electric vehicle such as a hybrid vehicle. Also, the volume energy density is not of a level that can be used for electric vehicles.

  The present invention has been made in view of the above circumstances. An object of the present invention is to provide a positive electrode active material satisfying a high charge / discharge capacity, cycle characteristics, and energy density. Another object of the present invention is to provide a non-aqueous electrolyte secondary battery having a high volumetric energy density and good cycle characteristics that can be applied to electric vehicles and the like.

In order to achieve the above object, the present inventors have conducted intensive studies and have completed the present invention. The present inventors have used a lithium transition metal composite oxide in which tungsten is contained in a lithium transition metal composite oxide of a specific range of solid solution system as a positive electrode active material, so that a lithium-excess layered lithium transition metal composite oxide It was found that the cycle characteristics can be improved without impairing the high charge / discharge capacity. Moreover, it discovered that the volume energy density was also improved at this time. The positive electrode active material of the present invention has a general formula xLi ₂ MnO _3. (1-x) LiNi _a Co _1-ab Mn _b O ₂ (where 0.3 ≦ x ≦ 0.7, 0 <a ≦ 0. 60, 0 <b ≦ 0.50), wherein tungsten is contained in an amount of 0.1 mol% to 5.0 mol% in the lithium transition metal composite oxide.

  The tungsten is preferably present as a subphase of the lithium transition metal composite oxide. In particular, the subphase preferably contains a composite oxide of lithium and tungsten.

The positive electrode active material preferably has a tap density of 1.7 g / cm ³ or more.

  The non-aqueous electrolyte secondary battery of the present invention is characterized by using the positive electrode active material of the present invention.

  Since the positive electrode active material of the present invention has the above characteristics, it can satisfy all of high charge / discharge capacity, cycle characteristics, and volume energy density. Therefore, by using the positive electrode active material of the present invention for the positive electrode, a non-aqueous electrolyte secondary battery having a high volumetric energy density and improved cycle characteristics can be obtained.

FIG. 1 is a schematic view of an example of the form of the positive electrode active material of the present invention.

  Hereinafter, the positive electrode active material of the present invention will be described in detail.

The positive electrode active material of the present invention has a composition represented by the general formula: xLi ₂ MnO _3. (1-x) LiNi _a Co _1-ab Mn _b O ₂ (provided that 0.3 ≦ x ≦ 0.7, 0 <a In the lithium transition metal composite oxide represented by ≦ 0.60, 0 <b ≦ 0.50), tungsten is contained in an amount of 0.1 mol% to 5.0 mol%.

  x is 0.3 ≦ x ≦ 0.7. When x is smaller than 0.3 or larger than 0.7, the discharge capacity is significantly decreased, which is not preferable. A preferred range is 0.3 ≦ x ≦ 0.6, and a more preferred range is 0.4 ≦ x ≦ 0.6.

Regarding cobalt, nickel, and manganese in LiNi _a Co _1-a-b Mn _b O ₂ , nickel and manganese are essential, so that the ratio of any one of the three elements does not protrude and the charge / discharge capacity is increased. It is necessary to balance the cycle characteristics and ease of manufacture. Based on this, 0 <a ≦ 0.60 and 0 <b ≦ 0.50. Preferably, 0.20 ≦ a ≦ 0.50 and 0.20 ≦ b ≦ 0.50. In particular, a = b is more preferable because a lithium transition metal composite oxide having a uniform composition distribution and a small amount of unreacted raw materials can be easily obtained.

  If the content of tungsten is too small, the effect of improving the cycle characteristics cannot be found, and if it is too large, the volume energy density is lowered. If it is 0.1 mol% or more and 5.0 mol% or less with respect to a main component, high volume energy density and cycling characteristics can be made compatible. More preferably, it is 0.5 mol% or more and 2.0 mol% or less. Within this range, load characteristics are also improved.

  It is preferable that at least a part of tungsten in the positive electrode active material exists as a subphase of the lithium transition metal composite oxide. The other part may be dissolved in a transition metal layer such as nickel. FIG. 1 is an example of a form in which a part of tungsten is a subphase of a lithium transition metal composite oxide. In FIG. 1, the positive electrode active material 1 includes a secondary particle 11 in which primary particles 111 of a lithium transition metal composite oxide are aggregated and a subphase 12. Note that the lithium transition metal composite oxide in the positive electrode active material of the present invention may be in the form of only primary particles or a form in which primary particles and secondary particles are mixed. The subphase 12 exists in a region including the surface of the primary particle 111, and when the lithium transition metal composite oxide forms the secondary particle 11, as a result, the subphase 12 exists in a region including the interface of the primary particle 111. Will be.

The solid solution tungsten improves the lithium ion conductivity of the positive electrode active material and makes it difficult for the capacity to decrease even when a high current density is applied. That is, load characteristics are improved. On the other hand, tungsten present in the subphase prevents the transition metal from eluting from the positive electrode active material during charge and discharge, and contributes to improvement of cycle characteristics. Tungsten present in the subphase can take various forms, but at least a part thereof is preferably in the form of a composite oxide of lithium and tungsten. This is because such a subphase also contributes to the improvement of lithium ion conductivity and the load characteristics are improved. Examples of the composite oxide of lithium and tungsten include Li ₂ WO ₄ and Li ₄ WO _5, but are not particularly limited. When present as a composite oxide of lithium and tungsten, this subphase is water-soluble, and its presence can be confirmed by the method described later.

The smaller the specific surface area of the positive electrode active material, the more preferable the transition metal is prevented from being eluted. Preferably it is 3.0 m < ² > / g or less, More preferably, it is 2.0 m < ² > / g or less, More preferably, it is 1.7 m < ² > / g or less. When the elution of the transition metal is prevented, the adverse effect on the negative electrode and the like is improved, and as a result, the cycle characteristics of the entire battery are improved.

The tap density of the positive electrode active material is preferably 1.7 g / cm ³ or more because the volume energy density is sufficiently high. More preferably, it is 1.8 g / cm ³ or more. There is no particular upper limit as long as the positive electrode active material can be taken as powder. Actually, the upper limit is about 2.5 g / cm ³ .

[Production of positive electrode active material]
Hereinafter, the manufacturing method of the positive electrode active material of this invention is demonstrated. The positive electrode active material of the present invention can be synthesized by appropriately using known methods, but each step will be described in detail below.

[Mixing process]
A raw material compound that decomposes into an oxide at a high temperature is mixed in accordance with the target composition (so-called dry method), or a raw material compound that is soluble in a solvent is dissolved in a solvent, and the precursor is prepared by adjusting the temperature, adjusting the pH, or adding a complexing agent The mixed raw material is appropriately adjusted by causing body precipitation (so-called coprecipitation method) or combining these methods. As raw materials that decompose into oxides at high temperatures, oxides, hydroxides, nitrates, sulfates, carbonates, and the like of each element can be used. For example, lithium carbonate, lithium nitrate, lithium hydroxide, or the like can be used as the lithium source. When lithium hydroxide is used, it is preferable because the proportion of tungsten existing as a subphase of the lithium transition metal composite oxide is increased with respect to tungsten in the obtained positive electrode active material. Nickel sources include nickel carbonate, nickel sulfate, nickel hydroxide, nickel oxide, nickel peroxide, etc., and cobalt sources include cobalt oxide, niobium trioxide, tricobalt tetroxide, cobalt hydroxide, cobalt nitrate, cobalt sulfate. As the manganese source, manganese dioxide, nimanganese trioxide, trimanganese tetroxide, manganese carbonate, manganese nitrate, manganese sulfate and the like can be mentioned. Examples of the tungsten source include tungsten dioxide, tungsten trioxide, lithium tungstate, ammonium tungstate, and an organic compound of tungstic acid. Note that raw material compounds of all elements including tungsten are mixed in this mixing step.

  The mixing ratio of the respective raw materials may be determined according to the target composition of the lithium transition metal composite oxide and the tungsten content. However, if the tungsten content is increased, lithium is slightly excessive. By mixing in this way, in the tungsten in the positive electrode active material obtained, the proportion of tungsten existing as a subphase of the lithium transition metal composite oxide can be increased.

  When obtaining a composite oxide by the coprecipitation method, the reaction conditions are appropriately adjusted so that the obtained composite oxide becomes dense secondary particles. If it is dense, the tap density of the obtained positive electrode active material can be increased and the specific surface area can be decreased. The density of the complex oxide is sufficient to be determined visually by a scanning electron microscope (SEM). You may judge by measuring the tap density of complex oxide.

[Baking process]
The mixed raw material obtained in the mixing step is fired. The firing temperature is appropriately adjusted according to the purpose because the specific surface area of the positive electrode active material to be obtained is low if it is high. If the firing temperature is too low, the reaction between lithium and other elements will be insufficient, or a sufficient crystallite size will not be obtained. If it is too high, lithium will volatilize or sintering will tend to occur. So be careful. In consideration of these, although it depends on the target composition, generally 700 ° C. or more and 1100 ° C. or less are preferable. More preferably, it is 800 degreeC or more and 1000 degrees C or less. More preferably, it is 850 degreeC or more and 950 degrees C or less. A firing time of 10 hours or more is sufficient as a time for maintaining the maximum temperature.

[Post-processing]
After firing, if necessary, treatments such as crushing, pulverization, and dry sieving are performed to obtain the positive electrode active material of the present invention.

  Hereinafter, more specific examples will be described in Examples.

A nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.167 / 0.167 / 0.667) having a tap density of 1.3 g / cm ³ is obtained by a coprecipitation method. The composite oxide, lithium hydroxide, and tungsten oxide (VI) are mixed so that the mixing ratio thereof is Li: (Ni + Co + Mn): W = 1.50: 1.00: 0.005. Bake at 10 ° C. for 10 hours. 0.5 mol% of tungsten is contained in the lithium transition metal composite oxide expressed by 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co _0.33 Mn _0.33 O ₂ after dispersion treatment after firing A positive electrode active material is obtained.

The composition is 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co ₀ except that the mixing ratio is Li: (Ni + Co + Mn): W = 1.51: 1.00: 0.010 and the composition is 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co ₀ A positive electrode active material in which 1.0 mol% of tungsten is contained in the lithium transition metal composite oxide represented by _.33 Mn _0.33 O ₂ is obtained.

The composition was 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co ₀ except that the mixing ratio was Li: (Ni + Co + Mn): W = 1.53: 1.00: 0.020, and the composition was 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co ₀ A positive electrode active material in which 2.0 mol% of tungsten is contained in the lithium transition metal composite oxide represented by _.33 Mn _0.33 O ₂ is obtained.

[Comparative Example 1]
Lithium transition metal composite having the same composition as in Example 1 except that tungsten oxide (VI) is not mixed and the composition represented by 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co _0.33 Mn _0.33 O ₂ An oxide is obtained.

Lithium transition metal composite oxidation in the same manner as in Example 2 except that the firing temperature is 800 ° C. and the composition is represented by 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co _0.33 Mn _0.33 O ₂ A positive electrode active material containing 1.0 mol% tungsten is obtained.

[Comparative Example 2]
Lithium transition metal composite oxide represented by the composition 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co _0.33 Mn _0.33 O ₂ in the same manner as in Comparative Example 1 except that the firing temperature is 800 ° C. Get.

A nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.200 / 0.200 / 0.600) having a tap density of 1.3 g / cm ³ is obtained by a coprecipitation method. The composite oxide, lithium hydroxide, and tungsten oxide (VI) were mixed so that the mixing ratio was Li: (Ni + Co + Mn): W = 1.40: 1.00: 0.005, and the atmosphere was Bake at 900 ° C. for 10 hours. 0.5 mol% of tungsten is contained in the lithium transition metal composite oxide having a composition of 0.4Li ₂ MnO ₃ .0.6LiNi _0.33 Co _0.33 Mn _0.33 O ₂ after dispersion treatment after firing. The positive electrode active material is obtained.

The composition was 0.4 Li ₂ MnO ₃ .0.6LiNi _0.33 Co _{0 in the same} manner as in Example 5 except that the mixing ratio was Li: (Ni + Co + Mn): W = 1.41: 1.00: 0.010. A positive electrode active material in which 1.0 mol% of tungsten is contained in a lithium transition metal composite oxide represented by _.33 Mn _0.33 O ₂ is obtained.

The composition was 0.4 Li ₂ MnO ₃ .0.6LiNi _0.33 Co ₀ except that the mixing ratio was Li: (Ni + Co + Mn): W = 1.43: 1.00: 0.020 and the same as in Example 5. A positive electrode active material in which 2.0 mol% of tungsten is contained in the lithium transition metal composite oxide represented by _.33 Mn _0.33 O ₂ is obtained.

The composition ratio was 0.4Li ₂ MnO ₃ .0.6LiNi _0.33 Co ₀ except that the mixing ratio was Li: (Ni + Co + Mn): W = 1.46: 1.00: 0.040. obtaining a positive electrode active material of tungsten is contained 4.0 mol% in the lithium transition metal composite oxide represented by _.33 Mn _0.33 O _2.

[Comparative Example 3]
Lithium transition metal composite oxidation represented by the composition 0.4Li ₂ MnO ₃ .0.6LiNi _0.33 Co _0.33 Mn _0.33 O ₂ in the same manner as in Example 5 except that tungsten oxide (VI) was not mixed. Get things.

[Comparative Example 4]
Lithium transition metal composite oxidation in the same manner as in Comparative Example 3 except that the firing temperature is 800 ° C. and the composition is represented by 0.4Li ₂ MnO ₃ .0.6LiNi _0.33 Co _0.33 Mn _0.33 O ₂ Get things.

Lithium transition metal having the same composition as in Example 7 except that the lithium compound to be mixed is lithium carbonate, and the composition is represented by 0.4Li ₂ MnO ₃ .0.6LiNi _0.33 Co _0.33 Mn _0.33 O ₂ A positive electrode active material containing 2.0 mol% of tungsten in the composite oxide is obtained.

[Comparative Example 5]
Lithium transition metal having the same composition as Comparative Example 3 except that the lithium compound to be mixed is lithium carbonate, and the composition is represented by 0.4Li ₂ MnO ₃ .0.6LiNi _0.33 Co _0.33 Mn _0.33 O ₂ A composite oxide is obtained.

By the coprecipitation method, a nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.167 / 0.167 / 0.667) having a tap density of 1.0 g / cm ³ is obtained. The composite oxide, lithium hydroxide, and tungsten oxide (VI) were mixed so that the mixing ratio was Li: (Ni + Co + Mn): W = 1.51: 1.00: 0.010, and the atmosphere was Bake at 900 ° C. for 10 hours. 1.0 mol% of tungsten is contained in the lithium composite oxide expressed by 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co _0.33 Mn _0.33 O ₂ after dispersion treatment after firing. A positive electrode active material is obtained.

The composition was 0.5 Li ₂ MnO ₃ .0.5LiNi _0.33 Co ₀ except that the mixing ratio was Li: (Ni + Co + Mn): W = 1.53: 1.00: 0.020, and the composition was 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co ₀ A positive electrode active material in which 2.0 mol% of tungsten is contained in the lithium composite oxide represented by _.33 Mn _0.33 O ₂ is obtained.

[Comparative Example 6]
A lithium transition metal composite having the same composition as in Example 10 except that tungsten oxide (VI) is not mixed, and the composition represented by 0.5Li ₂ MnO ₃ .0.5LiNi _0.33 Co _0.33 Mn _0.33 O ₂ An oxide is obtained.

A nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.230 / 0.230 / 0.540) having a tap density of 1.3 g / cm ³ is obtained by a coprecipitation method. The composite oxide, lithium hydroxide, and tungsten oxide (VI) were mixed so that the mixing ratio was Li: (Ni + Co + Mn): W = 1.30: 1.00: 0.020, and the atmosphere was Bake at 900 ° C. for 10 hours. After the firing, the lithium transition metal composite oxide represented by 0.3Li ₂ MnO ₃ .0.7LiNi _0.33 Co _0.33 Mn _0.33 O ₂ is dispersed and treated with 2.0 mol% of tungsten. The positive electrode active material is obtained.

A nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.130 / 0.130 / 0.740) having a tap density of 1.3 g / cm ³ is obtained by a coprecipitation method. The composite oxide, lithium hydroxide, and tungsten oxide (VI) were mixed so that the mixing ratio was Li: (Ni + Co + Mn): W = 1.60: 1.00: 0.020, and the atmosphere was Bake at 900 ° C. for 10 hours. The lithium transition metal composite oxide having a composition of 0.6Li ₂ MnO ₃ .0.4LiNi _0.33 Co _0.33 Mn _0.33 O ₂ after dispersion treatment after firing contains 2.0 mol% of tungsten. The positive electrode active material is obtained.

A nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.090 / 0.090 / 0.820) having a tap density of 1.3 g / cm ³ is obtained by the coprecipitation method. The composite oxide, lithium hydroxide, and tungsten oxide (VI) were mixed so that the mixing ratio was Li: (Ni + Co + Mn): W = 1.70: 1.00: 0.020, and the atmosphere was Bake at 900 ° C. for 10 hours. After the firing, the lithium transition metal composite oxide represented by 0.7Li ₂ MnO ₃ .0.3LiNi _0.33 Co _0.33 Mn _0.33 O ₂ is dispersed and treated with 2.0 mol% of tungsten. The positive electrode active material is obtained.

A nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.150 / 0.300 / 0.550) having a tap density of 1.3 g / cm ³ is obtained by a coprecipitation method. The composite oxide, lithium hydroxide, and tungsten oxide (VI) were mixed so that the mixing ratio was Li: (Ni + Co + Mn): W = 1.40: 1.00: 0.020, and the atmosphere was Bake at 900 ° C. for 10 hours. The lithium transition metal composite oxide having a composition of 0.4Li ₂ MnO ₃ .0.6LiNi _0.25 Co _0.50 Mn _0.25 O ₂ after dispersion treatment after firing contains 2.0 mol% of tungsten. The positive electrode active material is obtained.

A nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.090 / 0.420 / 0.490) having a tap density of 1.3 g / cm ³ is obtained by the coprecipitation method. The composite oxide, lithium hydroxide, and tungsten oxide (VI) were mixed so that the mixing ratio was Li: (Ni + Co + Mn): W = 1.40: 1.00: 0.020, and the atmosphere was Bake at 900 ° C. for 10 hours. The lithium transition metal composite oxide having a composition of 0.4 Li ₂ MnO ₃ .0.6LiNi _0.15 Co _0.70 Mn _0.15 O ₂ after dispersion treatment after firing contains 2.0 mol% of tungsten. The positive electrode active material is obtained.

A nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.300 / 0.120 / 0.580) having a tap density of 1.3 g / cm ³ is obtained by a coprecipitation method. The composite oxide, lithium hydroxide, and tungsten oxide (VI) were mixed so that the mixing ratio was Li: (Ni + Co + Mn): W = 1.40: 1.00: 0.020, and the atmosphere was Bake at 900 ° C. for 10 hours. The lithium transition metal composite oxide having a composition of 0.4Li ₂ MnO ₃ .0.6LiNi _0.50 Co _0.20 Mn _0.30 O ₂ after dispersion treatment after firing contains 2.0 mol% of tungsten. The positive electrode active material is obtained.

A nickel cobalt manganese composite oxide (Ni / Co / Mn = 0.360 / 0.120 / 0.520) having a tap density of 1.3 g / cm ³ is obtained by a coprecipitation method. The composite oxide, lithium hydroxide, and tungsten oxide (VI) were mixed so that the mixing ratio was Li: (Ni + Co + Mn): W = 1.40: 1.00: 0.020, and the atmosphere was Bake at 900 ° C. for 10 hours. The lithium transition metal composite oxide represented by the composition 0.4Li ₂ MnO ₃ .0.6LiNi _0.60 Co _0.20 Mn _0.20 O ₂ after dispersion treatment after firing contains 2.0 mol% of tungsten. The positive electrode active material is obtained.

[Comparative Example 7]
By the coprecipitation method, a cobalt manganese complex oxide (Co / Mn = 0.600 / 0.400) having a tap density of 1.3 g / cm ³ is obtained. The cobalt oxide, lithium hydroxide, and tungsten oxide (VI) are mixed so that the mixing ratio thereof is Li: (Ni + Co + Mn): W = 1.40: 1.00: 0.020. Bake at 10 ° C. for 10 hours. Composition fired dispersion treatment to obtain a positive electrode active material of tungsten is contained 2.0 mol% in the lithium transition metal composite oxide represented by 0.4Li ₂ MnO ₃ · 0.6LiCoO _2.

[Visual evaluation of positive electrode active material]
In Examples 1 to 18 and Comparative Examples 1 to 7, it can be confirmed by SEM that secondary particles in which primary particles are aggregated are formed.

[Evaluation of positive electrode active material]
About Examples 1-18 and Comparative Examples 1-7, a positive electrode active material is evaluated in the following ways.

[Center particle size of secondary particles]
In the laser diffraction method, the 50% integrated value (D50) in the volume frequency distribution is set as the center particle size of the secondary particles.

[Tap density]
After 20 g of the sample is put into the receiver and the receiver is tapped 150 times, the volume is measured, and the obtained density is defined as the tap density.

[Specific surface area]
The value measured by the BET method is taken as the specific surface area.

[Elemental analysis]
Elemental analysis of the positive electrode active material or the like is performed by ICP-AES, and the composition and tungsten content of the lithium transition metal composite oxide in the positive electrode active material are obtained.

[Tungsten present in water-soluble subphase]
The positive electrode active material is dispersed in pure water and stirred at room temperature for a predetermined time. After completion of the stirring, the liquid is separated and elemental analysis of the filtrate is performed. From the result of elemental analysis of the filtrate, the amount of tungsten present in the subphase as a composite oxide of lithium and tungsten can be known. In the positive electrode active material, the ratio of tungsten present in the subphase as a composite oxide of lithium and tungsten to the total tungsten in the positive electrode active material is W _ws .

[Production of secondary battery]
A secondary battery for evaluation is produced in the following manner.

[For cycle characteristics evaluation]
A paste is prepared by kneading 90% by weight of a positive electrode active material powder, 5% by weight of carbon powder as a conductive agent, and a normal methylpyrrolidone (NMP) solution of polyvinylidene fluoride (PVDF) (5% by weight as PVDF). It adjusts, this is apply | coated to the electrical power collector which consists of aluminum foil, it is made to dry and shape | molds in plate shape, and it is set as a positive electrode plate.

  A carbon material is used as the negative electrode active material. A paste was prepared by kneading 97.5% by weight of the negative electrode active material powder and 2.5% by weight of carboxymethylcellulose (CMC) aqueous solution, and applying this to a current collector made of copper foil, followed by drying, To form a negative electrode plate.

Ethylene carbonate (EC) and methyl ethyl carbonate (MEC) are mixed at a volume ratio of 3: 7. Lithium hexafluorophosphate (LiPF ₆ ) is dissolved as an electrolyte in the obtained mixed solvent to prepare a nonaqueous electrolytic solution having a concentration of 1 mol / L.

  A porous polypropylene film is used as the separator.

  A lead electrode is attached to the positive electrode plate and the negative electrode plate, and the positive electrode, the separator, and the negative electrode are stacked in this order. These are stored in a laminate pack, an electrolyte solution is injected, and the laminate pack is sealed to obtain a laminate type secondary battery. This is used for battery cycle evaluation.

[For charge / discharge capacity evaluation]
A positive electrode plate is produced in the same manner as the battery for evaluating cycle characteristics.

  Metal lithium is used as the negative electrode active material and is molded into a thin sheet to form a negative electrode plate.

  The electrolyte solution is adjusted in the same manner as the cycle characteristic evaluation battery except that MEC is diethyl carbonate.

  The same separator as the battery for evaluating cycle characteristics is used.

  A lead electrode is attached to the positive electrode plate, and the positive electrode, the separator, and the negative electrode are sequentially accommodated in the container. The negative electrode is electrically connected to a stainless steel container bottom, and the container bottom serves as a negative electrode terminal. The separator is fixed by the side of the container made of Teflon (registered trademark). The tip of the positive lead electrode is led out of the container and becomes a positive terminal. The positive and negative terminals are electrically insulated by the container side. After storage, the electrolyte is injected and sealed with a stainless steel container lid to obtain a sealed test battery. This is used for evaluation of charge / discharge capacity.

[Evaluation of battery characteristics]
Using the secondary battery for evaluation described above, battery characteristics are evaluated in the following manner for Examples 1 to 18 and Comparative Examples 1 to 7.

[Cycle characteristic evaluation]
Aging is performed with a weak current so that the electrolyte is sufficiently absorbed into the positive electrode and the negative electrode. In an environment of 25 ° C., constant current and constant voltage charging and constant current discharging are repeated 100 times at a full charge voltage of 4.5 V, a discharge voltage of 2.0 V, and a current density of 1.26 mA / cm ² with respect to the positive electrode. The ratio of the discharge capacity at the 100th time to the discharge capacity at the 1st time is calculated and set as the capacity maintenance rate S. Further, the negative electrode and the separator are taken out from the laminate pack, and the surface precipitate is dissolved in the acid. The obtained solution is subjected to elemental analysis by ICP, and the amount of transition metal eluted from the positive electrode active material is determined. The high capacity retention ratio S and the small amount of transition metal elution Me are indicators for good cycle characteristics.

[Initial charge capacity]
Constant current and constant voltage at a full charge voltage of 4.6 V and a charge rate of 0.2 C (1 C: current density at which discharge is completed in 1 hour from a fully charged state; 1 C = about 260 mAh / g in the evaluation battery in this specification) The charged capacity (charge termination condition is rate 0.008C) is defined as an initial charge capacity Q _c0 .

[Initial discharge capacity]
After charging to full-charge voltage 4.6 V, discharge voltage 2.0 V, the constant current discharged capacity at a discharge rate 0.05C and initial discharge capacity _{Q d0.}

[Initial charge / discharge efficiency]
A ratio (= Q _d0 / Q _c0 ) of the initial discharge capacity Q _{d0 to} the initial charge capacity Q _{c0 is defined} as an initial charge / discharge efficiency E _co .

[Load discharge capacity]
After constant current and constant voltage charging at a full charge voltage of 4.6 V and a charge rate of 0.2 C, constant current discharge is performed in the order of a discharge voltage of 2.0 V, discharge rates of 0.2 C, 0.5 C, 1 C, and 2 C, respectively. Discharge rate of the discharge capacity when the 2C and load discharge capacity Q _L. That the load discharge capacity Q _L is high, it means that the load characteristic is good. Further, regarding the battery voltage when the discharge rate is 2C, the time average is defined as an average voltage E.

[Volume energy density]
The product of the load discharge capacity Q _L , the average voltage E and the tap density is defined as a volume energy density T.

  Regarding Examples 1 to 11 and Comparative Examples 1 to 6, the production conditions are shown in Table 1, the characteristics of the positive electrode active material are shown in Table 2, the charge / discharge capacities are shown in Table 4, the cycle characteristics are shown in Table 6, the load characteristics and the volume energy. The densities are shown in Table 8, respectively. Moreover, about Example 3, 7, 12-18 and the comparative example 7, it shows in Table 1, 3, 5, 7, 9 similarly, respectively.

From Table 6, it can be seen that the cycle characteristics tend to be improved when the content of tungsten is large. In addition, when combined with the results in Table 4, it can be seen that if the tungsten content is up to about 4.0 mol%, the capacity retention rate is high and more preferable. Further, when Examples 2, 3 and Comparative Example 1, and Examples 10, 11 and Comparative Example 6 are combined with the results shown in Table 2, the cycle characteristics tend to be better when the specific surface area is lower. It turns out that the effect is remarkable at 7 m < ² > / g or less.

From Examples 3 and 9 in Tables 1 and 2, it can be seen that when the lithium raw material of the positive electrode active material is lithium hydroxide, the proportion of tungsten present in the subphase as a composite oxide of lithium and tungsten is high. . Further, when combined with the results in Table 8, it can be seen that the load characteristics are improved when the proportion of tungsten in which the subphase is present is high. It can also be seen that when the tap density is high, both load characteristics and volume energy density are good. In particular, if the tap density is 1.7 g / cm ³ or more, the volume energy density can be set to about 1200 Wh / L, which is preferable for an electric vehicle.

From Table 5, it can be seen that the initial charge capacity increases as x increases, but the initial discharge capacity reaches a maximum around 0.5. Considering the initial charge / discharge efficiency, it can be said that the preferable range of x is 0.3 ≦ x ≦ 0.6, and the more preferable range is 0.4 ≦ x ≦ 0.6. On the other hand, from Table 7 and Table 9, when a = b, the cycle characteristics and the volume energy density tend to be high, and the ratios of cobalt, nickel, and manganese in LiNi _a Co _1-ab Mn _b O ₂ are the same. It can be seen that it is particularly high.

  The positive electrode active material for a non-aqueous electrolyte secondary battery of the present invention can be used for a non-aqueous electrolyte secondary battery. The nonaqueous electrolyte battery of the present invention can be used as a power source for mobile devices such as mobile phones, notebook computers, digital cameras, and batteries for electric vehicles.

DESCRIPTION OF SYMBOLS 1 Positive electrode active material 11 Secondary particle of lithium transition metal complex oxide 111 Primary particle of lithium transition metal complex oxide 12 Subphase

Claims (14)

Formula _{xLi 2 MnO 3 · (1-} x) LiNi a Co 1-a-b Mn b O 2 ( where 0.
3 ≦ x ≦ 0.7, 0 <a ≦ 0.60, 0 <b ≦ 0.50), tungsten is contained in an amount of 0.1 mol% to 5.0 mol% in the lithium transition metal composite oxide. a positive active material for nonaqueous electrolyte secondary batteries are
At least a portion of the tungsten is present as a subphase of the lithium transition metal composite oxide;
A positive electrode active material for a non-aqueous electrolyte secondary battery, wherein the positive electrode active material has a tap density of 1.7 g / cm ³ or more.   The positive electrode active material according to claim 1, wherein the subphase includes a composite oxide of lithium and tungsten.   The positive electrode active material according to claim 1, wherein 0.20 ≦ 1-ab ≦ 0.50. The specific surface area of the positive electrode active material is 1.7 m. ² The positive electrode active material according to any one of claims 1 to 3, which is / g or less.

The positive electrode active material according to claim 1, wherein a = b. The positive electrode active material according to claim 1, wherein 0.4 ≦ x ≦ 0.6. The nonaqueous electrolyte secondary battery using the positive electrode active material as described in any one of Claims 1 thru | or 6 .   Preparing a nickel cobalt manganese composite oxide having a tap density of 1.3 g / cm 3 or more;
  Mixing the composite oxide and lithium compound and tungsten compound to obtain a mixture;
  Firing the mixture, and a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery,
  The positive electrode active material has the general formula xLi ₂ MnO ₃ (1-x) LiNi _a Co _1-ab Mn _b O ₂ (Provided that 0.3 ≦ x ≦ 0.7, 0 <a ≦ 0.60, 0 <b ≦ 0.50), tungsten is 0.1 mol% or more in the lithium transition metal composite oxide. Contains 0 mol% or less
  At least a portion of the tungsten is present as a subphase of the lithium transition metal composite oxide;
  The positive electrode active material has a tap density of 1.7 g / cm. ³ The manufacturing method which is the above.   The manufacturing method according to claim 8, wherein the subphase includes a composite oxide of lithium and tungsten.   The positive electrode active material according to claim 8, wherein 0.20 ≦ 1-ab ≦ 0.50.   The specific surface area of the positive electrode active material is 1.7 m. ² The production method according to any one of claims 8 to 10, which is not more than / g. The manufacturing method according to claim 8, wherein a = b. It is 0.4 <= x <= 0.6, The manufacturing method as described in any one of Claims 8 thru | or 12. A method for producing a non-aqueous electrolyte secondary battery using a positive electrode active material obtained by the production method according to claim 8.

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