JP2019175697A - Manufacturing method for positive electrode active material for non-aqueous electrolyte secondary battery, molded body, and manufacturing method for non-aqueous electrolyte secondary battery - Google Patents

Abstract

A simple method for producing a positive electrode active material having higher productivity and higher crystallinity is provided.
A lithium mixture containing at least one of nickel composite hydroxide and nickel composite oxide and a lithium compound is molded, and has a thickness of 10 mm or more and a cross section perpendicular to the thickness direction. S20 to obtain a molded body having a major axis of 30 mm or more and a density of 1.6 g / cm ³ or more, and firing the molded body in an oxidizing atmosphere at 730 ° C. or more and 930 ° C. or less for less than 10 hours, Obtaining a lithium nickel composite oxide S30.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery, a molded body, and a method for producing a non-aqueous electrolyte secondary battery.

  In recent years, with the widespread use of portable electronic devices such as mobile phones and laptop computers, development of small and lightweight non-aqueous electrolyte secondary batteries having high energy density is strongly desired. In addition, development of secondary batteries having excellent output characteristics and charge / discharge cycle characteristics is strongly desired as batteries for electric vehicles including hybrid cars.

  As a secondary battery satisfying such requirements, there is a positive electrode active material for a non-aqueous electrolyte secondary battery, and a lithium ion secondary battery is a typical secondary battery. This 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 the active material of the negative electrode and the positive electrode.

  Such a lithium ion secondary battery is currently being actively researched and developed. Among them, a lithium ion secondary battery using a layered or spinel type lithium metal composite oxide as a positive electrode material, Since a high voltage of 4V class can be obtained, practical use is progressing as a battery having a high energy density.

As materials mainly proposed so far, lithium cobalt composite oxide (LiCoO ₂ ), lithium nickel composite oxide (LiNiO ₂ ), lithium nickel cobalt manganese composite oxide (LiNi _{1 / 3} Co _1/3 Mn _1/3 O ₂ ), lithium manganese composite oxide using manganese (LiMn ₂ O ₄ ), and the like.

Among these, lithium nickel composite oxide (LiNiO ₂ ) is attracting attention from the viewpoint of having a higher discharge capacity when nickel cheaper than cobalt is used and when used for a positive electrode of a secondary battery. Yes.

  The lithium nickel composite oxide can be obtained by mixing a raw material such as a nickel-containing compound (precursor) and a lithium-containing compound (lithium compound) to prepare a lithium mixture, and then firing the lithium mixture. Firing of the lithium mixture is usually performed at a temperature of about 700 ° C. to 900 ° C. for 10 hours or longer. And in the case of baking, a lithium compound and a precursor react and the lithium nickel complex oxide which has high crystallinity is obtained.

  With a further increase in demand for lithium ion secondary batteries in recent years, it is required to produce a lithium nickel composite oxide having high crystallinity at a low cost and with high productivity.

  In the firing step of the lithium mixture, the powder of the lithium mixture is generally placed in a container such as a mortar and fired in a firing furnace. In addition, some methods for obtaining a lithium nickel composite oxide by granulating a lithium mixture to form a compact and then firing it are disclosed.

For example, in Patent Document 1 below, at least a nickel salt and a lithium salt are mixed in a predetermined amount to form a raw material mixture, and when the raw material mixture is fired to synthesize LiNiO ₂ , the raw material mixture can be granulated. And a method for producing a LiNiO ₂ -based layered composite oxide characterized by firing the granulated product. According to Patent Document 1, a composite having a desired crystal structure can be manufactured with high productivity including the work surface by the above manufacturing method. In the example of Patent Document 1, specifically, as the size of the granulated product, a granulated product of about 0.5 mm is put in an alumina container, heated to 700 ° C., and held for 24 hours. And firing.

In Patent Document 2 below, a raw material mixture containing a lithium raw material is formed into a molded body through steps such as granulation, and then held in an oxidizing atmosphere at a temperature of 700 ° C. to 1000 ° C. for 2 to 15 hours. The synthesis of composite oxides is described. Moreover, in the Example of patent document 2, Ni main component raw material powder and Li raw material are mixed, and it forms at a pressure of ² t / cm <2> with a die press, and makes this pellet at 800 degreeC for 10 hours, It is described that firing was performed in a pure oxygen atmosphere.

In Patent Document 3 below, when a composition containing LiCoO ₂ or LiCoO ₂ as a main component is synthesized, the mixed powder is press-molded at a pressure of 100 kg / cm ² to 1000 kg / cm ² , It is described that the thickness is set to 2 to 10 mm and the gap between the press-molded bodies is set to 1 mm or more and fired. Moreover, in the Example of patent document 3, the mixed powder which mixed the raw material is press-molded by the press pressure of 500 kg / cm < ² > to the molded object of diameter 50mm and thickness 5mm, and the piece of the alumina spacer of thickness 1mm is press-molded. It is described that it is sandwiched in an appropriate place on the body and fired at 740 ° C. for 10 hours and at 820 ° C. for 20 hours.

The following Patent Document 4 describes that a raw material containing a lithium compound is slurried, and a dried product obtained by spraying or freeze-drying is fired after press molding. According to Patent Document 4, press molding is extremely useful in that the intermolecular movement distance is shortened and the crystal growth during firing is promoted. In the example of Patent Document 4, a dry gel is formed at a pressure of ² t / cm ² using a static compressor and is formed into a pellet shape having a diameter of 14 mm and a thickness of 2 mm. Among them, it is described that baking was performed at 750 ° C. for 48 hours.

JP 2000-72446 A JP-A-11-135123 Japanese Patent Laid-Open No. 06-290780 International Publication No. 98/06670

  However, when the powder of the lithium mixture is baked in a container as in the prior art, a long baking time is required to produce a lithium nickel composite oxide having poor thermal conductivity and high crystallinity. Become. In addition, when the flow rate of the atmospheric gas in the firing furnace is increased in order to increase the firing efficiency, the powder may rise from the container and may be absorbed by the exhaust duct to lower the yield.

  Moreover, in the said patent documents 1-4, since the granulated material or the molded object is formed and baked, it is thought that baking efficiency improves to some extent. However, the firing conditions specifically disclosed as examples in Patent Documents 1 to 4 require firing for 10 hours or more, and produce lithium nickel composite oxide having high crystallinity with higher productivity. There is a need for a way to do that.

  In Patent Document 1, since the granule is packed in the container and fired, the heat conduction is poor. For example, in order to increase the firing efficiency, when the atmospheric gas flow rate in the firing furnace is increased, the particle size is 1 mm or less. In the case of the granulated product, as in the case of the powder described above, the product may soar from the container and the yield may decrease. On the other hand, in Patent Document 3, it is described that a gap is provided between the press-formed bodies using a spacer. However, in the firing process, two-stage firing is required. Firing is performed.

  In view of the above-mentioned problems, the present invention aims to provide a method for producing a positive electrode active material having high crystallinity with higher productivity, and a molded body that can be suitably used for the production method. And

In the first aspect of the present invention, lithium (Li), nickel (Ni), cobalt (Co), and optionally other metals (M) are included, and the molar ratio of each metal element is Li: Ni: Co: M = s: (1-xy): x: y (where 0.95 ≦ s ≦ 1.30, 0 ≦ x ≦ 0.40, 0 ≦ y ≦ 0.40, and 0.55 ≦ (1-xy) ≦ 1.0, and M is at least one element selected from Mn, V, Mo, Nb, Ti, Zr, W, and Al. A method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery containing a nickel composite oxide,
A lithium mixture containing nickel composite hydroxide and at least one of nickel composite oxide and a lithium compound is molded, and the thickness is 10 mm or more and the major axis of the cross section perpendicular to the thickness direction is 30 mm or more A compact having a density of 1.6 g / cm ³ or more and firing the compact in an oxidizing atmosphere at 730 ° C. or more and 930 ° C. or less for less than 10 hours to obtain a lithium nickel composite oxide And a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery.

Moreover, it is preferable that the density of a molded object is 1.8 g / cm < ³ > or more. Moreover, it is preferable that the compact is placed on a plate-like member disposed in a firing furnace and fired. Moreover, it is preferable that a molded object contains at least one of nickel composite hydroxide and nickel composite oxide, and lithium hydroxide, and does not contain a binder. Moreover, it is preferable that lithium hydroxide is anhydrous lithium hydroxide with a moisture content of 5% or less. Moreover, it is preferable that a molded object contains at least one of nickel composite hydroxide and nickel composite oxide, lithium carbonate, and a binder. Moreover, it is preferable that a binder is 1 or more types selected from polyvinyl alcohol, polyacrylamide, and carboxymethylcellulose. In addition, it is preferable that the lithium mixture is calcined in an oxidizing atmosphere at a temperature of 200 ° C. or higher and 800 ° C. or lower and lower than the firing temperature. Moreover, it is preferable to crush the lithium nickel composite oxide obtained by firing. Further, in the lithium nickel composite oxide, it is preferable that the lithium seat occupation ratio of the lithium main layer obtained from the Rietveld analysis of the X-ray diffraction pattern is 94.0% or more. Further, 5 g of lithium nickel composite oxide is dispersed in 100 ml of pure water, and the amount of lithium eluted in the supernatant after standing for 10 minutes is 0.15% by mass or less based on the total amount of lithium nickel composite oxide. Is preferred.

In the second aspect of the present invention, nickel (Ni), cobalt (Co), and optionally other metals (M) are included, and the molar ratio of each element is Ni: Co: M = (1-x -Y): x: y (where 0 ≦ x ≦ 0.40, 0 ≦ y ≦ 0.40, and 0.55 ≦ (1-xy) ≦ 1.0, and M is Mn And at least one element selected from V, Mo, Nb, Ti, Zr, W, and Al.) And obtained by oxidizing a nickel composite hydroxide and a nickel composite hydroxide. A molded body containing at least one of nickel composite oxide and lithium hydroxide, does not contain a binder, has a thickness of 10 mm or more, a major axis of a cross section perpendicular to the thickness direction of 30 mm or more, and a density of 1.6 g. / Cm ³ or more, and a molded article used for producing a positive electrode active material for a nonaqueous electrolyte secondary battery is Provided.

  In the third aspect of the present invention, a non-aqueous electrolyte secondary battery manufacturing method comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, the positive electrode active material for a non-aqueous electrolyte secondary battery obtained by the above manufacturing method. The manufacturing method of a nonaqueous electrolyte secondary battery provided with manufacturing a positive electrode using is provided.

  According to the present invention, it is possible to provide a method for easily producing a positive electrode active material having high crystallinity with high productivity, and a molded body that can be suitably used for the production method.

Drawing 1 is a figure showing an example of a manufacturing method of a cathode active material for nonaqueous system electrolyte rechargeable batteries of an embodiment. Drawing 2 is a figure showing an example of a manufacturing method of a cathode active material for nonaqueous system electrolyte rechargeable batteries of an embodiment. Drawing 3 is a figure showing an example of a manufacturing method of a cathode active material for nonaqueous system electrolyte rechargeable batteries of an embodiment. FIG. 4 is a diagram illustrating an example of a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to the embodiment. FIG. 5 is a diagram illustrating an example of a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to the embodiment. 6A is a diagram showing an example of the arrangement of the compacts in the firing furnace, and FIG. 6B is a diagram showing an example of the arrangement of the lithium mixture powder in the firing furnace. FIG. 7 is a schematic explanatory diagram of the coin-type battery used in the example.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the embodiments described below. In the drawings, they may be schematically expressed as appropriate, or may be expressed by changing the scale.

1. The manufacturing method of the positive electrode active material for nonaqueous electrolyte secondary batteries This embodiment is a manufacturing method of the positive electrode active material (henceforth "positive electrode active material") for nonaqueous electrolyte secondary batteries containing lithium nickel complex oxide. It is. Lithium-nickel composite oxide (hereinafter also simply referred to as “composite oxide”) includes lithium (Li), nickel (Ni), cobalt (Co), and optionally other metals (M). The molar ratio of Li: Ni: Co: M = s: (1-xy): x: y (where 0.95 ≦ s ≦ 1.30, 0 ≦ x ≦ 0.40, 0 ≦ y) ≦ 0.40 and 0.55 ≦ (1-xy) ≦ 1.0, and M is at least one selected from Mn, V, Mo, Nb, Ti, Zr, W, and Al. Element). The lithium nickel metal composite oxide may have a hexagonal crystal structure having a layered structure, and may include secondary particles in which a plurality of primary particles are aggregated.

  1-5 is a figure which shows an example of the manufacturing method of the positive electrode active material which concerns on this embodiment. As shown in FIG. 1 and the like, the method for producing a positive electrode active material includes, for example, obtaining a lithium mixture containing a nickel composite hydroxide and a lithium compound (step S10), forming the lithium mixture, Obtaining a formed body (step S20) and firing the formed body to obtain a lithium nickel composite oxide (step S30). Hereinafter, each step will be described.

[Step of obtaining lithium mixture (step S10)]
The lithium mixture is obtained by mixing at least one of nickel composite hydroxide and nickel composite oxide and a lithium compound (step S10). In addition, the lithium mixture may contain a binder that settles particles as described later (see FIG. 3). When a lithium mixture contains a binder, the intensity | strength of the molded object obtained can be improved. In the present specification, the nickel composite hydroxide and / or nickel composite oxide contained in the lithium mixture is also collectively referred to as “precursor”.

(Nickel composite hydroxide)
The nickel composite hydroxide used in the present embodiment is not particularly limited, and a known nickel composite hydroxide can be used. For example, a nickel composite hydroxide (precursor) obtained by a crystallization method is used. Can be used. The nickel composite hydroxide obtained by the crystallization method has a uniform composition throughout the particles. A compact containing a nickel composite hydroxide and a lithium compound obtained by a crystallization method can produce a lithium nickel composite oxide having high crystallinity by firing for a very short time.

  The nickel composite hydroxide uses, for example, an alkaline aqueous solution in the presence of a complexing agent such as an ammonium ion supplier while stirring an aqueous solution containing nickel (Ni), cobalt (Co), and optionally a metal M. It can manufacture by performing the crystallization reaction which neutralizes. In addition, as a metal salt used when preparing the said aqueous solution of each of Ni, Co, and the metallic element M, a sulfate, nitrate, a chloride etc. can be used, for example.

  The nickel composite hydroxide obtained by the crystallization method is composed of secondary particles in which primary particles are aggregated, and the positive particles are also aggregated in the positive electrode active material obtained by using the nickel composite hydroxide particles as a precursor. It is composed of secondary particles. The nickel composite hydroxide may contain a small amount of single primary particles in addition to the secondary particles.

  Further, when the nickel composite hydroxide contains the metal element M, for example, in the crystallization reaction, it may be crystallized together with Ni and Co, and may be uniformly dispersed in the nickel composite hydroxide. After forming the nickel composite hydroxide by crystallization, the compound containing the metal element M is coated on the surface of the obtained nickel composite oxide particles, or added and mixed simultaneously with the addition of the lithium compound. Also good.

  The nickel composite hydroxide can include, for example, nickel (Ni), cobalt (Co), and optionally another metal (M), and the molar ratio of each element is Ni: Co: W = ( 1-xy): x: y (where 0 ≦ x ≦ 0.40, 0 ≦ y ≦ 0.40, and 0.55 ≦ (1-xy) ≦ 1.0, M Is at least one element selected from Mn, V, Mo, Nb, Ti, Zr, W, and Al. Further, the nickel composite hydroxide may contain a small amount of metal elements other than those described above.

Nickel composite hydroxide, for example, the general formula (2): _{Ni 1-x over} y _Co x _M in y _{(OH) 2 +} β (Equation (2), 0 ≦ x ≦ 0.40,0 ≦ y ≦ 0. 40, 0.55 ≦ (1-xy) ≦ 1.0, and −0.2 ≦ β ≦ 0.2, and M is Mn, V, Mo, Nb, Ti, Zr, And at least one element selected from W and Al.

  The ratio of each metal element contained in the nickel composite hydroxide is inherited to the compact and the lithium nickel composite oxide. Therefore, the composition of the entire nickel composite hydroxide can be the same as the composition of the metal other than lithium in the lithium nickel composite oxide to be obtained.

  In addition, it does not specifically limit as a crystallization method, For example, a continuous crystallization method, a batch method, etc. can be used. For example, the continuous crystallization method is a method of continuously collecting nickel composite hydroxide overflowed from the reaction vessel, and can easily produce a large amount of nickel composite hydroxide having the same composition. Moreover, since the nickel composite oxide obtained by the continuous crystallization method has a wide particle size distribution, it is possible to improve the packing density of a molded product obtained using the nickel composite oxide.

  For example, the batch method can obtain nickel composite hydroxide having a more uniform particle size and a narrow particle size distribution. The molded body obtained using the nickel composite hydroxide obtained by the batch method can more uniformly react with the lithium compound during firing. Moreover, the nickel composite hydroxide obtained by the batch method can reduce the mixing of fine powder, which is one of the causes of reducing the cycle characteristics and output characteristics when used in a secondary battery. In addition, the average particle diameter (D50) of nickel composite hydroxide is, for example, 5 μm or more and 30 μm or less.

(Nickel composite oxide)
The nickel composite oxide used in the present embodiment is not particularly limited, and a known nickel composite oxide can be used. FIG. 2 is a diagram showing an example of a manufacturing method when nickel composite oxide is used. As shown in FIG. 2, the nickel composite oxide may be obtained by subjecting the nickel composite hydroxide to oxidation roasting (heat treatment) (step S1). The kind of metal element contained in the nickel composite oxide and the molar ratio of each metal element are the same as those of the nickel composite hydroxide described above.

  Oxidation roasting (step S1) is preferably performed, for example, at 350 ° C. to 800 ° C. for 2 hours to 8 hours, and may be performed at 600 ° C. to 800 ° C. for 6 hours to 8 hours. When the oxidation roasting temperature is less than 350 ° C., a large amount of moisture may remain in the obtained precursor (mainly nickel composite oxide). On the other hand, when the temperature of oxidation roasting exceeds 800 ° C., moisture in the precursor is removed, but not only is not industrially suitable from the viewpoint of cost, processing time, etc., but also the crystal of the nickel composite oxide itself. Growth may progress and reactivity with the lithium compound may decrease.

  When the nickel composite oxide and the lithium compound are mixed (step S10), molded (step S20), and then fired (step S30), the firing is performed in a shorter time (for example, 1 hour to less than 10 hours). A lithium nickel composite oxide having a sufficiently large crystallite diameter and high crystallinity can be obtained. In the manufacturing method of the present embodiment, as described later, the composition of the molded body, the flow rate of the atmospheric gas in the firing furnace, the arrangement of the molded body, and the like are appropriately adjusted without performing oxidation roasting, as described later. Lithium nickel composite oxide can be obtained by firing for less than an hour.

(Lithium compound)
It does not specifically limit as a lithium compound, A well-known lithium compound can be used, For example, lithium hydroxide, lithium nitrate, lithium carbonate, lithium acetate, the mixture containing these 2 or more types, etc. can be used. Among these, it is preferable to use lithium hydroxide or lithium carbonate.

  When lithium hydroxide is used as the lithium compound, as will be described later, a molded body having sufficient strength can be obtained without using a binder, and contamination of impurities into the positive electrode active material can be further suppressed. Yes (see FIG. 4). Moreover, since lithium hydroxide has high reactivity, the molded object obtained using this can be sintered earlier (sintered in a shorter time), and the firing time can be shortened.

The lithium hydroxide may be a lithium hydroxide hydrate such as lithium hydroxide monohydrate (LiOH.H ₂ O), or may be anhydrous lithium hydroxide (LiOH). Anhydrous lithium hydroxide can be obtained, for example, by heat-treating lithium hydroxide hydrate. When anhydrous lithium hydroxide is used, the generation of moisture in the firing process can be further suppressed, and not only the synthesis reaction of the lithium-nickel composite oxide is promoted, but also the metal component in the molded body reduces moisture. Productivity is also expected to increase due to the increase. As anhydrous lithium hydroxide, lithium hydroxide having a moisture content of 5% or less is preferably used.

  When lithium carbonate is used as the lithium compound, since lithium carbonate is cheaper than lithium hydroxide, it is more excellent from the viewpoint of cost. The temperature required for high crystallization of the lithium nickel composite oxide is about 760 ° C. or higher, which is close to the melting temperature of lithium carbonate (melting point: 723 ° C.). For this reason, when lithium carbonate is used as the lithium compound, high crystallization of the lithium nickel composite oxide is difficult as compared with the case where lithium hydroxide (melting point: 462 ° C.) is used. Furthermore, the difficulty of high crystallization of the lithium nickel composite oxide becomes more remarkable as the Ni ratio contained in the precursor (nickel composite hydroxide / nickel composite oxide) increases. However, in the manufacturing method of the present embodiment, the reactivity of the lithium compound can be increased as compared with the conventional manufacturing method by firing the molded body under appropriate conditions as described later. Even when lithium is used, a lithium-nickel composite oxide having high crystallinity can be produced by short-time firing.

(Lithium mixture)
The precursor (nickel composite hydroxide / nickel composite oxide) and the lithium compound are the ratio of the sum of the number of atoms of nickel, cobalt and M in the precursor (Me) to the number of lithium atoms (Li) (Li / Me ratio) is 0.95 or more and 1.30 or less, preferably 1.00 or more and 1.10 or less, more preferably more than 1.00 and 1.05 or less. It becomes. Since Li / Me does not substantially change before and after firing (step S30) described later, the Li / Me ratio in the lithium mixture is substantially maintained even in the lithium nickel composite oxide. Therefore, the precursor and the lithium compound can be mixed so that the Li / Me ratio in the lithium nickel composite oxide particles to be obtained is the same. When the Li / Me ratio is less than 0.95, part of the nickel composite oxide may remain unreacted and sufficient battery performance may not be obtained. On the other hand, when the Li / Me ratio is more than 1.30, sintering is promoted, and the particle size and crystallite size of the positive electrode active material are increased, so that sufficient battery performance may not be obtained.

  The lithium mixture is preferably mixed well before firing. If the mixing is not sufficient, the Li / Me ratio varies among individual particles, which may cause problems such as insufficient battery characteristics. For mixing, a general mixer (mixing device) can be used. For example, a mixer such as a shaker mixer, a Laedige mixer, a Julia mixer, or a V blender can be used. Moreover, this mixing should just fully mix so that the shape of a precursor may not be destroyed.

(binder)
The lithium mixture may include a binder. When the binder is included, the moldability of the lithium mixture is improved, and molded bodies having various shapes can be easily formed. As shown in FIG. 3, for example, when lithium carbonate is used as the lithium compound, the lithium mixture preferably includes a binder. In addition, as shown in FIG. 3, the nickel composite oxide in the case of making a lithium mixture contain a binder may be the nickel composite oxide obtained by the oxidation roasting of step S1 shown in FIG. By molding a lithium mixture containing a binder, a molded body having sufficient strength can be easily obtained. As the binder, a known binder can be used, for example, polyvinyl alcohol (PVA), polyacrylamide (PAM), carboxymethyl cellulose (CMC), etc., and one or more selected from these can be used. Among these, it is preferable to use carboxymethylcellulose.

  The content of the binder in the lithium mixture is, for example, 0.05% by mass or more and 2.0% by mass or less, preferably 0.08% by mass or more and 1.0% by mass or less, with respect to the entire lithium mixture (total mass). is there. When content of a binder is the said range, the molded object which has moderate intensity | strength can be manufactured. If the binder content is too high, the adhesive strength of each particle constituting the compact becomes too strong, resulting in a decrease in the efficiency of discharging the product gas generated by the reaction between lithium and the nickel composite oxide, or the binder being decomposed. As a result, the amount of carbon dioxide generated increases, and the generated gas cannot be discharged inside the molded body, so that the internal pressure of the molded body increases and the molded body may be crushed.

  The lithium mixture may not contain a binder. As shown in FIG. 4, for example, when lithium hydroxide is used as the lithium compound, a molded body can be formed only from the precursor and lithium hydroxide without using a binder. In particular, when anhydrous lithium hydroxide having a moisture content of 5% or less is used as the lithium compound, the lithium mixture can obtain a molded article having good strength without including a binder. When a binder is not used, the content of impurities (for example, carbon and the like) in the obtained lithium nickel composite oxide can be reduced.

[Calcination (Step S15)]
As shown in FIG. 5, the lithium mixture may be calcined at 200 ° C. or more and 800 ° C. or less and lower than the firing temperature described later before firing (under an oxidizing atmosphere) ( Step S15). For example, the calcination is performed before the lithium mixture is formed (before step S20). The calcination may be performed when the lithium mixture as shown in FIG. 5 does not contain a binder, or may be carried out when the lithium mixture as shown in FIG. 3 contains a binder. For example, when the lithium mixture as shown in FIG. 3 contains a binder, the lithium compound and the nickel composite hydroxide are mixed and calcined, and after calcining, the binder is mixed to form a lithium mixture, and the lithium mixture May be formed (step S20). That is, calcination may be carried out in the process of adjusting the lithium mixture when the lithium mixture contains a binder. The calcination is preferably performed at a temperature of 250 ° C. or higher and 800 ° C. or lower, preferably 300 ° C. or higher and 600 ° C. or lower for 1 hour to 8 hours, preferably 2 hours to 6 hours. Note that the oxidizing atmosphere refers to an air atmosphere or an atmosphere having a higher oxygen concentration than the air, and an air atmosphere is preferable from the viewpoint of cost.

  When calcined before firing, lithium is sufficiently diffused, and a more uniform lithium nickel composite oxide can be obtained. In addition, in the manufacturing method of this embodiment, it is 10 hours by adjusting suitably the composition of a molded object, the atmospheric gas flow rate in a kiln, arrangement | positioning of a molded object, etc. so that it may mention later, without performing calcination. Lithium nickel composite oxide can be obtained by firing less than

[Molding of Molded Body (Step S20)]
Subsequently, a lithium mixture is shape | molded and a molded object is obtained (step S20). For example, a lithium mixture is pressure-molded to obtain a molded body. FIG. 6A is a diagram illustrating an example of the molded body 20. The molded body 20 has a thickness t of 10 mm or more, a major axis l of a cross section perpendicular to the thickness direction of 30 mm or more, and a density of 1.6 g / cm ³ or more. The compact 20 has a higher density than the conventional lithium mixture powder 10 (see FIG. 6B). Therefore, when the molded body 20 is fired, the heat transfer coefficient increases, so that a lithium nickel composite oxide can be obtained in a very short time.

Further, when the molded body 20 is molded without using a binder, the molded body 20 includes nickel (Ni), cobalt (Co), and optionally another metal (M), and the molar ratio of each element is Ni: Co. : M = (1-xy): x: y (where 0 ≦ x ≦ 0.40, 0 ≦ y ≦ 0.40, and 0.55 ≦ (1-xy) ≦ 1.0) M is at least one element selected from Mn, V, Mo, Nb, Ti, Zr, W, and Al.) Nickel composite hydroxide and nickel composite oxide It is preferable that it is 10 mm or more in thickness, 30 mm or more in major axis, and the density is 1.6 g / cm < ³ > or more.

Further, when the molded body 20 is molded using a binder, the molded body 20 includes nickel (Ni), cobalt (Co), and optionally another metal (M), and the molar ratio of each element is Ni: Co: M = (1-xy): x: y (where 0 ≦ x ≦ 0.40, 0 ≦ y ≦ 0.40, and 0.55 ≦ (1-xy) ≦ 1.0) M is at least one element selected from Mn, V, Mo, Nb, Ti, Zr, W, and Al.) And a nickel composite hydroxide represented by It preferably includes at least one and lithium carbonate, and has a thickness of 10 mm or more, a major axis of 30 mm or more, and a density of 1.6 g / cm ³ or more.

(Thickness of molded body)
The thickness t of the molded body 20 is 10 mm or more, and from the viewpoint of productivity, it is preferably 10 mm or more and 200 mm or less, more preferably 10 mm or more and 100 mm or less, more preferably 10 mm or more and 50 mm or less, Preferably they are 20 mm or more and 40 mm or less. When the thickness t of the molded body 20 is in the above range, a positive electrode active material having high crystallinity can be easily manufactured with high productivity. In the present embodiment, the thickness t of the molded body 20 is the maximum thickness in the pressing direction. For example, when the thickness t of the molded body 20 is not constant, the largest thickness is set as the thickness t of the molded body 20. In addition, when the pressing direction is not fixed in one direction or when it is unknown, the thickness in the direction perpendicular to the mounting surface at the time of firing may be the maximum.

(Long diameter of molded body)
The major axis 1 of the molded body 20 is 30 mm or more, and preferably 70 mm or more, more preferably 140 mm or more from the viewpoint of productivity. Further, the upper limit of the major axis l of the molded body 20 can be appropriately adjusted depending on the size in the furnace of the firing furnace, etc., preferably 400 mm or less, more preferably 300 mm or less, even 200 mm or less. Good. When the major axis is 30 mm or more, a large amount of lithium mixture can be processed in the firing step.

  In addition, the “major axis” of the molded body 20 means a length that maximizes the distance between any two points in a cross section (usually a pressing surface) perpendicular to the thickness direction. The maximum diameter of the circle circumscribing the outer edge of the cross section perpendicular to the thickness direction. Further, when the shape of the cross section perpendicular to the thickness direction is not constant, the diameter of a circle circumscribing the outer edge of the largest cross section is meant. The shape of the cross section perpendicular to the thickness direction is not particularly limited, and may be a circle, an ellipse, a rectangle, a polygon, and other shapes (eg, indefinite shape).

(L / t ratio of molded product)
The ratio of the major axis l to the thickness t of the molded body 20 (l / t ratio) is preferably 1.5 or more and 20 or less, more preferably 2 or more and 15 or less, and more preferably 3 or more and 11 or less. It is.

(Shape of molded body)
Further, the shape of the molded body 20 is not particularly limited as long as it satisfies the above range of size (major axis, thickness), and a plate shape, a columnar shape, or the like can be used. From the viewpoint of productivity, a plate-like shape is preferable as shown in FIG. Moreover, when the shape of the molded object 20 is a rectangular plate shape, the filling density to the furnace at the time of baking can be made high.

(Molded body density)
The density of the molded body 20 is 1.6 g / cm ³ or more, preferably 1.8 g / cm ³ or more, more preferably 1.8 g / cm ³ or more and 2.6 g / cm ³ or less, more preferably not more than 1.8 g / cm ³ or more 2.3 g / cm ^3, more preferably not more than 2.0 g / cm ³ or more 2.2 g / cm ^3. When the density of the molded body 20 is in the above range, a positive electrode active material having high crystallinity can be produced with high productivity. On the other hand, when the density of the molded body 20 is less than 1.6 g / cm ³ , the strength of the molded body decreases, the molded body collapses during handling of the molded body or during firing, and the heat transfer coefficient decreases or yields. May be worsened. Moreover, when the density of the molded object 20 exceeds 2.6 g / cm < ³ >, sintering at the time of baking advances too much and a yield may deteriorate significantly in the crushing process mentioned later. In addition, it is preferable that the density inside the molded object 20 and the density between the some molded objects 20 are uniform as a whole. When the density of the inside of a molded object and between molded objects is uniform, generation | occurrence | production of what is called a burning unevenness produced by the difference in the heat transfer rate by a density difference is suppressed, and the variation in quality can be suppressed.

(pressure)
The molded body 20 is manufactured, for example, by pressure molding a lithium mixture. The pressure (surface pressure) at the time of producing the molded body is not particularly limited, and the surface pressure may be controlled so as to achieve a target density. Surface pressure is preferably not more than 300kgf ^/ cm 2 (29.4MPa) above 1000kgf ^/ cm 2 (98.1MPa), and more preferably 500kgf ^/ cm 2 (49.0MPa) above 800kgf ^/ cm 2 (78.5MPa ) When the surface pressure is within the above range, a molded body having the above density can be easily molded while maintaining the shape of the precursor particles. When the surface pressure is less than 300 kgf / cm ² (29.4 MPa), the lithium mixture may not be formed. On the other hand, when the surface pressure exceeds 1000 kgf / cm ² (98.1 MPa), the molded body 20 can be formed, but the quality of the obtained positive electrode active material may be deteriorated by breaking the precursor particles. .

(Slicing)
The molded body 20 is manufactured by, for example, charging a lithium mixture into a predetermined mold (mold) and then performing pressure molding. In this case, after putting the raw material (lithium mixture) into the mold and before press molding, the cutting may be performed, or after the cutting, the mold may be vibrated. Thereby, the lithium mixture can be more uniformly and stably filled into the mold, and as a result, the density inside the molded body 20 becomes more uniform as a whole. Moreover, when manufacturing the some molded object 20, you may measure the injection | throwing-in amount to the formwork of a lithium mixture. Thereby, the input amount of the lithium mixture into the mold becomes uniform, and the density variation between the molded bodies 20 can be suppressed.

(Molded product manufacturing equipment)
The apparatus for producing the molded body 20 is not particularly limited as long as it can pressurize (press) the lithium mixture. For example, a powder molding press, a tablet machine (tablet), a briquette machine An apparatus such as a roller compactor or a hydraulic press can be used, and a hydraulic press is preferably used. Moreover, when manufacturing the molded object 20, by using together with lubricants, such as a stearic acid, adhesion of the raw material to the formwork which manufactures the molded object 20 can be prevented, and it can respond also to mass production.

[Baking (Step S30)]
Next, the obtained molded body is fired at 730 ° C. or higher and 930 ° C. or lower in an oxidizing atmosphere (step S30). By firing the molded body 20, the precursor and the lithium compound react with each other to produce a lithium nickel composite oxide. When the firing temperature was less than 730 ° C., lithium was not sufficiently diffused, and unreacted lithium compound particles remained or the crystal structure of the lithium-nickel composite oxide was not sufficiently obtained. A secondary battery using a positive electrode active material may not have sufficient battery characteristics. On the other hand, when the firing temperature is higher than 930 ° C., severe sintering occurs between the lithium nickel composite oxide particles and abnormal grain growth may occur, thereby reducing the specific surface area. In addition, a decrease in the specific surface area of the positive electrode active material may increase the resistance of the positive electrode and decrease the battery capacity.

  During firing, the temperature is gradually increased from room temperature, and is maintained in a temperature range of 730 ° C. to 930 ° C. for less than 10 hours. The firing temperature can be appropriately adjusted within a range of 730 ° C. or higher and 930 ° C. or lower depending on the composition of the precursor, the type of lithium compound, the shape of the molded body, and the like. It may be 800 degreeC or more and 900 degreeC or less. Moreover, the temperature increase rate of a baking furnace is not specifically limited, For example, it is 3 degree-C / min or more, Preferably it is 5 degree-C / min or more, More preferably, it is 8 degree-C / min or more. Moreover, the upper limit of the temperature increase rate of a baking furnace is 15 degrees C / min or less, Preferably it is 10 degrees C / min or less. When the heating rate of the firing furnace is in the above range, the firing efficiency is more excellent. When the heating rate of the firing furnace exceeds 15 ° C./min, the temperature variation in the molded body becomes large, and local sintering may occur. Note that the firing temperature and the heating rate of the firing furnace may not be constant, and may be changed stepwise, for example.

  The firing time is less than 10 hours, preferably 8 hours or less, more preferably 7.5 hours or less, still more preferably 6 hours or less, and may be 2.2 hours or less. Note that in this specification, the firing time means a time for holding at the firing temperature. Conventionally, when the above lithium mixture is fired, the firing is performed in an air atmosphere or an oxidizing atmosphere for about 15 to 20 hours. In the manufacturing method of the present embodiment, the above-described molded body 20 is fired. Thus, a lithium nickel composite oxide having high crystallinity can be obtained in a very short time (for example, a time that is half or less of the conventional firing time). In addition, although the minimum of baking time should just be a range with which reaction with a precursor and a lithium compound is fully performed, it may be 1 hour or more, for example, and may be 2 hours or more, for example.

  The atmosphere during firing is an oxidizing atmosphere, and preferably has a higher oxygen concentration than the air atmosphere (air stream). In this embodiment, the proportion of nickel (Ni) that is the obtained lithium metal composite oxide is 55 atomic% or more, and the proportion of nickel is relatively high. As the proportion of nickel increases, the Ni valency increases and more oxygen is required to produce a layered compound with Li, and it is necessary to infiltrate oxygen into the interior of the molded body 20 for reaction. .

  The atmosphere during firing preferably has an oxygen concentration of 25% by volume or more, more preferably an atmosphere having an oxygen concentration of 30% by volume or more and 100% by volume, and further has an oxygen concentration of 100% by volume. preferable. When the firing atmosphere has an oxygen concentration in the above range, the lithium nickel composite oxide having a layered crystal structure can be more reliably formed by sufficiently infiltrating oxygen into the compact 20.

  The flow rate of the atmospheric gas is not particularly limited, and may be, for example, less than 20 L / min or less than 10 L / min from the viewpoint of cost. Even if the flow rate of the atmospheric gas is within the above range, the lithium compound and the precursor can be reacted. Note that the flow rate of the atmospheric gas may exceed 20 L / min. For example, in the case of a batch-type firing furnace, an atmospheric gas flow rate in the above range can be suitably used. The lower limit of the flow rate of the atmospheric gas can be appropriately adjusted depending on the size in the firing furnace, the shape of the molded body 20, and the like, and is, for example, 2 L / min or more.

  The furnace used for firing is not particularly limited as long as it can be heated in an oxygen stream, a vertical furnace, a horizontal furnace, or the like may be used. Among these, an electric furnace that does not generate gas is preferable. Further, a batch type furnace may be used, and a continuous type furnace may be used. Among these, it is preferable to use a horizontal furnace such as a rotary hearth furnace or a roller hearth kiln from the viewpoint that more molded bodies can be efficiently conveyed and fired.

  FIG. 6A is a diagram showing a state in which the molded body 20 is placed on the plate-like member 1 when firing, and FIG. 6B is a diagram showing a lithium mixture 20 in a powder state in the container 2 when firing. It is a figure which shows the state which put. Conventionally, when the powder 10 of a lithium mixture or a granulated product is fired, the powder or the granulated product is placed in a container 2 such as a mortar and fired as shown in FIG.

  At the time of firing, the molded body 20 may be placed in the container 2 and fired as in the conventional case, but as shown in FIG. 6A, the container 2 is not used and the plate-like member 1 such as a setter is directly used. Alternatively, the molded body 20 may be placed and fired. The setter is a member (furnace material) with which the molded body comes into contact in the firing furnace, and as shown in FIG. 6 (A), is a plate-like member 1 such as a shelf board or a floorboard on which the molded body can be placed. Is preferred. When the plate-like member 1 is used without using the container 2, the contact area between the molded body 20 and the atmospheric gas can be increased to further promote the reaction between the precursor and the lithium compound. When firing, the plate-like molded body 20 may be fired by placing it alone on the plate-like member 1 as shown in FIG. 7A, or a plurality of plate-like molded bodies 20 may be stacked. The cake (aggregate) may be placed on the plate member 1 and fired.

(Lithium mixture throughput)
In the manufacturing method of the present embodiment, since the density is higher than the case where the powder 10 of the lithium mixture is fired by firing the molded body 20 obtained by molding the lithium mixture, Can increase production. For example, in the manufacturing method of the present embodiment, when the molded body 20 according to the present embodiment is fired, compared with the case where the powder 10 of the lithium mixture is fired, for example, the throughput of the lithium mixture calculated by the following formula However, it can be 2 times or more, preferably 2.5 times or more, more preferably 3 times or more, and further preferably 5 times or more.
Treatment amount: (T _(powder) / T _{(molded body)} ) × (L _{(molded body)} / L _(powder) × loss coefficient) (formula)
(In the above formula, T 1 _{(molded body)} is the holding time in the furnace at the time of firing the molded body (the time when the temperature is raised to the firing temperature (temperature raising time) and the holding time at the firing temperature (firing time)). T _(powder) is the holding time in the furnace when the powder is fired _(the sum of the time when the temperature is raised to the firing temperature (temperature rise time) and the holding time at the firing temperature (fire time)) L 1 _{(molded body)} represents the weight of the molded body per unit volume during firing (“unit volume during firing” multiplied by “density of molded body”), and L 2 _(powder) Indicates the weight of the lithium mixture of the powder per unit volume at the time of firing (a value obtained by multiplying the “unit volume at the time of firing” by “the density of the powder”), and the loss coefficient is 1.0 for the powder. Is the relative filling rate of the molded body, and the volume ratio of the lithium mixture (molded body) in the above "unit volume during firing" (It is a value according to.)
In addition, said processing amount is a value when the processing amount in the powder described in Comparative Example 3 is 1.0 in the case of the molded body 20 according to the present embodiment (Examples 1 to 23).
(T _(powder) / T _{(molded body)} ) in the above processing amount indicates the total time of the temperature rise time and firing time of the lithium mixture powder (powder) relative to the firing time of the molded body 20, in other words, The effect regarding the baking time at the time of baking the molded object 20 with respect to powder is shown.
In addition, (L _{(molded product)} / L _(powder) × loss coefficient) in the above processing amount is the same as that when firing the molded product 20 with respect to the input weight per unit volume when firing the lithium mixture powder (powder). The input weight per unit volume is shown, in other words, the effect on the input weight per unit volume when the molded body 20 is fired on the powder.
The unit volume at the time of firing is an arbitrarily set value. For example, the unit volume may be set to a value larger than the volume of one molded body 20 or to a value smaller than the volume of one molded body 20. It may be set. For example, when the unit volume at the time of firing is set to a value larger than the volume of one molded body 20, the input weight of the molded body 20 per unit volume at the time of firing is a plurality of molded bodies per unit volume. 20 (aggregate 30) is filled (that is, L _{(molded product)} × loss coefficient).
The loss coefficient is a value that varies depending on the shape of the molded body 20 or the mode of arrangement of the molded body 20 (the mode of arrangement of the molded bodies 20 in the aggregate 30 composed of a plurality of molded bodies 20). It is not specifically limited, It can set arbitrarily. The loss coefficient can be adjusted to a desired value by changing the shape of the molded body 20 and the arrangement of the molded body 20. For example, in the case of the aggregate 30 composed of the molded bodies 20 (rectangular columnar shapes) shown in the examples of the present embodiment, for example, 0.9 is set, but the loss coefficient is not limited to these examples.
In the manufacturing method of the present embodiment, (T _(powder) / T _{(molded body)} )> 1 and (L _{(molded body)} / L _(powder) × loss coefficient)> 1 are shown in the above processing amount. Compared with the case where the powder is fired, the firing time and the weight per unit volume at the time of firing can be improved.

[Crushing]
The lithium nickel composite oxide after firing (step S30) may retain the shape of the molded body 20 before firing. Further, the particles of the lithium nickel composite oxide obtained by firing (step S30) may be aggregated or slightly sintered. In such a case, the manufacturing method of this embodiment may include a crushing step of crushing the aggregate or sintered body of the lithium nickel composite oxide particles. By crushing, the average particle diameter and particle size distribution of the positive electrode active material obtained can be adjusted to a suitable range. Note that pulverization means that mechanical energy is applied to an aggregate composed of a plurality of secondary particles generated by sintering necking between secondary particles during firing, and the secondary particles themselves are hardly destroyed. An operation of separating and loosening aggregates.

  As a crushing method, a known means can be used, for example, a pin mill or a hammer mill can be used. At this time, it is preferable to adjust the crushing force to an appropriate range so as not to destroy the secondary particles.

2. Positive electrode active material for non-aqueous electrolyte secondary battery By the manufacturing method according to the above-described embodiment, a lithium nickel composite oxide (positive electrode active material) excellent in crystallinity can be obtained with high productivity by firing in a short time. Hereinafter, the characteristics of the lithium nickel composite oxide obtained by the manufacturing method according to the present embodiment will be described.

(composition)
The lithium nickel composite oxide contains lithium (Li), nickel (Ni), cobalt (Co), and optionally another metal (M), and the molar ratio of each metal element is Li: Ni: Co: M = s: (1-xy): x: y (where 0.95 ≦ s ≦ 1.30, 0 ≦ x ≦ 0.40, 0 ≦ y ≦ 0.40, and 0.55 ≦ (1) −xy) ≦ 1.0, and M is at least one element selected from Mn, V, Mo, Nb, Ti, Zr, W, and Al.

Lithium nickel composite oxide, for example, have a hexagonal crystal structure having a layered structure, the general formula _{(1): Li s Ni 1} -x-y Co x M y O 2 + α ( formula (1), 0.95 ≦ s ≦ 1.30, 0 ≦ x ≦ 0.40, 0 ≦ y ≦ 0.40, 0.55 ≦ (1-xy) ≦ 1.0, and M is And at least one element selected from Mn, V, Mo, Nb, Ti, Zr, W, and Al. Further, (1-xy) corresponding to the content of nickel (Ni) may be less than 1.

(Lithium seat occupancy rate)
In the lithium nickel composite oxide, for example, the lithium site occupancy of the 3a site, which is the lithium main layer obtained from the Rietveld analysis of the X-ray diffraction pattern, is 94% or more, preferably 95% or more, more preferably 96% or more. When the lithium seat occupancy is in the above range, the sintering reaction between the precursor and the lithium compound is sufficiently performed in the firing step (step S30), and the lithium nickel composite oxide has high crystallinity. Show. When a highly crystalline lithium nickel composite oxide is used as a positive electrode active material of a secondary battery, excellent battery characteristics (high battery capacity, etc.) are exhibited.

(Eluted lithium amount)
In the lithium nickel composite oxide, the lithium nickel composite oxide is dispersed in pure water, and the amount of lithium eluted in the supernatant after standing (the amount of lithium eluted) is 0.15 mass relative to the total amount of the lithium nickel composite oxide. % Or less, preferably 0.14% by mass or less, more preferably 0.13% by mass or less, and still more preferably 0.12% by mass or less. The amount of lithium eluted can be measured by a neutralization titration method. For example, ultrapure water is added to 100 mL of 10 g of lithium nickel composite oxide powder and stirred to disperse the powder, and the supernatant after standing for 10 minutes is titrated with hydrochloric acid having a concentration of 1 mol / L. The second neutralization point was measured, and the alkali content neutralized with hydrochloric acid was defined as lithium eluted from the lithium nickel composite oxide. From the titration results, the mass ratio of lithium to the lithium nickel composite oxide was determined. The amount of eluted lithium can be used.

  The eluted lithium is considered to be derived from an unreacted lithium compound present on the particle surface of the positive electrode active material, an excessive amount of lithium present in the crystal, or the like. That is, the amount of eluted lithium can be used as one of the indicators of the remaining amount of unreacted lithium compound derived from the raw material. The smaller the amount of eluted lithium, the smaller the amount of unreacted lithium compound, It can be said that the sintering reaction between the body and the lithium compound proceeds. Moreover, the gelation of the positive electrode mixture paste described later can be suppressed as the amount of eluted lithium is smaller.

(Initial charge / discharge efficiency)
The initial charge / discharge efficiency (initial discharge capacity / initial charge capacity) in an evaluation 2032 type coin-type battery CBA (see FIG. 7) produced using lithium nickel composite oxide as the positive electrode active material is, for example, 87%. Or more, preferably 88% or more, more preferably 90% or more. When the initial charge / discharge efficiency is in the above range, the sintering reaction between the precursor and the lithium compound is sufficiently performed in the firing step (step S30), and the lithium nickel composite oxide has high crystallinity. Show. The initial discharge capacity is about 24 hours after the coin-type battery CBA used in the example is manufactured. After the open circuit voltage OCV (Open Circuit Voltage) is stabilized, the current density with respect to the positive electrode is 0.1 mA. It is a value obtained by measuring the capacity when charged to a cutoff voltage of 4.3 V as / cm ² and discharged to a cutoff voltage of 3.0 V after a pause of 1 hour.

3. Non-aqueous electrolyte secondary battery The non-aqueous electrolyte secondary battery manufacturing method according to the present embodiment (hereinafter also referred to as “secondary battery manufacturing method”) uses a positive electrode, a negative electrode, and a non-aqueous electrolyte. An electrolyte secondary battery is obtained, and the positive electrode is obtained using the positive electrode active material obtained by the above-described production method. In addition, the secondary battery obtained by the manufacturing method according to the present embodiment may include, for example, a positive electrode, a negative electrode, a separator, and a nonaqueous electrolytic solution, or may include a positive electrode, a negative electrode, and a solid electrolyte. Further, the secondary battery may be composed of the same components as those of known lithium ion secondary batteries.

  Hereinafter, as an example of the manufacturing method of the secondary battery according to the present embodiment, each constituent material of the secondary battery using the nonaqueous electrolytic solution and the manufacturing method thereof will be described. Note that the embodiments described below are merely examples, and the method for manufacturing a secondary battery is subjected to various changes and improvements based on the embodiments described in this specification based on the knowledge of those skilled in the art. Can be implemented. Moreover, the use of the secondary battery obtained by the manufacturing method according to the present embodiment is not particularly limited.

(Positive electrode)
A positive electrode contains said positive electrode active material. The positive electrode can be manufactured, for example, as follows. Note that the method for manufacturing the positive electrode is not limited to the following, and other methods may be used.

  First, the positive electrode active material, the conductive material, and the binder (binder) are mixed, and if necessary, activated carbon or a solvent for adjusting viscosity is added, and this is kneaded to mix the positive electrode mixture. Make a paste. The constituent material of the positive electrode mixture paste is not particularly limited, and a material equivalent to a known positive electrode mixture paste may be used.

  The mixing ratio of the respective materials in the positive electrode mixture paste is not particularly limited, and is appropriately adjusted according to the required performance of the secondary battery. The mixing ratio of the materials can be in the same range as the known positive electrode mixture paste of the secondary battery. For example, when the total mass of the solid content of the positive electrode mixture excluding the solvent is 100 parts by mass, The content of the active material may be 60 parts by mass or more and 95 parts by mass or less, the content of the conductive material may be 1 part by mass or more and 20 parts by mass or less, and the content of the binder may be 1 part by mass or more and 20 parts by mass or less.

  As the conductive agent, for example, graphite (natural graphite, artificial graphite, expanded graphite, etc.), carbon black materials such as acetylene black, ketjen black, and the like can be used.

  The binder (binder) plays a role of holding the active material particles. For example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), fluorine rubber, ethylene propylene diene rubber, styrene butadiene, and cellulose resin. Polyacrylic acid or the like can be used.

  If necessary, a positive electrode active material, a conductive material, and activated carbon may be dispersed, and a solvent that dissolves the binder (binder) may be added to the positive electrode mixture paste. Specifically, an organic solvent such as N-methyl-2-pyrrolidone (NMP) may be used as the solvent. Further, activated carbon may be added to the positive electrode mixture in order to increase the electric double layer capacity.

  Next, the obtained positive electrode mixture paste is applied to, for example, the surface of a current collector made of aluminum foil, dried, and the solvent is scattered to produce a sheet-like positive electrode. If necessary, pressurization may be performed by a roll press or the like in order to increase the electrode density. The sheet-like positive electrode can be cut into an appropriate size or the like according to the target battery and used for battery production.

(Negative electrode)
For the negative electrode, metallic lithium, a lithium alloy, or the like may be used. In addition, for the negative electrode, a negative electrode active material that can occlude and desorb lithium ions is mixed with a binder, and an appropriate solvent is added to form a paste of the negative electrode mixture. You may apply | coat to the surface, dry, and what was compressed and formed so that the electrode density might be increased as needed.

  As the negative electrode active material, for example, natural graphite, artificial graphite, a fired organic compound such as phenol resin, or a powdery carbon material such as coke can be used. As the negative electrode binder, a fluorine-containing resin such as PVDF can be used as in the positive electrode. In addition, as a solvent for dispersing these active materials and binders, an organic solvent such as N-methyl-2-pyrrolidone can be used.

(Separator)
A separator is interposed between the positive electrode and the negative electrode. The separator separates the positive electrode and the negative electrode and retains the electrolyte, and a thin film such as polyethylene or polypropylene and a film having many minute holes can be used.

(Non-aqueous electrolyte)
The nonaqueous electrolytic solution is obtained by dissolving a lithium salt as a supporting salt in an organic solvent. Examples of the organic solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and trifluoropropylene carbonate; chain carbonates such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, and dipropyl carbonate; and tetrahydrofuran, 2- One kind selected from ether compounds such as methyltetrahydrofuran and dimethoxyethane, sulfur compounds such as ethylmethylsulfone and butanesultone, phosphorus compounds such as triethyl phosphate and trioctyl phosphate, etc. are used alone or in admixture of two or more. be able to.

As the supporting salt, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiN (CF ₃ SO ₂ ) ₂ , or a composite salt thereof can be used. Furthermore, the non-aqueous electrolyte solution may contain a radical scavenger, a surfactant, a flame retardant, and the like.

(Battery shape and configuration)
The shape of the non-aqueous electrolyte secondary battery of the present embodiment constituted by the positive electrode, the negative electrode, and the non-aqueous electrolyte that have been described above can be various types such as a cylindrical type and a laminated type. In any case, the positive electrode and the negative electrode are laminated via a separator to form an electrode body, and the obtained electrode body is impregnated with a non-aqueous electrolyte and communicated with the positive electrode current collector and the outside. The positive electrode terminal and the negative electrode current collector and the negative electrode terminal communicating with the outside are connected using a current collecting lead or the like and sealed in a battery case to complete a non-aqueous electrolyte secondary battery. . In addition, when employ | adopting a solid electrolyte, the solid electrolyte may serve as the separator.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Hereinafter, the evaluation method of the characteristic of the obtained positive electrode active material and the nonaqueous electrolyte secondary battery using this positive electrode active material is demonstrated. In addition, each sample of Wako Pure Chemical Industries, Ltd. reagent special grade was used for manufacture of a nickel composite hydroxide in this Example, and preparation of a positive electrode active material and a secondary battery.

[Drop strength]
The drop strength of the molded body was evaluated by the following method.
The obtained molded body was dropped from a height of 100 cm onto an iron plate having a thickness of 0.5 mm, and the presence or absence of cracks was observed. The case where cracks of the molded body were not observed was evaluated as “◯”, and the case where cracks of the molded body were observed was evaluated as “x”.

[Processing volume of lithium mixture]
The treatment amount (calcination amount) of the lithium mixture was determined by the following formula and evaluated by converting the value of Comparative Example 3 to 1.0.
The treatment amount of the lithium mixture (sometimes abbreviated as “treatment amount”) was evaluated. The processing amount of the lithium mixture was determined by the following formula.
Treatment amount: (T _(powder) / T _{(molded body)} ) × (L _{(molded body)} / L _(powder) × loss coefficient) (formula)
(In the above formula, T 1 _{(molded body)} is the holding time in the furnace at the time of firing the molded body (the time when the temperature is raised to the firing temperature (temperature raising time) and the holding time at the firing temperature (firing time)). T _(powder) is the holding time in the furnace when the powder is fired _(the sum of the time when the temperature is raised to the firing temperature (temperature rise time) and the holding time at the firing temperature (fire time)) L 1 _{(molded body)} represents the weight of the molded body per unit volume during firing (“unit volume during firing” multiplied by “density of molded body”), and L 2 _(powder) Indicates the weight of the lithium mixture of the powder per unit volume at the time of firing (a value obtained by multiplying the “unit volume at the time of firing” by “the density of the powder”), and the loss coefficient is 1.0 for the powder. Is the relative filling rate of the molded body, and the volume ratio of the lithium mixture (molded body) in the above "unit volume during firing" (It is a value according to.)
In the examples of the molded bodies (Examples 1 to 23, Comparative Examples 1 and 4 to 5), in the above formula, the processing amount of Comparative Example 3 (powder, holding time in the furnace: 15 hours) is 1.0, A unit or powder in a rectangular parallelepiped space of 100 cm in length, 100 cm in width, and 30 mm in thickness (height) (30 mm height in a unit hearth area (1 m ² ) of 100 cm in length and 100 cm in width). The volume when the body was charged (100 cm × 100 cm × 3 cm = 30000 [cm ³ ]) was set, and the loss factor of the molded body was set to 0.9.
For example, the processing amount of Example 3 is as follows: T _(powder) (Comparative Example 3) = 15 hours (temperature rising time: 2.7 hours, firing time: 12.3 hours), T _{(molded body} ) ₎ = 8 hours (temperature rising time: 2.8 hours, firing time: 5.2 hours), L _{(molded product)} × loss coefficient = 30000 cm ³ (unit volume) × 1.74 (density) × 0.9 ( Loss coefficient) = 47.0 [kg], L _(powder) (Comparative Example 3) = 30000 cm ³ (unit volume) × 1.00 (density) = 30.0 [kg], these values 2.9 is calculated as the processing amount. In addition, the loss coefficient of a present Example and a comparative example is a value calculated and set as an average value in an Example and a comparative example.

[Eluted lithium content]
The amount of eluted lithium (Li) refers to the amount of lithium dissolved in water when the positive electrode active material is dispersed in water, and was measured by the following method. First, ultrapure water was added to 100 ml of the obtained positive electrode active material (composite oxide) powder up to 100 ml and stirred to disperse the powder, followed by titration with hydrochloric acid having a concentration of 1 mol / liter. Measured to neutralization point. The alkali content neutralized with hydrochloric acid was defined as lithium on the surface of the composite oxide powder, and the mass ratio of lithium to the composite oxide was determined from the titration results. Tables 1 to 3 show the amount of lithium eluted in pure water (the amount of eluted lithium) with respect to the entire positive electrode active material.

[Lithium seat occupancy]
X-ray diffraction measurement was performed on the obtained positive electrode active material. X-ray diffraction measurement was performed by a powder X-ray diffraction method using Cu—Kα rays using a powder X-ray diffractometer (manufactured by PANalytical, X′Prt PRO). The obtained powder X-ray diffraction pattern was subjected to Rietveld analysis to determine the lithium site occupancy at the 3a site.

[Production and evaluation of secondary battery for evaluation]
A 2032 type coin-type battery CBA (see FIG. 7) was prepared by the following method, and the battery characteristics of the positive electrode active material were evaluated.

(Production of coin-type battery)
52.5 mg of positive electrode active material, 15 mg of acetylene black, and 7.5 mg of polytetrafluoroethylene resin (PTFE) are mixed and press molded to a diameter of 11 mm and a thickness of 100 μm at a pressure of 100 MPa to produce a positive electrode PE (electrode for evaluation). did. The produced positive electrode PE was dried at 120 ° C. for 12 hours in a vacuum dryer. Using the dried positive electrode PE, negative electrode NE, separator SE, and electrolytic solution, a coin-type battery CBA shown in FIG. 6 was produced in a glove box in an Ar atmosphere in which the dew point was controlled at −80 ° C.

Lithium metal is used for the negative electrode NE, and an equivalent mixed solution (made by Toyama Pharmaceutical Co., Ltd.) of ethylene carbonate (EC) and diethyl carbonate (DEC) using 1M LiPF ₆ as a supporting electrolyte is used for the electrolyte. It was. As the separator SE, a polyethylene porous film having a film thickness of 25 μm was used. The coin-type battery CBA has a gasket GA and a wave washer WW, and was assembled into a coin-shaped battery by the positive electrode can PC and the negative electrode can NC.

(Evaluation of initial charge / discharge capacity)
When the produced coin-type battery CBA is left for about 24 hours and the open circuit voltage OCV (Open Circuit Voltage) is stabilized, the current density with respect to the positive electrode is 0.1 mA / cm ² and charged to a cutoff voltage of 4.3 V. The capacity was the initial charge capacity, and the capacity when the battery was discharged to a cut-off voltage of 3.0 V after 1 hour of rest was taken as the initial discharge capacity.

[Battery efficiency]
The battery efficiency (initial charge / discharge efficiency) was calculated by the ratio of the initial discharge capacity to the initial charge capacity [(initial discharge capacity / initial charge capacity) × 100]. Moreover, the case where the battery efficiency (initial charge / discharge efficiency) was 87% or more was evaluated as “◯”, and the case where the battery efficiency was less than 87% was evaluated as “x”.

[Example 1]
(Lithium mixture manufacturing process)
As a precursor, a nickel composite hydroxide represented by Ni _0.70 Co _0.15 Mn _0.15 (OH) ₂ obtained by a crystallization method and a Li / Me ratio = 1.05 The weighed lithium hydroxide was sufficiently mixed using a shaker mixer device (TURBULA Type T2C manufactured by Willy et Bacofen (WAB)) to obtain a lithium mixture. The composition of the obtained lithium mixture is shown in Table 1.

(Molding process)
The obtained lithium mixture was put into a mold, and was pressed at a surface pressure (pressure) of 600 kgf / cm ² (58.8 MPa) using a press (“table press” model number: TB-50H, ASONE Co., Ltd.). Thus, a molded body having the density and size (vertical, horizontal, thickness, major axis, etc.) shown in Table 6 was obtained. Table 1 shows the characteristics of the obtained molded body. The shape of the molded body was a rectangular plate shape (cuboid shape) of length × width: 30 mm × 30 mm and thickness: 10 mm. The major axis is the length of the diagonal of a square in a cross section of a square of length x width: 30 mm x 30 mm in the cross section perpendicular to the thickness direction (pressurization surface) where the distance between any two points is maximum. (30 ² +30 ² ) ^1/2 mm = 42.4 mm.

(Baking process)
The obtained molded body was fired using a roller hearth kiln manufactured by NGK Corporation as a firing furnace. An assembly composed of a plurality of compacts was formed, the formed assembly was placed on an alumina setter, introduced into a firing furnace, and fired. The aggregate is formed by arranging a plurality of molded bodies in the vertical and horizontal directions so that the atmosphere gas passes through the aggregate, and stacking them to form the outer shape of the aggregate into a rectangular parallelepiped shape. The “loss coefficient” indicating the degree of filling per unit volume (vertical × horizontal × height: 100 cm × 100 cm × 3 cm = 30000 [cm ³ ]) was formed to be about 0.9. Firing is performed in an oxygen atmosphere (oxygen concentration: 100% by volume) from room temperature to the firing temperature (temperature raising time: 2.8 hours), and firing is performed at 870 ° C. (firing temperature) for 5.2 hours (firing time). Then, firing was performed at an atmospheric gas flow rate (10 L / min), and then pulverized to obtain lithium nickel composite oxide (positive electrode active material) particles. The holding time in the furnace was 8 hours, which is the sum of the temperature raising time (2.8 hours) and the firing time (5.2 hours). Table 1 shows the manufacturing conditions and the evaluation results of the obtained positive electrode active material.

[Examples 2 to 6]
In the molding step, the molded body and the positive electrode active material were subjected to the same conditions as in Example 1 except that the surface pressure (pressure), the density of the obtained molded body, and the size (thickness, major axis) were as shown in Table 1. The material was obtained and evaluated. Table 1 shows the production conditions and the evaluation results of the obtained molded body and positive electrode active material.

[Example 7]
Each metal element shown in Table 1 is used as the metal M, and the surface pressure (pressure) is adjusted in the molding step so that the density of the obtained molded body is as shown in Table 1, and the size of the molded body The positive electrode active material was obtained and evaluated under the same conditions as in Example 1 except that the thickness (thickness and major axis) was as shown in Table 1 and firing was performed at 850 ° C. Table 1 shows the manufacturing conditions and the evaluation results of the obtained positive electrode active material.

[Comparative Example 1]
In the molding step, the surface pressure (pressure) is adjusted so that the density of the obtained molded body is less than 1.6 g / cm ³ and the size (thickness, major axis) of the molded body is as shown in Table 1. The molded body and the positive electrode active material were obtained and evaluated under the same conditions as in Example 1 except that firing was performed at 850 ° C. for 9.8 hours. Table 1 shows the production conditions and the evaluation results of the obtained molded body and positive electrode active material.

[Comparative Examples 2 and 3]
The lithium mixture (powder) was charged into a mortar having a length of 100 mm, a width of 100 mm, and a height of 100 mm so that the input weight was almost the same, and the thickness was set to 30 mm. Except that, a molded body and a positive electrode active material were obtained and evaluated in the same manner as in Example 1. Table 1 shows the production conditions and the evaluation results of the obtained molded body and positive electrode active material.

[Evaluation result 1]
In the examples, a lithium mixture was used to produce a molded body having a thickness of 10 mm or more, a major axis of 30 mm or more, and a density of 1.6 g / cm ³ or more, followed by firing to obtain a positive electrode active material. . The positive electrode active materials obtained in the examples have a high lithium seat occupancy with a small amount of eluted lithium and a firing time of less than 10 hours. Moreover, it was shown that the secondary battery using the positive electrode active material obtained in the examples has high battery efficiency. Moreover, in the Example, it was shown that there is much processing amount in a baking process and production efficiency is high. Moreover, in the Example, it was shown that a strong molded object can be manufactured even if it uses the lithium mixture which does not contain a binder.

On the other hand, in Comparative Example 1 in which the density of the molded body was less than 1.6 g / cm ³ , the amount of the eluted lithium of the obtained positive electrode active material was large and the lithium seat occupation ratio was low as compared with the Examples. Moreover, in the secondary battery using the positive electrode active material obtained in the comparative example, the battery efficiency was low. In addition, the amount of treatment in the firing step was small.

  Further, in Comparative Example 2 in which the lithium mixture was not molded and the powder was baked for less than 10 hours in the same manner as in the past, the amount of lithium eluted in the obtained positive electrode active material as compared with the Example The lithium seat occupancy was low and the battery efficiency was low. In addition, the amount of treatment in the firing step was small.

  Further, in Comparative Example 3, which was baked for 12.3 hours in a powder state as in Comparative Example 2, the amount of eluted lithium in the positive electrode active material, lithium seat occupancy, and battery efficiency were implemented. Similar to the example. Moreover, compared with the Example, there was little processing amount in a baking process.

  From the above, when the powder of the lithium mixture is fired as in the prior art, a firing time of 10 hours or more is necessary. By forming and firing a molded body satisfying a specific condition, the firing time is less than 10 hours. It was shown that a lithium nickel composite oxide (positive electrode active material) having high crystallinity can be obtained with high productivity in the firing time.

  Next, examples and comparative examples in which the type of lithium compound, the mixing amount (Li / Me ratio) and the like are mainly different from those in Example 7 will be described below.

[Examples 8 to 12, Comparative Examples 4 and 5]
A molded body and a positive electrode active material were obtained and evaluated under the same conditions as in Example 7 except that the production conditions shown in Table 2 were used. Table 2 shows the production conditions and the evaluation results of the obtained molded body and positive electrode active material.

  In Example 8, as the lithium compound, dry lithium hydroxide having a moisture content of 4.8% (anhydrous lithium hydroxide was used).

  In Examples 9 and 10 and Comparative Example 4, as shown in Table 2, a lithium mixture containing a binder was used. As the binder, polyvinyl alcohol (PVA), polyacrylamide (PAM), or carboxymethyl cellulose (CMC) was used. In Example 9 and Comparative Example 4, carboxymethyl cellulose (CMC) was included as a binder in an amount of 2.0% by mass based on the total mass of the lithium mixture. In Example 10, as a binder, based on the total mass of the lithium mixture. And 0.5% by mass of polyvinyl alcohol (PVA), 0.5% by mass of polyacrylamide (PAM), and 1.0% by mass of carboxymethyl cellulose (CMC).

[Evaluation result 2]
In Example 8, a molded body was molded using lithium hydroxide having a moisture content of 5% or less (anhydrous lithium hydroxide) as the lithium compound, and the amount of lithium eluted was very large in a firing time of 2.2 hours. A positive electrode active material reduced and excellent in battery efficiency was obtained. Therefore, it was shown that the firing efficiency is greatly improved when anhydrous lithium hydroxide is used. Also,

  In Examples 9 and 10, a molded body was molded using lithium carbonate as a lithium compound, the amount of eluted lithium was small with a firing time of less than 10 hours, a high lithium seat occupancy rate, and It has been shown to have high battery efficiency. Therefore, even when using lithium carbonate, which is superior in cost compared with lithium hydroxide but difficult to obtain a lithium nickel composite oxide having high crystallinity, the lithium nickel composite oxide having high crystallinity is It was shown to be obtained.

  Further, in Examples 11 and 12 in which the Li / Me ratio was 0.95 or more and 1.30 or less, it was shown that a positive electrode active material having a reduced amount of eluted lithium and excellent battery efficiency was obtained. On the other hand, in Comparative Example 4 in which the Li / Me ratio was less than 0.95, the lithium seat occupancy was low, the amount of eluted lithium was large, and the battery efficiency was low. Moreover, in the comparative example 5 whose Li / Me ratio is more than 1.30, the lithium seat occupancy was low, the amount of eluted lithium was large, and the battery efficiency was low.

  Next, an example in which the composition of the nickel composite hydroxide mainly differs from that in Example 7 and the like and an example in which a calcination step is added will be described below.

[Examples 13 to 23]
A molded body and a positive electrode active material were obtained and evaluated under the same conditions as in Example 7 except that the production conditions shown in Table 3 were used.

  In Examples 14, 15, 17, and 23, as shown in Table 3, a lithium mixture containing a binder was used. The binder content in Examples 13, 15, and 17 is the same as that in Example 9, and in Example 23, it is the same as that in Example 10.

  In Examples 21 to 23, calcining was performed under conditions of 250 ° C. (8 hours), 500 ° C. (4 hours), and 800 ° C. (1 hour) in an air atmosphere before firing. Table 3 shows the production conditions and the evaluation results of the obtained molded body and positive electrode active material.

[Evaluation result 3]
In Examples 13 to 23, the nickel content is in the range of 55 atomic% or more and 100 atomic% or less, all of which have a firing amount of less than 10 hours, a small amount of eluted lithium, and a high lithium seat occupancy. It was also shown that a positive electrode active material having high battery efficiency can be obtained.

  In addition, in Examples 21 to 23 in which calcining was performed before firing, a positive electrode active material having a high lithium seat occupancy and excellent battery efficiency can be obtained in which the amount of eluted lithium is extremely reduced. Indicated.

  From the above, in the positive electrode active material obtained by the manufacturing method according to the present embodiment, the sintering reaction between the precursor and the lithium compound in the molded body (lithium mixture) proceeds very efficiently in the firing step. It is apparent that a positive electrode active material having high crystallinity and excellent battery characteristics can be obtained even by firing for a short time.

  The technical scope of the present invention is not limited to the aspects described in the above-described embodiments. One or more of the requirements described in the above embodiments and the like may be omitted. In addition, the requirements described in the above-described embodiments and the like can be combined as appropriate. In addition, as long as it is permitted by law, the disclosure of all documents cited in the above-described embodiments and the like is incorporated as a part of the description of the text.

DESCRIPTION OF SYMBOLS 1 ... Plate-shaped member 2 ... Container 10 ... Lithium mixture (powder)
20 ... Molded body 30 ... Aggregate CBA ... Coin-type battery NC ... Negative electrode can NE ... Negative electrode PC ... Positive electrode can PE ... Positive electrode SE ... Separator GA ... Gasket WW ... Wave washer

Claims (13)

Lithium (Li), nickel (Ni), cobalt (Co) and optionally other metals (M) are included, and the molar ratio of each metal element is Li: Ni: Co: M = s: (1-x− y): x: y (where 0.95 ≦ s ≦ 1.30, 0 ≦ x ≦ 0.40, 0 ≦ y ≦ 0.40, and 0.55 ≦ (1-xy) ≦ 1) 0.0, and M is at least one element selected from Mn, V, Mo, Nb, Ti, Zr, W, and Al.) A non-aqueous electrolyte containing a lithium nickel composite oxide A method for producing a positive electrode active material for a secondary battery, comprising:
A lithium mixture containing at least one of nickel composite hydroxide and nickel composite oxide and a lithium compound is molded, and the thickness is 10 mm or more, and the major axis of the cross section perpendicular to the thickness direction is 30 mm. And obtaining a molded body having a density of 1.6 g / cm ³ or more,
A method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery, comprising firing the molded body in an oxidizing atmosphere at 730 ° C. or more and 930 ° C. or less for less than 10 hours to obtain a lithium nickel composite oxide. . The manufacturing method of the positive electrode active material for nonaqueous electrolyte secondary batteries of Claim 1 whose density of the said molded object is 1.8 g / cm < ³ > or more.   The manufacturing method of the positive electrode active material for nonaqueous electrolyte secondary batteries of Claim 1 or Claim 2 which mounts the said molded object on the plate-shaped member arrange | positioned in a baking furnace, and bakes.   The said compact | molding | casting contains at least one of the said nickel composite hydroxide and the said nickel composite oxide, and lithium hydroxide, The binder is not included in any one of Claims 1-3. The manufacturing method of the positive electrode active material for non-aqueous electrolyte secondary batteries.   The method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 4, wherein the lithium hydroxide is anhydrous lithium hydroxide having a moisture content of 5% or less.   The non-aqueous system according to any one of claims 1 to 3, wherein the compact includes at least one of the nickel composite hydroxide and the nickel composite oxide, lithium carbonate, and a binder. A method for producing a positive electrode active material for an electrolyte secondary battery.   The method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 6, wherein the binder is at least one selected from polyvinyl alcohol, polyacrylamide, and carboxymethylcellulose.   The lithium mixture is calcined at 200 ° C. to 800 ° C. in an oxidizing atmosphere and at a temperature lower than the firing temperature, according to claim 1. A method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery.   The manufacturing method of the positive electrode active material for nonaqueous electrolyte secondary batteries as described in any one of Claims 1-8 provided with crushing the lithium nickel complex oxide obtained by baking.   The non-lithium composite oxide according to any one of claims 1 to 9, wherein the lithium nickel composite oxide has a lithium seat occupancy of 94% or more of a lithium main layer obtained from a Rietveld analysis of an X-ray diffraction pattern. A method for producing a positive electrode active material for an aqueous electrolyte secondary battery.   The lithium nickel composite oxide is dispersed in pure water and the amount of lithium eluted in the supernatant after standing is 0.15% by mass or less based on the total amount of the lithium nickel composite oxide. Item 11. A method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of Items 10 to 10. It contains nickel (Ni), cobalt (Co), and optionally other metals (M), and the molar ratio of each element is Ni: Co: M = (1-xy): x: y (however, , 0 ≦ x ≦ 0.40, 0 ≦ y ≦ 0.40, and 0.55 ≦ (1-xy) ≦ 1.0, and M is Mn, V, Mo, Nb, Ti, At least one element selected from Zr, W and Al.) And at least one of a nickel composite hydroxide obtained by oxidizing the nickel composite hydroxide; A molded body containing lithium hydroxide,
Does not contain binder
10 mm or more in thickness, the major axis of the cross section perpendicular to the thickness direction is 30 mm or more, and the density is 1.6 g / cm ³ or more.
The molded object used for manufacture of the positive electrode active material for non-aqueous electrolyte secondary batteries. A method for producing a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte,
A non-aqueous electrolyte secondary battery comprising: producing a positive electrode using the positive electrode active material for a non-aqueous electrolyte secondary battery obtained by the production method according to any one of claims 1 to 11. Manufacturing method.

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