JP5092292B2 - Positive electrode active material, method for producing the same, and nonaqueous electrolyte secondary battery - Google Patents

Description

  The present invention relates to a positive electrode active material, a method for producing the same, and a nonaqueous electrolyte secondary battery. For example, a positive electrode active material containing a composite oxide containing lithium (Li) and cobalt (Co), a method for producing the same, and The present invention relates to a nonaqueous electrolyte secondary battery using the positive electrode active material.

  In recent years, with the spread of portable devices such as video cameras and notebook personal computers, the demand for small and high-capacity secondary batteries is increasing. Currently used secondary batteries include nickel-cadmium batteries using an alkaline electrolyte, but the battery voltage is as low as about 1.2 V, and it is difficult to improve the energy density. For this reason, a lithium metal secondary battery using lithium metal having a specific gravity of 0.534, which is the lightest of the solid simple substance, the potential is extremely base, and the current capacity per unit weight is the largest among the metal negative electrode materials. It was done.

  However, in a secondary battery using lithium metal as a negative electrode, dendritic lithium (dendrites) is deposited on the surface of the negative electrode during charging and grows by charge / discharge cycles. The growth of the dendrite has problems such as deterioration of the cycle characteristics of the secondary battery, and further breaking through a diaphragm (separator) disposed so that the positive electrode and the negative electrode are not in contact with each other, thereby causing an internal short circuit.

  Therefore, for example, as described in Patent Document 1, a secondary battery that repeats charging and discharging by using a carbonaceous material such as coke as a negative electrode and doping and dedoping alkali metal ions is provided. was suggested. As a result, it has been found that the above-described problem of deterioration of the negative electrode due to repeated charge / discharge can be avoided.

JP 62-90863 A

  On the other hand, as positive electrode active materials, inorganic compounds such as transition metal oxides and transition metal chalcogens containing alkali metals are known as those capable of obtaining a battery voltage of around 4V. Among these, lithium composite oxides such as lithium cobaltate or lithium nickelate are most promising in terms of high potential, stability, and long life.

In particular, a positive electrode active material mainly composed of lithium cobaltate is a positive electrode active material exhibiting a high potential, and is expected to increase the energy density by increasing the charging voltage. However, there is a problem that the cycle characteristics deteriorate when the charging voltage is increased. Therefore, conventionally, a method of modifying the positive electrode active material by using a small amount of LiMn _1/3 Co _1/3 Ni _1/3 O ₂ or the like, or coating the surface with another material has been performed. .

By the way, the technique for modifying the positive electrode active material by the surface coating of the positive electrode active material described above has a problem of achieving high coverage. In order to solve this problem, various methods have been proposed. For example, it has been confirmed that the method of depositing with a metal hydroxide is excellent in covering properties. As such a method, for example, Patent Document 2 discloses the surface of lithium nickelate (LiNiO ₂ ) particles. Discloses the deposition of cobalt (Co) and manganese (Mn) through its hydroxide deposition process. For example, Patent Document 3 discloses that a non-manganese metal is deposited on the surface of a lithium manganese composite oxide through a hydroxide deposition process.

JP-A-9-265985 JP-A-11-71114

  However, when heat treatment is performed after depositing a metal hydroxide on the composite oxide particles, there is a problem that sintering is likely to proceed between the particles and the particles are likely to be bound to each other. As a result, when mixed with a conductive agent or the like when producing the positive electrode, the bonded portion and particles are broken or cracked, the coating layer is peeled off, and the damaged surface of the particles is exposed. End up. Such a damaged surface is very active compared to the surface formed at the time of firing, and the deterioration reaction of the electrolytic solution and the positive electrode active material is likely to occur.

  Accordingly, an object of the present invention is to provide a positive electrode active material capable of further improving chemical stability by suppressing the binding between particles, a method for producing the same, and a high capacity and charge / discharge cycle characteristic using these. The object is to provide a water electrolyte secondary battery.

In order to solve the above-mentioned problem, the first invention
Composite oxide particles including at least lithium (Li) as a first layer and cobalt (Co);
Oxidation including lithium (Li) as the second layer and at least one covering element of nickel (Ni) and manganese (Mn) provided on at least a part of the surface of the composite oxide particle A coating layer made of material,
A surface layer containing boron (B), which is a third layer, provided by adding borate to at least a part of the coating layer and firing the same;
Is a positive electrode active material.

In the first invention, the composite oxide particles preferably have an average composition represented by Chemical Formula 1.
(Chemical formula 1)
_{Li (1 + x) Co (} 1-y) M y O (2-z)
(In the chemical formula 1, M is magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), and tungsten (W), x, y, and z are −0. 10 ≦ x ≦ 0.10, 0 ≦ y <0.50, −0.10 ≦ z ≦ 0.20.

  In 1st invention, it is preferable that the structural ratio of nickel (Ni) and manganese (Mn) in a coating layer exists in the range of 100: 0 to 30:70 by molar ratio.

  In the first invention, the oxide of the coating layer is 40 mol% or less of the total amount of nickel (Ni) and manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti). , Vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), tungsten (W) It is preferable to replace the at least one metal element.

  In 1st invention, it is preferable that the quantity of a coating layer exists in the range of 0.5 weight%-50 weight% of complex oxide particle.

  In 1st invention, it is preferable that an average particle diameter exists in the range of 2.0 micrometers-50 micrometers.

The second invention is
It consists of a hydroxide containing nickel (Ni) and / or manganese (Mn) on at least a part of the surface of the composite oxide particles containing at least lithium (Li) as the first layer and cobalt (Co). After forming the layer, a step of depositing a borate in at least a part of the composite oxide particles,
After depositing a borate, by heating, it provided on at least part of the surface of the composite oxide particles, and lithium (Li) as the second layer, nickel (Ni) and manganese ( Forming a coating layer made of an oxide containing at least one coating element of Mn) and a surface layer containing boron (B) as a third layer provided on at least a part of the coating layer And a process of
It is a manufacturing method of the positive electrode active material which has this.

In the second invention, the composite oxide particles preferably have an average composition represented by Chemical Formula 1.
(Chemical formula 1)
_{Li (1 + x) Co (} 1-y) M y O (2-z)
(In the chemical formula 1, M is magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), and tungsten (W), x, y, and z are −0. 10 ≦ x ≦ 0.10, 0 ≦ y <0.50, −0.10 ≦ z ≦ 0.20.

In the second invention, the formation of a hydroxide containing nickel (Ni) and / or manganese (Mn)
It is preferable to carry out by adding the compound of nickel (Ni) and / or the compound of manganese (Mn) after dispersing the composite oxide particles in a solvent mainly composed of water having a pH of 12 or more.

  Furthermore, in the second invention, it is preferable that the solvent mainly composed of water contains lithium hydroxide.

  In 2nd invention, it is preferable that the structural ratio of nickel (Ni) and manganese (Mn) in a coating layer exists in the range of 100: 0 to 30:70 by molar ratio.

  In the second invention, the oxide of the coating layer is 40 mol% or less of the total amount of nickel (Ni) and manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti). , Vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), tungsten (W) It is preferable to replace the at least one metal element.

  In 2nd invention, it is preferable that the quantity of a coating layer exists in the range of 0.5 weight%-50 weight% of complex oxide particle.

  In the second invention, the positive electrode active material preferably has an average particle size in the range of 2.0 μm to 50 μm.

The third invention is
A positive electrode having a positive electrode active material, a negative electrode, and an electrolyte;
The positive electrode active material is
Composite oxide particles including at least lithium (Li) as a first layer and cobalt (Co);
Oxidation including lithium (Li) as the second layer and at least one covering element of nickel (Ni) and manganese (Mn) provided on the surface of at least a part of the composite oxide particles A coating layer made of material,
A surface layer containing boron (B), which is a third layer, provided by adding borate to at least a part of the coating layer and firing the same;
Is a non-aqueous electrolyte secondary battery.

  In this invention, since at least a part of the composite oxide particles includes a coating layer made of an oxide containing lithium (Li) and at least one of the coating elements of nickel (Ni) and manganese (Mn), High charge voltage characteristics and high energy density characteristics associated therewith can be realized, and it has good charge / discharge cycle characteristics under high charge voltage conditions.

  In this invention, the adhesion between particles can be suppressed by applying boric acid to the composite oxide particles provided with a hydroxide containing at least one of nickel (Ni) and manganese (Mn). .

  According to this invention, the stability of the positive electrode active material can be further improved. Moreover, the battery using this positive electrode active material can obtain a high capacity | capacitance, and can improve charging / discharging efficiency.

  Embodiments of the present invention will be described below with reference to the drawings. The positive electrode active material according to one embodiment of the present invention includes an oxide containing lithium (Li) and at least one covering element of nickel (Ni) and manganese (Mn) in at least a part of the composite oxide particles. And a surface layer containing boric acid is provided on at least a part of the coating layer.

First, the reason why the positive electrode active material is configured as described above will be described. The positive electrode active material mainly composed of lithium cobalt oxide (LiCoO ₂ ) can realize high charge voltage and high energy density accompanying it, but if the charge / discharge cycle at high capacity is repeated at high charge voltage, the capacity of the positive electrode active material is increased. There is a lot of decline. Since this cause is caused by the surface of the positive electrode active material particles, the necessity of surface treatment of the positive electrode active material has been pointed out.

  Therefore, various surface treatments have been proposed, but the surface is made of a material that can suppress or contribute to the capacity reduction from the viewpoint of eliminating the capacity reduction per volume or weight or minimizing the capacity reduction. By performing the treatment, it is possible to achieve a high charge voltage property and a high energy density property associated therewith and to obtain a positive electrode active material excellent in charge / discharge cycle characteristics at a high charge voltage.

Accordingly, the inventors of the present application have made a intensive study, and although slightly inferior in the high charge voltage property and the high energy density property associated therewith, the positive electrode active material mainly composed of lithium cobaltate (LiCoO ₂ ) is used as lithium (Li). And providing a coating layer made of an oxide containing at least one of the covering elements of nickel (Ni) and manganese (Mn), has high charging voltage and high energy density associated therewith, and It has been found that a positive electrode active material having a high capacity and excellent charge / discharge cycle characteristics can be obtained under high charge voltage conditions.

  As a method of providing a coating layer on the composite oxide particles, lithium (Li) compound, nickel (Ni) compound and / or manganese (Mn) compound are dry-mixed as composite oxide particles and finely pulverized particles. A method of providing a coating layer made of an oxide containing lithium (Li) and at least one of the coating elements of nickel (Ni) and manganese (Mn) on the surface of the composite oxide particles; Lithium (Li) compound, nickel (Ni) compound and / or manganese (Mn) compound are dissolved or mixed in a solvent, wet-coated and fired, and lithium (Li) and nickel (Ni ) And manganese (Mn), and a method of providing a coating layer made of an oxide containing at least one coating element on the surface of the composite oxide particle. However, these methods yielded results in which a highly uniform coating could not be achieved.

  Therefore, the inventors of the present application have further studied diligently. As a result, nickel (Ni) and / or manganese (Mn) was deposited as a hydroxide and heated and dehydrated to form a coating layer. It was found that highly uniform coating can be realized. In this deposition treatment, a nickel (Ni) compound and / or a manganese (Mn) compound is dissolved in a water-based solvent system, and then the composite oxide particles are dispersed in the solvent system. The basicity of the dispersion is increased by adding a base to the system, and a hydroxide containing nickel (Ni) and / or manganese (Mn) is precipitated on the surface of the composite oxide particles.

  Furthermore, the inventors of the present application have found that the uniformity of coating on the composite oxide particles can be further improved by performing this deposition treatment in a solvent system mainly composed of water having a pH of 12 or higher. That is, the metal composite oxide particles are dispersed in advance in a solvent system mainly composed of water having a pH of 12 or more, and a nickel (Ni) compound and / or a manganese (Mn) compound is added to the metal composite oxide. A hydroxide containing nickel (Ni) and / or manganese (Mn) is deposited on the surface of the product particles.

  Then, by the deposition treatment, the composite oxide particles deposited with hydroxide containing nickel (Ni) and / or manganese (Mn) are heated and dehydrated to form a coating layer on the surface of the composite oxide particles. . Thereby, the uniformity of the coating on the surface of the composite oxide particles can be improved.

  However, the inventors of the present application have made further studies and applied a hydroxide containing nickel (Ni) and / or manganese (Mn) to the surface of the composite oxide particles, and washed to fire this. In the process of dehydration and drying, the particles are bound to each other via a hydroxide containing nickel (Ni) and / or manganese (Mn) on the surface, and when the particles are crushed, the particles are relatively bonded. Interfacial delamination between hydroxide and composite oxide particles containing weak nickel (Ni) and / or manganese (Mn), or hydroxide containing nickel (Ni) and / or manganese (Mn) having weak cohesive strength Cohesive failure occurs. In connection with this, it discovered that the characteristic improvement of the positive electrode active material by providing a coating layer was impaired.

  Furthermore, the inventors of the present application leave lithium particles (Li) in a state in which particles having a hydroxide containing nickel (Ni) and / or manganese (Mn) are in contact with each other while leaving the particles bonded together. It was found that the sintering between the particles tends to proceed as the baking is performed.

  When sintering between particles proceeds, there is a problem described below. In the formation of the positive electrode, it is necessary to increase the input amount of mechanical energy in the pulverization of the particles in order to uniformly mix the particles with the carbon particles as the finalizing agent and the conductive agent. Along with this, the positive electrode active material composed of composite oxide particles provided with a coating layer is damaged or broken, and the total amount of defects as powder increases.

Note that the breakage or breakage occurs in the form of breakage of the connecting portion between the sintered particles, formation of cracks in the particles themselves, crushing of the particles themselves, peeling of the coating layer, and the like. In particular, in the composite oxide particles provided with the coating layer, the surface shape of the particles is not smooth and has irregularities on the surface as compared with particles such as a positive electrode active material mainly composed of lithium cobaltate (LiCoO ₂ ). There is a tendency. For this reason, when an external force is applied, it is considered that the slip between particles is poor, the external force is easily concentrated locally, and is easily damaged or destroyed.

  As a result, the surface where the coating layer is not provided is exposed. That is, a surface not provided with a coating layer that does not function to improve charge / discharge cycle characteristics and an active new surface are exposed. Therefore, the high-capacity charge / discharge cycle characteristics deteriorate under high charge voltage conditions. The exposed surface is active and has a high surface energy as is well known. For this reason, the decomposition reaction of the electrolytic solution and the elution activity of the surface are extremely high as compared with the surface formed by normal firing.

  Accordingly, the inventors of the present application have made extensive studies for the purpose of improving the deterioration of the positive electrode function and improving the manufacturing process based on the sintering between particles, and water containing nickel (Ni) and / or manganese (Mn). It has been found that the progress of sintering can be improved by further depositing boric acid on the surface of the composite oxide particles to which the oxide is deposited. Along with this, it was found that particle breakage or destruction can be reduced. Next, the composite oxide particles, the coating layer, and the surface layer will be described.

[Composite oxide]
The composite oxide particles contain at least lithium (Li) and cobalt (Co). For example, it is preferable that the average composition is represented by Chemical Formula 1. By using such composite oxide particles, a high capacity and a high discharge potential can be obtained.

(Chemical formula 1)
_{Li (1 + x) Co (} 1-y) M y O (2-z)
(In the chemical formula 1, M is magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), and tungsten (W), x, y, and z are −0. 10 ≦ x ≦ 0.10, 0 ≦ y <0.50, −0.10 ≦ z ≦ 0.20.

  Here, in Chemical Formula 1, the range of x is, for example, −0.10 ≦ x ≦ 0.10, more preferably −0.08 ≦ x ≦ 0.08, and further preferably −0.06 ≦. x ≦ 0.06. If the value decreases outside this range, the discharge capacity will decrease. If the value increases outside this range, it diffuses out of the particles and becomes an obstacle to the control of the basicity of the next processing step, and finally causes the harmful effects of gelation promotion during the kneading of the positive electrode paste. It becomes.

The range of y is, for example, 0 ≦ y <0.50, preferably 0 ≦ y <0.40, and more preferably 0 ≦ y <0.30. When it becomes larger than this range, the high charge voltage property of LiCoO ₂ and the high energy density property associated therewith are impaired.

  The range of z is, for example, −0.10 ≦ z ≦ 0.20, more preferably −0.08 ≦ z ≦ 0.18, and still more preferably −0.06 ≦ z ≦ 0.16. When the value decreases outside this range, and when the value increases outside this range, the discharge capacity tends to decrease.

  The composite oxide particles can be used as starting materials that are usually available as positive electrode active materials, but in some cases, the composite oxide particles may be used after pulverizing the secondary particles using a ball mill or a grinder. it can.

[Coating layer]
The coating layer is provided on at least a part of the composite oxide particles and is made of an oxide containing lithium (Li) and at least one coating element of nickel (Ni) and manganese (Mn). By providing this coating layer, it is possible to realize a high charge voltage property and a high energy density property associated therewith, and to improve charge / discharge cycle characteristics of a high capacity under a high charge voltage condition.

  The constituent ratio of nickel (Ni) and manganese (Mn) in the coating layer is preferably in the range of 100: 0 to 30:70 and in the range of 100: 0 to 40:60 in terms of molar ratio. Is more preferable. If the amount of manganese (Mn) increases beyond this range, the occlusion of lithium (Li) will decrease, eventually reducing the capacity of the positive electrode active material and increasing the electrical resistance when used in a battery. It is a factor. In addition, the range of the composition ratio of nickel (Ni) and manganese (Mn) is a range showing more effectiveness in suppressing the progress of sintering between particles in the firing of the precursor added with lithium (Li). is there.

  In addition, nickel (Ni) and manganese (Mn) in the oxide of the coating layer are replaced with magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron It can be replaced with at least one metal element selected from the group consisting of (Fe), cobalt (Co), copper (Cu), zinc (Zn), tin (Sn), and tungsten (W).

  Thereby, the stability of the positive electrode active material and the diffusibility of lithium ions can be improved. The substitution amount of the selected metal element is, for example, 40 mol% or less of the total amount of nickel (Ni) and manganese (Mn) of the oxide of the coating layer, preferably 30 mol% or less, and more Preferably it is 20 mol% or less. This is because if the substitution amount of the selected metal element is increased beyond this range, the occlusion of lithium (Li) is lowered and the capacity of the positive electrode active material is lowered.

  The amount of the coating layer is, for example, 0.5% to 50% by weight of the composite oxide particles, preferably 1.0% to 40% by weight, and more preferably 2.0% by weight. % To 35% by weight. This is because when the coating weight of the metal oxide exceeds this range, the capacity of the positive electrode active material decreases. This is because when the coating weight of the metal oxide is lower than this range, the stability of the positive electrode active material is lowered.

[Surface layer]
The surface layer is provided on at least a part of the coating layer and contains boron (B).

  The average particle diameter of the positive electrode active material is preferably 2.0 μm to 50 μm. If the average particle size is less than 2.0 μm, it peels off when pressed during positive electrode fabrication, and the surface area of the active material increases, so it is necessary to increase the amount of conductive agent and binder added, and the unit weight This is because the per-energy density tends to decrease. On the other hand, if the average particle size exceeds 50 μm, the particles tend to penetrate the separator and cause a short circuit.

[Method for producing positive electrode active material]
Next, the manufacturing method of the positive electrode active material by one Embodiment of this invention is demonstrated. According to an embodiment of the present invention, there is provided a method for producing a positive electrode active material, wherein a layer made of a hydroxide containing nickel (Ni) and / or manganese (Mn) is formed on at least a part of composite oxide particles, and then composite oxidation is performed. A first step of depositing boric acid on at least a part of the product particles; and by applying heat treatment after depositing boric acid, lithium (Li) and at least a part of the composite oxide particles; It can be roughly divided into a second step of forming a coating layer made of an oxide containing at least one of the coating elements of nickel (Ni) and manganese (Mn), and a surface layer containing boron (B).

(First step)
In the first step, a hydroxide containing nickel (Ni) and / or manganese (Mn) and boric acid are applied. In the first step, for example, first, the composite oxide particles are dispersed in a solvent system mainly composed of water in which a nickel (Ni) compound and / or a manganese (Mn) compound is dissolved. The basicity of the dispersion is increased by adding a base and the like, and a hydroxide containing nickel (Ni) and / or manganese (Mn) is precipitated on the surface of the composite oxide particles. The composite oxide particles are dispersed in a solvent mainly composed of basic water, and then a nickel (Ni) compound and / or a manganese (Mn) compound is added to the aqueous solution to obtain nickel (Ni). And / or a hydroxide containing manganese (Mn) may be deposited.

  As a raw material for the deposition treatment of hydroxide containing nickel (Ni), nickel compounds include, for example, nickel hydroxide, nickel carbonate, nickel nitrate, nickel fluoride, nickel chloride, nickel bromide, nickel iodide, Inorganic compounds such as nickel chlorate, nickel bromate, nickel iodate, nickel oxide, nickel peroxide, nickel sulfide, nickel sulfate, nickel hydrogen sulfate, nickel nitride, nickel nitrite, nickel phosphate, nickel thiocyanate, or Organic compounds such as nickel oxalate and nickel acetate can be used, and one or more of these may be used.

  In addition, as a raw material for the deposition treatment of hydroxide containing manganese (Mn), manganese compounds include, for example, manganese hydroxide, manganese carbonate, manganese nitrate, manganese fluoride, manganese chloride, manganese bromide, manganese iodide. , Manganese chlorate, manganese perchlorate, manganese bromate, manganese iodate, manganese oxide, manganese phosphinate, manganese sulfide, manganese sulfide, manganese nitrate, manganese hydrogen sulfate, manganese thiocyanate, manganese nitrite, manganese phosphate Inorganic compounds such as manganese dihydrogen phosphate and manganese hydrogen carbonate, or organic compounds such as manganese oxalate and manganese acetate can be used, and one or more of these may be used.

  The pH of the above-described solvent system mainly composed of water is, for example, pH 12 or more, preferably pH 13 or more, and more preferably pH 14 or more. The higher the pH value of the water-based solvent system described above, the better the uniformity of the deposition of hydroxide containing nickel (Ni) and / or manganese (Mn), and the higher the reaction accuracy, There are advantages in improving productivity and quality by shortening the processing time. Further, the pH of the solvent system mainly composed of water is determined by the balance with the cost of the alkali used.

  The temperature of the treatment dispersion is, for example, 40 ° C. or higher, preferably 60 ° C. or higher, and more preferably 80 ° C. or higher. The higher the value of the temperature of the treatment dispersion, the better the uniformity of the deposition of the hydroxide containing nickel (Ni) and / or manganese (Mn), the higher the reaction rate, and the production by shortening the treatment time. There is an advantage of improvement in quality and quality. Although it is determined in consideration of the cost and productivity of the equipment, it can be performed at 100 ° C. or higher using an autoclave, and production by shortening the processing time by improving the uniformity of deposition and improving the reaction rate. From the point of view, it can be recommended.

  Furthermore, the pH of a solvent system mainly composed of water can be reached by dissolving an alkali in the solvent system mainly composed of water. Examples of the alkali include lithium hydroxide, sodium hydroxide and potassium hydroxide, and mixtures thereof. Although these alkalis can be used as appropriate, it is excellent to use lithium hydroxide from the viewpoint of the purity and performance of the positive electrode active material according to one embodiment finally obtained. The advantage of using lithium hydroxide is that when the composite oxide particles in which a hydroxide containing nickel (Ni) and / or manganese (Mn) is formed are taken out from a solvent system mainly composed of water, This is because the amount of lithium in the positive electrode active material according to an embodiment finally obtained can be controlled by controlling the amount of the dispersion medium made of a solvent mainly composed of.

  Next, boric acid is applied to at least a part of the composite oxide particles in which a layer made of a hydroxide containing nickel (Ni) and / or manganese (Mn) is formed. In the boric acid deposition treatment, composite oxide particles formed with a hydroxide layer containing nickel (Ni) and / or manganese (Mn) are mixed with water containing nickel (Ni) and / or manganese (Mn). It is effective to carry out the process in a suspended state in a solvent system mainly composed of water to which an oxide is applied. Thus, in the step of dehydrating and drying the composite oxide particles formed with the hydroxide layer containing nickel (Ni) and / or manganese (Mn), the surface nickel (Ni) and / or manganese ( It is possible to suppress the particles from being bound to each other through a hydroxide containing Mn).

  Further, it is effective to perform boric acid deposition treatment in a cleaning stage after deposition treatment of a hydroxide containing nickel (Ni) and / or manganese (Mn). Thereby, the leakage of boric acid added to the suspension system can be prevented and the adsorptivity can be improved. Furthermore, by performing boric acid deposition treatment, it is possible to obtain a particle aggregation promoting effect without binding between particles in a suspension system, and to perform a washing operation and a recovery operation of particles from a dispersion medium. It can be done easily.

  In this invention, boric acid includes monomeric acids such as orthoboric acid and perboric acid, and condensed acids thereof in the concept of boric acid. Examples of raw materials for boric acid compounds that can be used for deposition treatment include orthoboric acid, acids such as hypoboric acid and metaboric acid, or ammonium borate, ammonium tetraborate, ammonium pentaborate, and tetrabora. Salts of lithium acid, lithium metaborate, magnesium borate, sodium borate, sodium metaborate, sodium tetraborate, sodium perborate, potassium metaborate, potassium borate, potassium tetraborate, etc. You may use 1 type, or 2 or more types.

  The boric acid deposition weight is, for example, 0.00001 wt% to 1.0 wt% with respect to the weight of the composite oxide particles. The deposition weight is preferably 0.0001% to 0.1% by weight. If the boric acid deposition weight increases beyond this range, the capacity of the positive electrode active material decreases. If the boric acid deposition weight is reduced from this range, the stability of the positive electrode active material is lowered.

(Second step)
In the second step, the composite oxide particles deposited in the first step are separated from the solvent system mainly composed of water, and then the hydroxide is dehydrated by heat treatment, whereby the composite oxide particles A surface layer containing lithium (Li) and an oxide containing an oxide containing at least one of nickel (Ni) and manganese (Mn) and a surface layer containing boron (B) are formed. Here, the heat treatment is preferably performed at a temperature of about 300 ° C. to 1000 ° C. in an oxidizing atmosphere such as air or pure oxygen. At this time, boric acid is deposited on a hydroxide containing nickel (Ni) and / or manganese (Mn), so that sintering between particles is suppressed and binding between particles is suppressed.

  In addition, after separating the composite oxide particles subjected to the deposition treatment in the first step from the solvent system, the composite oxide particles are impregnated with an aqueous solution of a lithium compound to adjust the amount of lithium if necessary. Thereafter, heat treatment may be performed.

  Examples of the lithium compound include lithium hydroxide, lithium carbonate, lithium nitrate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium chlorate, lithium perchlorate, lithium bromate, lithium iodate, and oxidation. Inorganic compounds such as lithium, lithium peroxide, lithium sulfide, lithium hydrogen sulfide, lithium sulfate, lithium hydrogen sulfate, lithium nitride, lithium azide, lithium nitrite, lithium phosphate, lithium dihydrogen phosphate, lithium hydrogen carbonate, Alternatively, an organic compound such as methyl lithium, vinyl lithium, isopropyl lithium, butyl lithium, phenyl lithium, lithium oxalate, or lithium acetate can be used.

  Further, after firing, the particle size may be adjusted by light pulverization or classification operation, if necessary.

  Next, a non-aqueous electrolyte secondary battery using the positive electrode active material according to one embodiment of the present invention described above will be described.

(1) First Example of Nonaqueous Electrolyte Secondary Battery (1-1) Configuration of Nonaqueous Electrolyte Secondary Battery FIG. 1 is a nonaqueous electrolyte secondary battery using a positive electrode active material according to an embodiment of the present invention. The cross-sectional structure of is shown.

  In this secondary battery, the open circuit voltage in a fully charged state per pair of positive electrode and negative electrode is, for example, 4.25V or more and 4.65V or less.

  This secondary battery is a so-called cylindrical type, and is a wound electrode in which a strip-shaped positive electrode 2 and a strip-shaped negative electrode 3 are wound via a separator 4 inside a substantially hollow cylindrical battery can 1. It has a body 20.

  The battery can 1 is made of, for example, iron (Fe) plated with nickel (Ni), and has one end closed and the other end open. Inside the battery can 1, a pair of insulating plates 5 and 6 are arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 20.

  At the open end of the battery can 1, a battery lid 7, a safety valve mechanism 8 and a thermal resistance element (PTC element) 9 provided inside the battery lid 7 are interposed via a gasket 10. It is attached by caulking, and the inside of the battery can 1 is sealed. The battery lid 7 is made of, for example, the same material as the battery can 1. The safety valve mechanism 8 is electrically connected to the battery lid 7 via a heat sensitive resistance element 9, and the disk plate 11 is reversed when the internal pressure of the battery becomes a certain level or more due to internal short circuit or external heating. Thus, the electrical connection between the battery lid 7 and the wound electrode body 20 is cut off. The heat-sensitive resistor element 9 limits the current by increasing the resistance value when the temperature rises, and prevents abnormal heat generation due to a large current. The gasket 10 is made of, for example, an insulating material, and asphalt is applied to the surface.

  The wound electrode body 20 is wound around, for example, the center pin 12. A positive electrode lead 13 made of, for example, aluminum (Al) or the like is connected to the positive electrode 2 of the spirally wound electrode body 20, and a negative electrode lead 14 made of, for example, nickel (Ni) or the like is connected to the negative electrode 3. The positive electrode lead 13 is electrically connected to the battery cover 7 by being welded to the safety valve mechanism 8, and the negative electrode lead 14 is welded and electrically connected to the battery can 1.

[Positive electrode]
FIG. 2 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. As shown in FIG. 2, the positive electrode 2 includes, for example, a positive electrode current collector 2A having a pair of opposed surfaces, and a positive electrode mixture layer 2B provided on both surfaces of the positive electrode current collector 2A. In addition, you may make it have the area | region where the positive mix layer 2B was provided only in the single side | surface of 2 A of positive electrode collectors. The positive electrode current collector 2A is made of, for example, a metal foil such as an aluminum (Al) foil. The positive electrode mixture layer 2B includes, for example, a positive electrode active material, and may include a conductive agent such as graphite and a binder such as polyvinylidene fluoride as necessary. As the positive electrode active material, the positive electrode active material according to the above-described embodiment can be used.

[Negative electrode]
As shown in FIG. 2, the negative electrode 3 includes, for example, a negative electrode current collector 3A having a pair of opposed surfaces, and a negative electrode mixture layer 3B provided on both surfaces of the negative electrode current collector 3A. In addition, you may make it have the area | region in which the negative mix layer 3B was provided only in the single side | surface of 3 A of negative electrode collectors. The negative electrode current collector 3A is made of a metal foil such as a copper (Cu) foil. The negative electrode mixture layer 3B includes, for example, a negative electrode active material, and may include a binder such as polyvinylidene fluoride as necessary.

The negative electrode active material includes a negative electrode material capable of inserting and extracting lithium (Li) (hereinafter referred to as a negative electrode material capable of inserting and extracting lithium (Li) as appropriate). Examples of negative electrode materials capable of inserting and extracting lithium (Li) include carbon materials, metal compounds, oxides, sulfides, lithium nitrides such as LiN ₃ , lithium metals, metals that form alloys with lithium, and high Examples include molecular materials.

  Examples of the carbon material include non-graphitizable carbon, graphitizable carbon, graphite, pyrolytic carbons, cokes, glassy carbons, organic polymer compound fired bodies, carbon fibers, and activated carbon. Among these, examples of coke include pitch coke, needle coke, and petroleum coke. An organic polymer compound fired body is a carbonized material obtained by firing a polymer material such as a phenol resin or a furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon. Some are classified as: Examples of the polymer material include polyacetylene and polypyrrole.

  Among such negative electrode materials capable of inserting and extracting lithium (Li), those having a charge / discharge potential relatively close to lithium metal are preferable. This is because the lower the charge / discharge potential of the negative electrode 3, the easier it is to increase the energy density of the battery. Among these, a carbon material is preferable because a change in crystal structure that occurs during charge / discharge is very small, a high charge / discharge capacity can be obtained, and good cycle characteristics can be obtained. In particular, graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density. Moreover, non-graphitizable carbon is preferable because excellent cycle characteristics can be obtained.

  Examples of the negative electrode material capable of inserting and extracting lithium (Li) include lithium metal alone, a metal element or metalloid element simple substance, alloy or compound capable of forming an alloy with lithium (Li). These are preferable because a high energy density can be obtained, and in particular, when used together with a carbon material, a high energy density can be obtained and excellent cycle characteristics can be obtained, and therefore, it is more preferable. Note that in this specification, alloys include those composed of one or more metal elements and one or more metalloid elements in addition to those composed of two or more metal elements. The structures include solid solutions, eutectics (eutectic mixtures), intermetallic compounds, or those in which two or more of them coexist.

Examples of such metal elements or metalloid elements include tin (Sn), lead (Pb), aluminum (Al), indium (In), silicon (Si), zinc (Zn), antimony (Sb), and bismuth. (Bi), cadmium (Cd), magnesium (Mg), boron (B), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), zirconium (Zr), yttrium (Y) or hafnium (Hf). These alloys or compounds, for example, those represented by the chemical formula Ma _s Mb _t Li _u or a chemical formula Ma _p Mc _q Md _r,. In these chemical formulas, Ma represents at least one of a metal element and a metalloid element capable of forming an alloy with lithium, Mb represents at least one of a metal element and a metalloid element other than lithium and Ma, Mc represents at least one of nonmetallic elements, and Md represents at least one of metallic elements and metalloid elements other than Ma. The values of s, t, u, p, q, and r are s> 0, t ≧ 0, u ≧ 0, p> 0, q> 0, and r ≧ 0, respectively.

  Among these, a simple substance, alloy or compound of Group 4B metal element or semimetal element in the short-period type periodic table is preferable, and silicon (Si) or tin (Sn), or an alloy or compound thereof is particularly preferable. These may be crystalline or amorphous.

In addition, inorganic compounds containing no lithium (Li) such as MnO ₂ , V ₂ O ₅ , V ₆ O ₁₃ , NiS, and MoS can also be used.

[Electrolyte]
As the electrolytic solution, a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent can be used. As the non-aqueous solvent, for example, it is preferable to contain at least one of ethylene carbonate and propylene carbonate. This is because the cycle characteristics can be improved. In particular, it is preferable to mix and contain ethylene carbonate and propylene carbonate because cycle characteristics can be further improved. The nonaqueous solvent preferably contains at least one of chain carbonates such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, or methyl propyl carbonate. This is because the cycle characteristics can be further improved.

  The non-aqueous solvent preferably further contains at least one of 2,4-difluoroanisole and vinylene carbonate. This is because 2,4-difluoroanisole can improve discharge capacity, and vinylene carbonate can further improve cycle characteristics. In particular, it is more preferable that they are mixed and contained because both the discharge capacity and the cycle characteristics can be improved.

  Non-aqueous solvents further include butylene carbonate, γ-butyrolactone, γ-valerolactone, those in which part or all of the hydrogen groups of these compounds are substituted with fluorine groups, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyl Tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, methyl acetate, methyl propionate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropironitrile, N, N-dimethylformamide N-methylpyrrolidinone, N-methyloxazolidinone, N, N-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, dimethyl sulfoxide or trimethyl phosphate may be included. Yes.

  Depending on the electrode to be combined, the reversibility of the electrode reaction may be improved by using a material in which part or all of the hydrogen atoms of the substance contained in the non-aqueous solvent group are substituted with fluorine atoms. Therefore, these substances can be used as appropriate.

Examples of the lithium salt that is an electrolyte salt include LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiClO ₄ , LiB (C ₆ H ₅ ) ₄ , LiCH ₃ SO ₃ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) _2. , LiC (SO ₂ CF ₃ ) ₃ , LiAlCl ₄ , LiSiF ₆ , LiCl, LiBF ₂ (ox), LiBOB, or LiBr are suitable, and one or more of these are used in combination. be able to. Among them, LiPF ₆ is preferable because it can obtain high ion conductivity and can improve cycle characteristics.

[Separator]
Below, the separator material which can be utilized for one Embodiment is demonstrated. As a separator material, it is possible to use those used in conventional batteries. Among these, it is particularly preferable to use a polyolefin microporous film that is excellent in short-circuit prevention effect and that can improve battery safety by a shutdown effect. For example, a microporous film made of polyethylene or polypropylene resin is preferable.

  Further, as the separator material, it is more preferable to use a laminate or mixture of polyethylene having a lower shutdown temperature and polypropylene having excellent oxidation resistance from the viewpoint of achieving both shutdown performance and float characteristics.

(1-2) Manufacturing Method of Nonaqueous Electrolyte Secondary Battery Next, a manufacturing method of the nonaqueous electrolyte secondary battery will be described. Hereinafter, a method for manufacturing a nonaqueous electrolyte secondary battery will be described by taking a cylindrical nonaqueous electrolyte secondary battery as an example.

  The positive electrode 2 is produced as described below. First, for example, a positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and this positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to form a positive electrode mixture. Use slurry.

  Next, after applying this positive electrode mixture slurry to the positive electrode current collector 2A and drying the solvent, the positive electrode mixture layer 2B is formed by compression molding with a roll press or the like, and the positive electrode 2 is produced.

  The negative electrode 3 is produced as described below. First, for example, a negative electrode active material and a binder are mixed to prepare a negative electrode mixture, and the negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a negative electrode mixture slurry.

  Next, after applying this negative electrode mixture slurry to the negative electrode current collector 3A and drying the solvent, the negative electrode mixture layer 3B is formed by compression molding using a roll press or the like, and the negative electrode 3 is produced.

  Moreover, the negative electrode mixture layer 3B may be formed by, for example, a gas phase method, a liquid phase method, or a firing method, or a combination of two or more thereof. As the vapor phase method, for example, a physical deposition method or a chemical deposition method can be used. Specifically, a vacuum deposition method, a sputtering method, an ion plating method, a laser ablation method, a thermal CVD (Chemical Vapor Deposition), or the like. A chemical vapor deposition method) or a plasma CVD method can be used. As the liquid phase method, a known method such as electrolytic plating or electroless plating can be used. A known method can also be used for the firing method, and for example, an atmosphere firing method, a reaction firing method, or a hot press firing method can be used.

  Next, the positive electrode lead 13 is attached to the positive electrode current collector 2A by welding or the like, and the negative electrode lead 14 is attached to the negative electrode current collector 3A by welding or the like. Next, the positive electrode 2 and the negative electrode 3 are wound through the separator 4, and the tip of the positive electrode lead 13 is welded to the safety valve mechanism 8, and the tip of the negative electrode lead 14 is welded to the battery can 1. The rotated positive electrode 2 and negative electrode 3 are sandwiched between a pair of insulating plates 5 and 6 and stored in the battery can 1.

  Next, an electrolytic solution is injected into the battery can 1 and the separator 4 is impregnated with the electrolytic solution. Next, the battery lid 7, the safety valve mechanism 8, and the heat sensitive resistance element 9 are fixed to the opening end of the battery can 1 by caulking through the gasket 10. Thus, a nonaqueous electrolyte secondary battery is produced.

(2) Second Example of Nonaqueous Electrolyte Secondary Battery (2-1) Configuration of Nonaqueous Electrolyte Secondary Battery FIG. 3 is a nonaqueous electrolyte secondary battery using a positive electrode active material according to an embodiment of the present invention. The structure of is shown. As shown in FIG. 3, this non-aqueous electrolyte secondary battery is sealed by housing the battery element 30 in an exterior material 37 made of a moisture-proof laminate film and welding the periphery of the battery element 30. The battery element 30 is provided with a positive electrode lead 32 and a negative electrode lead 33, and these leads are sandwiched between outer packaging materials 37 and pulled out to the outside. A resin piece 34 and a resin piece 35 are coated on both surfaces of the positive electrode lead 32 and the negative electrode lead 33 in order to improve the adhesion to the exterior material 37.

[Exterior material]
The packaging material 37 has, for example, a stacked structure in which an adhesive layer, a metal layer, and a surface protective layer are sequentially stacked. The adhesive layer is made of a polymer film. Examples of the material constituting the polymer film include polypropylene (PP), polyethylene (PE), unstretched polypropylene (CPP), linear low density polyethylene (LLDPE), and low density. A polyethylene (LDPE) is mentioned. The metal layer is made of a metal foil, and an example of a material constituting the metal foil is aluminum (Al). Moreover, as a material which comprises metal foil, it is also possible to use metals other than aluminum (Al), for example. Examples of the material constituting the surface protective layer include nylon (Ny) and polyethylene terephthalate (PET). The surface on the adhesive layer side is a storage surface on the side where the battery element 30 is stored.

[Battery element]
For example, as shown in FIG. 4, the battery element 30 includes a strip-shaped negative electrode 43 provided with a gel electrolyte layer 45 on both sides, a separator 44, and a strip-shaped positive electrode 42 provided with a gel electrolyte layer 45 on both sides. The battery element 30 is a wound type battery element 30 that is formed by laminating the separator 44 and wound in the longitudinal direction.

  The positive electrode 42 includes a strip-shaped positive electrode current collector 42A and a positive electrode mixture layer 42B formed on both surfaces of the positive electrode current collector 42A.

  One end of the positive electrode 42 in the longitudinal direction is provided with a positive electrode lead 32 connected by, for example, spot welding or ultrasonic welding. As a material of the positive electrode lead 32, for example, a metal such as aluminum can be used.

  The negative electrode 43 includes a strip-shaped negative electrode current collector 43A and a negative electrode mixture layer 43B formed on both surfaces of the negative electrode current collector 43A.

  Similarly to the positive electrode 42, the negative electrode lead 33 connected by, for example, spot welding or ultrasonic welding is also provided at one end portion of the negative electrode 43 in the longitudinal direction. As a material of the negative electrode lead 33, for example, copper (Cu), nickel (Ni) or the like can be used.

  The positive electrode current collector 42A, the positive electrode mixture layer 42B, the negative electrode current collector 43A, and the negative electrode mixture layer 43B are the same as in the first example.

  The gel electrolyte layer 45 includes an electrolytic solution and a polymer compound serving as a holding body that holds the electrolytic solution, and has a so-called gel shape. The gel electrolyte layer 45 is preferable because it can obtain high ionic conductivity and prevent battery leakage. The configuration of the electrolytic solution (that is, the liquid solvent, the electrolyte salt, and the additive) is the same as that in the first embodiment.

  Examples of the polymer compound include polyacrylonitrile, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, and polysiloxane. , Polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene or polycarbonate. In particular, from the viewpoint of electrochemical stability, polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene, or polyethylene oxide is preferable.

(2-2) Method for Producing Nonaqueous Electrolyte Secondary Battery Next, a method for producing a nonaqueous electrolyte secondary battery using a positive electrode active material according to an embodiment of the present invention will be described. First, a precursor solution containing a solvent, an electrolyte salt, a polymer compound, and a mixed solvent is applied to each of the positive electrode 42 and the negative electrode 43, and the mixed solvent is volatilized to form the gel electrolyte layer 45. The positive lead 32 is attached to the end of the positive current collector in advance by welding, and the negative lead 33 is attached to the end of the negative current collector 43A by welding.

  Next, the positive electrode 42 and the negative electrode 43 on which the gel electrolyte layer 45 is formed are laminated through a separator 44 to form a laminated body, and then the laminated body is wound in the longitudinal direction to form a wound battery element. 30 is formed.

  Next, a recess 36 is formed by deep-drawing an exterior material 37 made of a laminate film, the battery element 30 is inserted into the recess 36, and an unprocessed portion of the exterior material 37 is folded back to the upper portion of the recess 36. The outer peripheral part of is thermally welded and sealed. Thus, a nonaqueous electrolyte secondary battery is produced.

  Specific embodiments of the present invention will be described below with reference to examples, but the present invention is not limited thereto.

<Example 1>
First, 20 parts by weight of complex oxide particles having an average composition of Li _1.03 CoO _2.01 and an average particle diameter of 13 μm measured by a laser scattering method were stirred and dispersed in 300 parts by weight of pure water at 80 ° C. for 1 hour.

Next, 1.60 parts by weight of a commercially available reagent nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O) and a commercially available reagent manganese nitrate (Mn (NO ₃ ) ₂ .6H ₂ O) 1.65 Further, 2N LiOH aqueous solution was added to pH 13 over 30 minutes, and stirring and dispersion were continued at 80 ° C. for 3 hours, and then allowed to cool.

Next, this dispersion was decanted and washed, and 0.1 parts by weight of lithium tetraborate (Li ₂ B ₄ O ₇ .3H ₂ O) as a commercially available reagent was dissolved in 2.0 parts by weight of pure water. And then decantation washed, finally filtered and dried at 120 ° C. to form a precursor.

  Next, in order to adjust the amount of lithium, 10 parts by weight of the obtained precursor sample was impregnated with 2 parts by weight of 2N LiOH aqueous solution and uniformly mixed and dried to obtain a calcined precursor. The calcined precursor was heated at a rate of 5 ° C./min in an air flow using an electric furnace, held at 950 ° C. for 5 hours, then cooled to 150 ° C. at 7 ° C./min, and the positive electrode of Example 1 An active material was obtained.

<Example 2>
First, 20 parts by weight of the composite oxide particles used in Example 1 were stirred and dispersed in 300 parts by weight of a 2N LiOH aqueous solution at 80 ° C. for 2 hours (this system had a pH of 14.3). Next, 1.60 parts by weight of a commercially available reagent nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O) and a commercially available reagent manganese nitrate (Mn (NO ₃ ) ₂ .6H ₂ O) 1.65 An aqueous solution was prepared by adding pure water to 10 parts by weight, and 10 parts by weight of this aqueous solution was added over 2 hours. Further, stirring and dispersion were continued at 80 ° C. for 1 hour, and then allowed to cool.

Next, this dispersion was decanted and washed, and 0.1 parts by weight of a commercially available reagent sodium metaborate (NaBO ₂ .4H ₂ O) was dissolved in 2.0 parts by weight of pure water and added. Further, decantation washing was performed, and finally, filtration was performed, and the precursor was formed by drying at 120 ° C. Next, using an electric furnace, the obtained precursor was heated at a rate of 5 ° C. per minute under an air flow, held at 950 ° C. for 5 hours, then cooled to 150 ° C. at 7 ° C. per minute, and carried out. The positive electrode active material of Example 2 was obtained.

<Example 3>
Pure water is added to 3.20 parts by weight of nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O) as a commercial reagent and 3.30 parts by weight of manganese nitrate (Mn (NO ₃ ) ₂ .6H ₂ O) as a commercial reagent. Was added to prepare 20 parts by weight of an aqueous solution, and 20 parts by weight of this aqueous solution was added over 3 hours. 0.2 parts by weight of a commercially available reagent, lithium tetraborate (Li ₂ B ₄ O ₇ .3H ₂ O), was dissolved in 5.0 parts by weight of pure water and added. Otherwise, the positive electrode active material of Example 3 was obtained in the same manner as Example 2.

<Comparative Example 1>
In Example 1, composite oxide particles having an average composition of Li _1.03 CoO _2.01 and an average particle diameter measured by a laser scattering method of 13 μm were used as the positive electrode active material of Comparative Example 1.

<Comparative example 2>
The positive electrode active material of Comparative Example 2 was the same as Example 1 except that 0.1 part by weight of lithium tetraborate (Li ₂ B ₄ O ₇ .3H ₂ O) was not added. Was made.

The secondary batteries shown in FIGS. 1 and 2 were produced using the positive electrode active materials of Examples 1 to 3 and Comparative Examples 1 to 2 that were produced by evaluation . First, 86% by weight of the prepared positive electrode active material powder, 10% by weight of graphite as a conductive agent, and 4% by weight of polyvinylidene fluoride as a binder were mixed, and N-methyl-2pyrrolidone (NMP) as a solvent was mixed. After the dispersion, the positive electrode current collector 2A made of a strip-shaped aluminum foil having a thickness of 20 μm was applied and dried, and compression molded by a roller press to form the positive electrode mixture layer 2B, thereby producing the positive electrode 2. At that time, the gap of the positive electrode mixture layer 2B was adjusted to be 26% by volume ratio. Next, the positive electrode lead 13 made of aluminum was attached to the positive electrode current collector 2A.

  Further, 90% by weight of artificial graphite powder as a negative electrode active material and 10% by weight of polyvinylidene fluoride as a binder were mixed and dispersed in N-methyl-2-pyrrolidone as a solvent, and then a 10 μm thick strip-shaped copper The negative electrode current collector 3A made of foil was applied to both surfaces and dried, and compression molding was performed with a roller press to form the negative electrode mixture layer 3B, whereby the negative electrode 3 was produced. Next, a negative electrode lead 14 made of nickel was attached to the negative electrode current collector 3A.

The strip-shaped positive electrode 2 and the strip-shaped negative electrode 3 produced as described above were wound many times through a porous polyolefin film as a separator 4 to produce a spiral wound electrode body 20. Next, this wound electrode body 20 was housed in an iron battery can 1, and a pair of insulating plates 5 and 6 were disposed on both the upper and lower surfaces of the wound electrode body 20. Next, the positive electrode lead 13 was led out from the positive electrode current collector 2A and welded to the safety valve mechanism 8, and the negative electrode lead 14 was led out from the negative electrode current collector 3A and welded to the bottom of the battery can 1. Thereafter, an electrolytic solution is injected into the battery can 1 and the battery can 1 is caulked through the gasket 10, thereby fixing the safety valve mechanism 8, the heat sensitive resistance element 9 and the battery lid 7, and having an outer diameter of 18 mm, high A cylindrical secondary battery having a thickness of 65 mm was obtained. As the electrolytic solution, a solution obtained by dissolving LiPF ₆ as an electrolyte salt to 1.0 mol / l in a solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1 was used.

  About the secondary battery produced as mentioned above, it charges / discharges in a 45 degreeC temperature environment, calculates | requires the discharge capacity of the 1st cycle as an initial capacity, and calculates | requires the discharge capacity maintenance factor of the 200th cycle with respect to the 1st cycle. It was.

  Charging is performed at a constant current of 1000 mA until the battery voltage reaches 4.40 V, and then charged at a constant voltage of 4.40 V until the total charging time is 2.5 hours. The discharge was performed at a constant current of 800 mA until the battery voltage reached 2.75V. The measurement results are shown in Table 1.

  As shown in Table 1, Examples 1 to 3 had a high capacity, and compared with Comparative Example 1, the discharge capacity retention rate could be greatly improved. In addition, the discharge capacity retention rate could be improved as compared with Comparative Example 2 in which the surface layer containing boron (B) was not formed.

  The present invention is not limited to the above-described embodiments of the present invention, and various modifications and applications are possible without departing from the spirit of the present invention. For example, the shape is not particularly limited. It may be a cylindrical shape, a square shape, a coin shape, a button shape, or the like.

In the first example, a non-aqueous electrolyte secondary battery having an electrolyte as an electrolyte has been described. In the second example, a non-aqueous electrolyte secondary battery having a gel electrolyte as an electrolyte has been described, but the present invention is not limited thereto. It is not a thing.

  For example, as the electrolyte, in addition to the above-described ones, a polymer solid electrolyte using an ion conductive polymer or an inorganic solid electrolyte using an ion conductive inorganic material can be used. It may be used in combination with the electrolyte. Examples of the polymer compound that can be used for the polymer solid electrolyte include polyether, polyester, polyphosphazene, and polysiloxane. Examples of the inorganic solid electrolyte include ion conductive ceramics, ion conductive crystals, and ion conductive glass.

  Furthermore, for example, a conventional nonaqueous solvent-based electrolytic solution is used as the electrolytic solution of the nonaqueous electrolyte secondary battery without any particular limitation. Among these, the electrolyte solution of the secondary battery comprising a non-aqueous electrolyte containing an alkali metal salt includes propylene carbonate, ethylene carbonate, γ-butyrolactone, N-methylpyrrolidone, acetonitrile, N, N-dimethylformamide, dimethylsulfate. For example, foxoxide, tetrahydrofuran, 1,3-dioxolane, methyl formate, sulfolane, oxazolidone, thionyl chloride, 1,2-dimethoxyethane, diethylene carbonate, and derivatives and mixtures thereof are preferably used. The electrolyte contained in the electrolyte includes alkali metal, especially calcium halide, perchlorate, thiocyanate, borofluoride, phosphofluoride, arsenic fluoride, yttrium fluoride, trifluoromethylsulfate, etc. Is preferably used.

It is a schematic sectional drawing of the 1st example of the nonaqueous electrolyte secondary battery using the positive electrode active material by one Embodiment of this invention. FIG. 2 is an enlarged sectional view of a part of a wound electrode body shown in FIG. 1. It is the schematic of the 2nd example of the nonaqueous electrolyte secondary battery using the positive electrode active material by one Embodiment of this invention. FIG. 4 is an enlarged cross section of a part of the battery element shown in FIG. 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Battery can 2 ... Positive electrode 2A ... Positive electrode collector 2B ... Positive electrode mixture layer 3A ... Negative electrode collector 3B ... Negative electrode mixture layer 3 ... Negative electrode 4 .... Separator 5, 6 .... Insulating plate 7 .... Battery cover 8 .... Safety valve mechanism 9 .... Heat-sensitive element 10 ... Gasket 11 .... Disc plate 12. ..Center pin 13 ... Positive lead 14 ... Negative lead 20 ... Wound electrode body 30 ... Battery element 32 ... Positive lead 33 ... Negative lead 34, 35 ... Resin piece 35 ... Negative electrode lead 36 ... Recess 37 ... Exterior material 42 ... Positive electrode 42A ... Positive electrode current collector 42B ... Positive electrode mixture layer 43 ... Negative electrode 43A ... Negative electrode current collector 43B ...・ Negative electrode mixture layer 44 ... Separator 45 ... Gel electrolyte layer

Claims (15)

Composite oxide particles including at least lithium (Li) as a first layer and cobalt (Co);
Oxidation including lithium (Li) as the second layer and at least one covering element of nickel (Ni) and manganese (Mn) provided on at least a part of the surface of the composite oxide particle A coating layer made of material,
A surface layer containing boron (B), which is a third layer, provided by adding borate to at least a part of the coating layer and firing the same;
A positive electrode active material comprising: The positive electrode active material according to claim 1, wherein the composite oxide particles have an average composition represented by chemical formula (1).
(Chemical formula 1)
_{Li (1 + x) Co (} 1-y) M y O (2-z)
(In the chemical formula 1, M is magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), and tungsten (W), x, y, and z are −0. 10 ≦ x ≦ 0.10, 0 ≦ y <0.50, −0.10 ≦ z ≦ 0.20.   3. The positive electrode active material according to claim 1, wherein a composition ratio of the nickel (Ni) and the manganese (Mn) in the coating layer is in a range of 100: 0 to 30:70 in terms of molar ratio. .   The oxide of the coating layer contains 40 mol% or less of the total amount of nickel (Ni) and manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium ( V), chromium (Cr), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), at least selected from the group consisting of tungsten (W) The positive electrode active material according to claim 1, wherein the positive electrode active material is replaced with one kind of metal element.   5. The positive electrode active material according to claim 1, wherein an amount of the coating layer is in a range of 0.5 wt% to 50 wt% of the composite oxide particles.   The positive electrode active material according to any one of claims 1 to 5, wherein an average particle diameter is in a range of 2.0 µm to 50 µm. It consists of a hydroxide containing nickel (Ni) and / or manganese (Mn) on at least a part of the surface of the composite oxide particles containing at least lithium (Li) as the first layer and cobalt (Co). After forming the layer, a step of depositing a borate in at least a part of the composite oxide particles,
After depositing the borate, by heating, the composite is provided on at least part of the surface of the oxide particles, and lithium (Li) as the second layer, nickel (Ni) and A coating layer made of an oxide containing at least one coating element of manganese (Mn), and a surface layer containing boron (B) as a third layer provided on at least a part of the coating layer Forming a step;
The manufacturing method of the positive electrode active material which has this. The method for producing a positive electrode active material according to claim 7, wherein the composite oxide particles have an average composition represented by chemical formula (1).
(Chemical formula 1)
Li _{(1 + x)} Co _(1-y) MyO _(2-z)
(In the chemical formula 1, M is magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), and tungsten (W), x, y, and z are −0. 10 ≦ x ≦ 0.10, 0 ≦ y <0.50, −0.10 ≦ z ≦ 0.20. Formation of the hydroxide containing nickel (Ni) and / or manganese (Mn)
The composite oxide particles are dispersed in a solvent mainly composed of water having a pH of 12 or more, and then added with a nickel (Ni) compound and / or a manganese (Mn) compound. Of manufacturing positive electrode active material.   The method for producing a positive electrode active material according to claim 9, wherein the water-based solvent contains lithium hydroxide.   The positive electrode active material according to any one of claims 7 to 10, wherein a composition ratio of the nickel (Ni) and the manganese (Mn) in the coating layer is in a range of 100: 0 to 30:70 in terms of molar ratio. Manufacturing method.   The oxide of the coating layer contains 40 mol% or less of the total amount of nickel (Ni) and manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium ( V), chromium (Cr), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), at least selected from the group consisting of tungsten (W) The method for producing a positive electrode active material according to claim 7, wherein the positive electrode active material is replaced with one metal element.   The method for producing a positive electrode active material according to claim 7, wherein an amount of the coating layer is in a range of 0.5 wt% to 50 wt% of the composite oxide particles.   The method for producing a positive electrode active material according to claim 7, wherein the positive electrode active material has an average particle size in the range of 2.0 μm to 50 μm. A positive electrode having a positive electrode active material, a negative electrode, and an electrolyte;
The positive electrode active material is
Composite oxide particles including at least lithium (Li) as a first layer and cobalt (Co);
Oxidation including lithium (Li) as the second layer and at least one covering element of nickel (Ni) and manganese (Mn) provided on the surface of at least a part of the composite oxide particles A coating layer made of material,
A surface layer containing boron (B), which is a third layer, provided by adding borate to at least a part of the coating layer and firing the same;
A nonaqueous electrolyte secondary battery.

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