JP2010009960A - Manufacturing method of positive electrode active material, and positive electrode active material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive electrode active material which has a high charge current capacity and superior charge/discharge efficiency. <P>SOLUTION: The positive electrode active material is made, by making a sulfate adhere on a composite oxide particle which is mainly composed of lithium nickelate. In a secondary battery that uses the positive electrode active material fabricated by such a method and containing carbonate ions whose content is made 0.15 wt.% or lower, gas generation in the battery can be suppressed. A heat treatment is carried out at a temperature of 150°C or higher and 1,200°C or lower. The sulfate to be used is ammonium sulfate, lithium sulfate or a mixed salt thereof. The sulfate of 0.01 pt.wt. or higher and 20 pts.wt. or lower with respect to 100 pts.wt. of the composite oxide particle is made to adhere and is heat treated. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a positive electrode active material used for a non-aqueous electrolyte secondary battery, and more particularly, to a positive electrode active material that suppresses gas generation inside the battery.

  In recent years, with the widespread use of portable devices such as video cameras and notebook personal computers, the demand for small, high-capacity secondary batteries has increased. Currently used secondary batteries include nickel-cadmium batteries and nickel-hydrogen 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 this grows by a charge / discharge cycle. Dendritic growth not only deteriorates the charge / discharge cycle characteristics of the secondary battery, but in the worst case, it breaks through the diaphragm (separator) arranged so that the positive electrode and the negative electrode do not come into contact with each other, causing an internal short circuit. As a result, there is a problem that the battery is destroyed by firing.

  Thus, for example, as described in Patent Document 1 below, 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 has been proposed. 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 a positive electrode active material, a battery with a battery voltage of around 4 V has appeared due to the search and development of an active material exhibiting a high potential, and has attracted attention. As such active materials, inorganic compounds such as transition metal oxides containing alkali metals and transition metal chalcogens are known. Among these, lithium transition metal composite oxides mainly composed of nickel or cobalt such as Li _x NiO ₂ (0 <x ≦ 1.0) and Li _x CoO ₂ (0 <x ≦ 1.0) have a high potential, Most promising in terms of stability and long life. Among these, a positive electrode active material mainly composed of lithium nickelate (LiNiO ₂ ) is a positive electrode active material exhibiting a relatively high potential, and is expected to have a high charge current capacity and an increased energy density.

  However, along with further downsizing and higher functionality of portable devices, the positive electrode active material consisting of lithium transition metal composite oxide mainly composed of nickel (Ni) and cobalt (Co) has been further improved to further increase the charging current capacity. It is desired to make it higher. It is also desired to improve the charge / discharge efficiency by improving the positive electrode active material as described above.

For example, in a secondary battery using a composite oxide mainly composed of lithium nickelate (LiNiO ₂ ) as a positive electrode active material, gas is easily generated inside the battery. For this reason, for example, in a cylindrical battery or the like, the battery internal pressure is likely to increase, and in a thin battery in which a battery element is sealed in a laminate material, there is a problem that battery swelling is likely to occur.

  Accordingly, an object of the present invention is to solve the above-described problems, and to provide a positive electrode active material having a high charge current capacity and excellent charge / discharge efficiency.

  In order to solve the above-described problems, the present invention provides a composite process in which sulfate is applied to composite oxide particles containing lithium (Li) and nickel (Ni), and a composite in which sulfate is applied. It is a manufacturing method of the positive electrode active material which has a heating process which heat-processes an oxide particle.

The composite oxide particles have an average composition represented by the following chemical formula 1.
(Chemical formula 1)
Li _a Ni _x Co _y Al _z O ₂
(However, Ni, when the total amount of Ni is 1, within the range of 0.1 or less of Ni, manganese (Mn), chromium (Cr), iron (Fe), vanadium (V), magnesium ( Mg), titanium (Ti), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W), copper (Cu), zinc (Zn), gallium (Ga), indium (In), tin ( Sn, lanthanum (La), and cerium (Ce) can be substituted with one or more metal elements selected from the group consisting of a), lanthanum (La), and cerium (Ce), where a, x, y, and z are 0.3 ≦ a ≦ 1.05, 0.60 <x <0.90, 0.10 <y <0.40, 0.01 <z <0.20, values of x, y and z (There is a relationship of x + y + z = 1 between them.)

  In the positive electrode active material described above, the carbonate ion content is 0.15 wt% or less. In the heating step, it is preferable that the heat treatment be performed at a temperature of 150 ° C. or higher and 1200 ° C. or lower.

  In the above-described deposition step, it is preferable that 0.01 to 20 parts by weight of sulfate is deposited with respect to 100 parts by weight of the composite oxide particles. The sulfate to be deposited is preferably ammonium sulfate, lithium sulfate or a mixed salt thereof.

In the second invention, the composite oxide particles having an average composition represented by Chemical Formula 1 are subjected to heat treatment by adhering sulfate, and the carbonate ion content is 0.15 wt% or less. It is a certain positive electrode active material.
(Chemical formula 1)
Li _a Ni _x Co _y Al _z O ₂
(However, Ni, when the total amount of Ni is 1, within the range of 0.1 or less of Ni, manganese (Mn), chromium (Cr), iron (Fe), vanadium (V), magnesium ( Mg), titanium (Ti), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W), copper (Cu), zinc (Zn), gallium (Ga), indium (In), tin ( Sn, lanthanum (La), and cerium (Ce) can be substituted with one or more metal elements selected from the group consisting of a), lanthanum (La), and cerium (Ce), where a, x, y, and z are 0.3 ≦ a ≦ 1.05, 0.60 <x <0.90, 0.10 <y <0.40, 0.01 <z <0.20, values of x, y and z (There is a relationship of x + y + z = 1 between them.)

  The positive electrode active material described above preferably has a surface layer containing sulfate or a decomposition product of sulfate on at least a part of the surface of the composite oxide particle.

  When the positive electrode active material produced by the method as described above is subjected to heat treatment at a heating temperature of less than 500 ° C., for example, sulfate or a decomposition product of sulfate exists on the surface of the positive electrode active material, and charging is performed. This suppresses the oxidation activity on the surface of the composite oxide particles in the state. For this reason, decomposition | disassembly of the nonaqueous electrolyte etc. in the positive electrode active material surface can be suppressed. In addition, when the heat treatment is performed at a heating temperature of 500 ° C. or higher, the carbonate radical and sulfate contained in the composite oxide particles are replaced.

  According to the present invention, gas generation due to decomposition of the nonaqueous electrolytic solution or the like can be suppressed. Alternatively, gas generation from itself in the positive electrode active material can be suppressed.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

[Positive electrode active material]
The positive electrode active material according to one embodiment of the present invention is obtained by heat-treating a sulfate on the surface of the composite oxide particle, and containing the carbonate ion (Co ₃ ²⁻ ) in the positive electrode active material. The amount is 0.15% by weight or less, more preferably 0.10% by weight or less, and still more preferably 0.05% by weight or less. By reducing the content of the carbonate radical of the positive electrode active material, the amount of gas generated inside the battery of the secondary battery is reduced. In addition, content of a carbonic acid content can be measured by AGK method prescribed | regulated to JISR9101. For example, the sulfate component is deposited in a state of being chemically bonded to a substance on the surface of the composite oxide particle or in an ionic state.

  The composite oxide particles contain lithium (Li) and nickel (Ni). For example, it is preferable that the average composition is represented by the following chemical formula (1). By using such composite oxide particles, a discharge capacity can be realized.

(Chemical formula 1)
Li _a Ni _x Co _y Al _z O ₂
(However, Ni, when the total amount of Ni is 1, within the range of 0.1 or less of Ni, manganese (Mn), chromium (Cr), iron (Fe), vanadium (V), magnesium ( Mg), titanium (Ti), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W), copper (Cu), zinc (Zn), gallium (Ga), indium (In), tin ( Sn, lanthanum (La), and cerium (Ce) can be substituted with one or more metal elements selected from the group consisting of a), lanthanum (La), and cerium (Ce), where a, x, y, and z are 0.3 ≦ a ≦ 1.05, 0.60 <x <0.90, 0.10 <y <0.40, 0.01 <z <0.20, values of x, y and z (There is a relationship of x + y + z = 1 between them.)

  Here, in Chemical Formula 1, the range of a is, for example, 0.3 ≦ a ≦ 1.05. When the value is smaller than this range, the layered rock salt structure of the crystal structure that is the source of the function of the positive electrode active material is destroyed, recharging becomes difficult, and the capacity is greatly reduced. If the value increases outside this range, lithium diffuses out of the composite oxide particles described above, which hinders control of the basicity of the next processing step, and finally the gel during the kneading of the positive electrode paste. It will be a cause of the harmful effect of the promotion.

  The range of x is, for example, 0.60 <x <0.90, more preferably 0.65 <x <0.85, and still more preferably 0.70 <x <0.80. When the value decreases outside this range, the discharge capacity of the positive electrode active material decreases. If the value is increased outside this range, the stability of the crystal structure of the composite oxide particles decreases, which causes a decrease in the capacity of repeated charge / discharge of the positive electrode active material and a decrease in safety.

  The range of y is, for example, 0.10 <y <0.40, preferably 0.15 <y <0.35, and more preferably 0.20 <y <0.30. When the value is smaller than this range, the stability of the crystal structure of the composite oxide particles is lowered, which causes a reduction in the capacity of repeated charge / discharge of the positive electrode active material and a reduction in safety. When the value increases outside this range, the discharge capacity of the positive electrode active material decreases.

  The range of z is, for example, 0.01 <z <0.20, more preferably 0.02 <z <0.15, and further preferably 0.03 <z <0.10. If the value is smaller than the above range, the stability of the crystal structure of the composite oxide particles is lowered, which causes a reduction in the capacity of repeated charge / discharge of the positive electrode active material and a reduction in safety. When the value increases outside this range, the discharge capacity of the positive electrode active material decreases.

  The average particle diameter of the positive electrode active material is preferably 2.0 μm or more and 50 μm or less. When the average particle size is less than 2.0 μm, the positive electrode active material layer is peeled off when the positive electrode active material layer is pressed during the production of the positive electrode. Further, since the surface area of the positive electrode active material is increased, it is necessary to increase the amount of the conductive agent and the binder added, and the energy density per unit weight tends to be reduced. On the other hand, when the average particle diameter exceeds 50 μm, the particles tend to penetrate the separator and cause a short circuit.

[Method for producing positive electrode active material]
Next, a method for producing a positive electrode active material according to an embodiment of the present invention will be described. As the composite oxide particles, those usually available as a positive electrode active material can be used as a starting material, but in some cases, particles obtained by crushing secondary particles using a ball mill or a grinder may be used. it can.

  Lithium nickelate having a chemical composition as shown in Chemical Formula 1 can be produced by a known method. Specifically, for example, a nickel compound, a cobalt compound, an aluminum compound, a lithium compound, and the like are dissolved in water, and a sodium hydroxide solution is added while sufficiently stirring to prepare a nickel-cobalt-aluminum composite coprecipitated hydroxide. Thereafter, lithium nickelate can be produced by a method of firing the precursor obtained by washing and drying the nickel-cobalt-aluminum composite coprecipitated hydroxide. If necessary, the fired lithium nickelate may be pulverized.

  Examples of the raw material for the nickel compound include nickel hydroxide, nickel carbonate, nickel nitrate, nickel fluoride, nickel chloride, nickel bromide, nickel iodide, nickel perchlorate, nickel bromate, nickel iodate, nickel oxide, Use inorganic compounds such as nickel peroxide, nickel sulfide, nickel sulfate, nickel hydrogen sulfate, nickel nitride, nickel nitrite, nickel phosphate and nickel thiocyanate, or organic compounds such as nickel oxalate and nickel acetate. One or two or more of these may be used.

  Examples of cobalt compound raw materials include cobalt hydroxide, cobalt carbonate, cobalt nitrate, cobalt fluoride, cobalt chloride, cobalt bromide, cobalt iodide, cobalt chlorate, cobalt perchlorate, cobalt bromate, and cobalt iodate. , Cobalt oxide, cobalt phosphinate, cobalt sulfide, cobalt hydrogen sulfide, cobalt sulfate, cobalt hydrogen sulfate, cobalt thiocyanate, cobalt nitrite, cobalt phosphate, cobalt dihydrogen phosphate, cobalt hydrogen carbonate, etc. Organic compounds such as cobalt acid and cobalt acetate can be used, and one or more of these may be used.

  Examples of the aluminum compound raw material include inorganic substances such as aluminum hydroxide, aluminum nitrate, aluminum fluoride, aluminum chloride, aluminum bromide, aluminum iodide, aluminum perchlorate, aluminum oxide, aluminum sulfide, aluminum sulfate, and aluminum phosphate. An organic compound such as an aluminum compound or an aluminum oxalate can be used, and one or more of these may be used.

  Examples of lithium compound raw materials include lithium hydroxide, lithium carbonate, lithium nitrate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium chlorate, lithium perchlorate, lithium bromate, and lithium iodate. Inorganic compounds such as lithium oxide, 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, and one or more of these may be used.

  The lithium nickelate produced as described above is a lithium composite oxide for a lithium ion secondary battery that can realize a high voltage and high energy density substantially the same as lithium cobaltate. This composite oxide has the advantage of high economic efficiency because it is unstable in resources and has a low content of cobalt, which is an expensive material.

  Further, this composite oxide has an advantage of a large current capacity as compared with lithium cobalt oxide, and it is desired to further increase the advantage. Furthermore, this composite oxide has a smaller charge current capacity than a discharge current capacity, and a so-called irreversible capacity, as compared with lithium cobalt oxide. For this reason, there is a drawback that the charge / discharge efficiency is low as a result, and improvement is desired.

  Therefore, in one embodiment of the present invention, the composite oxide particles such as lithium nickelate prepared by a known method are subjected to another step treatment to perform surface modification, thereby performing such composite oxidation. While increasing the discharge current capacity when using physical particles as the positive electrode material, the charge / discharge efficiency is improved. Specifically, as the positive electrode active material, for example, lithium, nickel, cobalt, aluminum, and a part of nickel as necessary, a small amount of manganese, chromium, iron, vanadium, magnesium, titanium, zirconium, niobium, molybdenum Aggregated secondary particles having layered crystals formed by substitution with one or more elements selected from the group consisting of tungsten, copper, zinc, gallium, indium, tin, lanthanum, and cerium (Composite oxide particles) are used. After applying a solution in which the deposition component is dissolved in a solvent to the composite oxide particles, the solvent is removed in a short time to deposit the deposition component, and the composite oxide particles are heated in an oxidizing atmosphere. Process. Thereby, the positive electrode active material for nonaqueous electrolyte secondary batteries which can improve a battery characteristic can be obtained.

  In addition, it is preferable that the above-mentioned deposition component is a sulfate. Nickel-based composite oxide particles have many carbonate radicals, and the discharge capacity is improved, while gas generation from the composite oxide particles easily occurs. By depositing sulfate, carbonate radicals and sulfate contained in the composite oxide particles are replaced, and gas generation is less likely to occur. In addition, the presence of sulfate or a sulfate decomposition product on the surface of the positive electrode active material can reduce the oxidizability of the surface of the positive electrode active material and make it difficult for gas generation due to decomposition of the electrolyte.

  Examples of sulfates that can be used in the present invention include ammonium sulfate, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, yttrium sulfate, titanium sulfate, zirconium sulfate, vanadium sulfate, chromium sulfate, Manganese sulfate, iron sulfate, ammonium iron sulfate, cobalt sulfate, nickel sulfate, copper sulfate, silver sulfate, zinc sulfate, aluminum sulfate, aluminum ammonium sulfate, gallium sulfate, indium sulfate, tin sulfate, antimony sulfate, bismuth sulfate, etc. It is done. Moreover, you may mix and use these.

  Hereinafter, the treatment applied to the composite oxide particles will be described.

  First, a solution in which a sulfate as described above is dissolved in a solvent as a deposition component is deposited on the heated composite oxide particles. The solution can be applied by, for example, a method of spraying the solution onto the dispersed composite oxide particles, or a method of dropping and mixing the solution onto the composite oxide particles. At this time, by heating the composite oxide particles, the solvent in which the deposition component is dissolved can be removed in a short time, and the deposition component can be deposited on the surface of the composite oxide particles. The heating temperature is preferably adjusted so as to be a temperature equal to or higher than the boiling point of the solution in which the deposition component is dissolved.

  As a solvent for dissolving the adherent component, for example, an inorganic solvent such as water can be used.

  By the above-mentioned method, the solvent in which the sulfate is dissolved can be removed in a short time, and the time during which the composite oxide particles are in contact with the solvent contained in the solution can be shortened. Usually, when the composite oxide particles come into contact with the solvent, lithium ions in the composite oxide particles are eluted in the solvent. However, the above method suppresses the elution of lithium ions, and the surface of the composite oxide particles is reduced. It is possible to suppress deterioration and the accompanying decrease in capacity of the positive electrode active material.

  At this time, the use amount of the sulfate as the deposition component is 0.01 parts by weight or more and 20 parts by weight or less, preferably 0.02 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the composite oxide particles described above. More preferably, it is 0.03 parts by weight or more and 10 parts by weight or less. If the amount of sulfate added is outside this range, the effect of suppressing gas generation in the positive electrode active material cannot be obtained. On the other hand, when the addition amount is larger than this range, the discharge capacity of the positive electrode active material decreases, which is not preferable.

  As described above, the method of depositing the liquid phase obtained by dissolving the deposition component in the solvent on the composite oxide particles can make the deposition of the deposition component uniform.

  Further, in addition to wet deposition of sulfate as described above, dry deposition of sulfate can also be performed. A known method can be used for dry deposition of sulfate. For example, using dry composite oxide particles and dry sulfate particles, applying them manually using a mortar, using a crusher, or high shear force that causes mechanical adhesion Examples include a method using a machine.

[Heating process]
Next, the composite oxide particles subjected to the sulfate precipitation treatment are fired by heat treatment. In this heat treatment, it is preferable that the sulfate deposited on the composite oxide particles is decomposed. The decomposition of sulfate promotes the diffusion of sulfate ions on the surface of the composite oxide particles, making it more uniform than using the conventional method of mixing and adhering solid particles to the composite oxide particles. The deposition component can be deposited.

  The heat treatment temperature is 150 ° C. or higher and 1200 ° C. or lower, preferably 300 ° C. or higher and 1200 ° C. or lower. More preferably, the heat treatment is performed at a temperature equal to or higher than the decomposition temperature of the deposited sulfate. Is preferred. For example, when ammonium sulfate is used as the deposition component, the heating temperature of the composite oxide particles is preferably set to 280 ° C. or higher, which is the decomposition temperature of ammonium sulfate.

  As described above, the composite oxide particles are heated at a temperature equal to or higher than the decomposition temperature of the deposition component, whereby the deposition of the deposition component can be made more uniform. For this reason, the deposition of the deposition component can be made more uniform by being used in combination with the method of depositing the liquid phase on the composite oxide particles and removing the solvent in a short time.

When this heat treatment is carried out at a low temperature of less than 500 ° C., the surface layer portion of the composite oxide particles is chemically eroded by the sulfate decomposition product, and the carbonate radical and sulfate are replaced. . Thereby, the substituted carbonate radical is released out of the system as carbon dioxide gas, and the carbonate radical content of the positive electrode active material mainly composed of lithium nickelate can be reduced. In the positive electrode active material of the present invention, the content of carbonate ions (CO ₃ ²⁻ ) can be reduced to 0.15 wt% or less by heat treatment, so that gas generation can be suppressed.

  At the same time, sulfate or a decomposition product of sulfate covers the surface of the composite oxide particle, and the oxidation activity on the surface of the composite oxide particle can be reduced. As a result, the generation of gas from the positive electrode active material can be suppressed, and the non-aqueous electrolyte and the like are decomposed due to the oxidation activity on the surface of the positive electrode active material in the charged state, resulting in gas generation. Can be suppressed.

  The processing temperature of the heat treatment at this low temperature is 150 ° C. or higher and lower than 500 ° C., more preferably 200 ° C. or higher and 450 ° C. or lower, and further preferably 250 ° C. or higher and 400 ° C. or lower. If the temperature falls outside this range, the sulfate decomposition reaction or sufficient physical and chemical deposition of the sulfate on the composite oxide particle surface cannot be achieved. Further, when the temperature rises outside this range, as will be described later, the surface concentration of the residual component of the sulfate decreases, thereby suppressing the gas generation mechanism of the positive electrode active material mainly composed of lithium nickelate of the present invention. There is a concern that the function to be reduced.

  In addition, when this heat treatment is performed at a high temperature of 500 ° C. or higher, the surface of the composite oxide particle is decomposed by a sulfate decomposition product as compared with the case where the heat treatment is performed at a low temperature of less than 500 ° C. Chemically eroded to deeper parts of the layer. Thereby, since more carbonate radicals are substituted with sulfate, gas generation from the positive electrode active material can be further suppressed.

  In addition, when heat processing are performed below 500 degreeC, the increase in a specific surface area, the discharge capacity fall of the secondary battery using this composite oxide particle, and the fall of charging / discharging efficiency are found. However, when the heat treatment is set to 500 ° C. or higher, a reduction in specific surface area and recovery of discharge capacity and charge / discharge efficiency of the secondary battery are found even after such a state is developed.

  The inventors have studied in detail about the recovery effect of such discharge capacity and charge / discharge efficiency, and by selecting the conditions, improvement over the recovery effect compared to the discharge capacity and charge / discharge efficiency before treatment is achieved. It turned out that an effect can be acquired. That is, the heat treatment temperature of the composite oxide particles according to one embodiment of the present invention is preferably 500 ° C. or higher and 1200 ° C. or lower, more preferably 550 ° C. or higher and 1100 ° C. or lower, and further preferably 600 ° C. or higher and 1000 ° C. or lower. If the temperature falls outside this range, as described above, the effect of improving the discharge capacity and efficiency of the positive electrode active material mainly containing lithium (Li) and nickel (Ni) cannot be obtained. On the other hand, when the temperature rises outside this range, the crystal structure of the positive electrode active material mainly containing lithium (Li) and nickel (Ni) is unstable, and the tendency to decrease the discharge capacity is conspicuous. It becomes. Note that the atmospheric condition of the heat treatment in one embodiment of the present invention is preferably an oxidizing atmosphere usually used for preparing lithium nickelate or the like, and is desirably performed in an oxygen atmosphere.

  In addition, in this invention, the discharge capacity fall of a positive electrode and the fall of efficiency are trace amounts, and if the gas generation can be suppressed, the objective can be achieved. For this reason, heat treatment at a high temperature of 500 ° C. or higher is not necessarily required. In addition, the heat treatment at a high temperature reduces the concentration of the sulfate residual component on the surface of the composite oxide particles. For this reason, there is a concern that the function of suppressing a gas generation mechanism that generates organic carbon dioxide or carbon monoxide by oxidizing organic components such as a non-aqueous electrolyte due to the strong oxidizing power of the positive electrode active material in a charged state is concerned. Is done.

  In one embodiment of the present invention, the composite oxide particles after the heat treatment may be adjusted in particle size by light pulverization or classification operation, if necessary. Thus, the positive electrode active material according to one embodiment is obtained. The positive electrode active material according to one embodiment is preferably used as an electrode active material, and in particular, is preferably used for an electrode for a nonaqueous electrolyte secondary battery.

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

(1-1) First Example of Nonaqueous Electrolyte Secondary Battery [Configuration of Nonaqueous Electrolyte Secondary Battery]
FIG. 1 shows a cross-sectional structure of a nonaqueous electrolyte secondary battery using a positive electrode active material manufactured by a method according to an embodiment of the present invention.

  This non-aqueous electrolyte secondary battery is a so-called coin-type battery. The disc-shaped positive electrode 2 accommodated in the outer can 6 and the disc-shaped negative electrode 4 accommodated in the outer cup 5 include: It is laminated via the separator 3. The separator 3 is impregnated with an electrolytic solution that is a liquid electrolyte, and the outer peripheral portions of the outer can 6 and the outer cup 5 are sealed by caulking through a gasket 7. The outer can 6 and the outer cup 5 are made of, for example, a metal such as stainless steel or aluminum (Al).

  The positive electrode 2 includes, for example, a positive electrode current collector 2A and a positive electrode mixture layer 2B provided on the positive electrode current collector 2A. The positive electrode current collector 2A is made of, for example, a metal foil such as a copper foil, a nickel foil, or a stainless steel foil. The positive electrode mixture layer 2B contains, for example, a positive electrode active material, and may contain a conductive agent such as carbon black or graphite and a binder such as polyvinylidene fluoride as necessary. As the positive electrode active material, the positive electrode active material according to the first embodiment described above can be used. Moreover, the other positive electrode active material may further be included.

  The negative electrode 4 includes, for example, a negative electrode current collector 4A and a negative electrode mixture layer 4B provided on the negative electrode current collector 4A. The negative electrode current collector 4A is made of, for example, a metal foil such as a copper foil, a nickel foil, or a stainless steel foil.

  The negative electrode mixture layer 4B includes, for example, one or more of a negative electrode material capable of occluding and releasing lithium, lithium metal, and a lithium alloy as a negative electrode active material. And a binder such as polyvinylidene fluoride.

  Examples of the negative electrode material capable of inserting and extracting lithium include carbonaceous materials, metal compounds, tin, tin alloys, silicon, silicon alloys, and conductive polymers, and any one or more of these are mixed. Used. When the positive electrode active material according to one embodiment of the present invention is used, a carbonaceous material is preferably used as the negative electrode material. The carbonaceous material is not particularly limited, and generally a material obtained by baking an organic material is used. Natural or artificial graphite can also be used. If the carbonaceous material has insufficient electronic conductivity for the purpose of current collection, it is also preferable to add a conductive agent.

Examples of the metal compound include an oxide such as a lithium complex oxide having a spinel structure (Li ₄ Ti ₅ O ₁₂ ), tungsten oxide (WO ₂ ), niobium oxide (Nb ₂ O ₅ ), or tin oxide (SnO). Examples of the conductive polymer include polyacetylene and polypyrrole.

  The separator 3 separates the positive electrode 2 and the negative electrode 4 and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes. As the material of the separator 3, those used in conventional batteries can be used, and among them, a polyolefin fine material that is excellent in short-circuit prevention effect and can improve battery safety by a shutdown effect. It is particularly preferred to use a porous film. For example, a microporous film made of polyethylene or polypropylene resin is preferable.

  Further, as the material of the separator 3, it is more preferable to use a material obtained by laminating or mixing polyethylene having a lower shutdown temperature and polypropylene having excellent oxidation resistance from the viewpoint of achieving both shutdown performance and float characteristics.

The electrolytic solution is obtained by dissolving an electrolyte salt in a non-aqueous solvent, and exhibits ion conductivity when the electrolyte salt is ionized. The electrolyte solution is not particularly limited, and a conventional nonaqueous solvent electrolyte solution or the like is used. As the electrolyte salt, alkali metal, particularly calcium halide, perchlorate, thiocyanate, borofluoride, phosphofluoride, arsenic fluoride, aluminum fluoride, trifluoromethyl sulfate, etc. are preferably used. . Specifically, for example, lithium hexafluorophosphate (LiPF ₆ ), lithium perchlorate (LiClO ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), lithium boron tetrafluoride (LiBF ₄ ), trifluoromethane Examples thereof include lithium salts such as lithium sulfonate (LiCF ₃ SO ₃ ) and lithium bis (trifluoromethanesulfonyl) imide (LiN (CF ₃ SO ₂ ) ₂ ). Any one electrolyte salt may be used alone, or two or more electrolyte salts may be mixed and used.

  Solvents for dissolving the electrolyte salt include propylene carbonate (PC), ethylene carbonate (EC), γ-butyrolactone, N-methylpyrrolidone, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,3- Dioxolane, methyl formate, sulfolane, oxazolidone, thionyl chloride, 1,2-dimethoxyethane, diethylene carbonate, and derivatives and mixtures thereof are preferably used. Any one of the solvents may be used alone, or two or more may be mixed and used.

  In this non-aqueous electrolyte secondary battery, when discharged, for example, lithium ions are released from the negative electrode 4 or lithium metal is eluted as lithium ions and reacts with the positive electrode mixture layer 2B through the electrolytic solution. . When charging is performed, for example, lithium ions are released from the positive electrode mixture layer 2B, and are inserted into the negative electrode 4 through the electrolytic solution or deposited as lithium metal.

  Such a non-aqueous electrolyte secondary battery is, for example, 4.25V or higher even when the open circuit voltage in a fully charged state per pair of positive electrode and negative electrode is in the range of 2.50V to 4.20V. It can also be used in high voltage specifications in the range of .55 V or less, preferably 4.25 V or more and 4.50 V or less. A battery with a high voltage specification can utilize the capacity of the positive electrode active material, which has not been used so far, which increases the amount of lithium released per unit mass of the positive electrode active material, and further increases the non-capacity of high capacity and high energy density. A water electrolyte secondary battery can be realized.

[Method for producing non-aqueous electrolyte secondary battery]
Next, the manufacturing method of the nonaqueous electrolyte secondary battery according to the first example will be described.

  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 (NMP). A positive electrode mixture slurry is obtained.

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

  The negative electrode 4 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 4A and removing the solvent, the negative electrode mixture layer 4B is formed by compression molding using a roll press or the like, and the negative electrode 4 is produced.

  Further, the negative electrode mixture layer 4B 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.

  Subsequently, the negative electrode 4 and the separator 3 are placed in this order at the center of the outer cup 5, the electrolyte is poured from above the separator 3, and the outer can 6 containing the positive electrode 2 is covered and caulked through the gasket 7. As a result, the nonaqueous electrolyte secondary battery as shown in FIG. 1 is formed.

(1-2) Second Example of Nonaqueous Electrolyte Secondary Battery [Configuration of Nonaqueous Electrolyte Secondary Battery]
FIG. 2 shows the structure of a non-aqueous electrolyte secondary battery using a positive electrode active material according to an embodiment of the present invention. As shown in FIG. 2, this nonaqueous electrolyte secondary battery is sealed by housing the battery element 10 in an exterior material 19 made of a moisture-proof laminate film and welding the periphery of the battery element 10. The battery element 10 is provided with a positive electrode terminal 15 and a negative electrode terminal 16, and these leads are sandwiched between outer packaging materials 19 and pulled out to the outside. An adhesive film 17 is coated on both surfaces of the positive electrode terminal 15 and the negative electrode terminal 16 in order to improve the adhesion to the exterior material 19.

  The exterior material 19 has, for example, a laminated structure in which an adhesive layer, a metal layer, and a surface protective layer are sequentially laminated. 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 10 is stored.

  For example, as shown in FIG. 3, the battery element 10 includes a strip-shaped negative electrode 12 having a gel electrolyte layer 13 provided on both sides, a separator 14, and a strip-shaped positive electrode 11 having a gel electrolyte layer 13 provided on both sides, This is a wound battery element 10 that is laminated with a separator 14 and wound in the longitudinal direction.

  The positive electrode 11 includes a strip-shaped positive electrode current collector 11A and a positive electrode mixture layer 11B formed on both surfaces of the positive electrode current collector 11A.

  One end of the positive electrode 11 in the longitudinal direction is provided with a positive electrode terminal 15 connected by, for example, spot welding or ultrasonic welding. As a material of the positive electrode terminal 15, for example, a metal such as aluminum can be used.

  The negative electrode 12 includes a strip-shaped negative electrode current collector 12A and a negative electrode mixture layer 12B formed on both surfaces of the negative electrode current collector 12A.

  Further, similarly to the positive electrode 11, a negative electrode terminal 16 connected by, for example, spot welding or ultrasonic welding is also provided at one end portion of the negative electrode 12 in the longitudinal direction. As the material of the negative electrode terminal 16, for example, copper (Cu), nickel (Ni), or the like can be used.

  The positive electrode current collector 11A, the positive electrode mixture layer 11B, the negative electrode current collector 12A, and the negative electrode mixture layer 12B are the same as in the first example.

  The gel electrolyte layer 13 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 13 is preferable because it can obtain high ionic conductivity and prevent battery leakage. The configuration of the electrolytic solution (that is, the liquid solvent and the electrolyte salt) is the same as that in the first example.

  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.

[Method for producing non-aqueous electrolyte secondary battery]
Next, a method for manufacturing the nonaqueous electrolyte secondary battery according to the second example 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 11 and the negative electrode 12, and the mixed solvent is volatilized to form the gel electrolyte layer 13. In addition, the positive electrode terminal 15 is attached to the end of the positive electrode current collector 11A in advance by welding, and the negative electrode terminal 16 is attached to the end of the negative electrode current collector 12A by welding.

  Next, the positive electrode 11 and the negative electrode 12 on which the gel electrolyte layer 13 is formed are laminated through a separator 14 to form a laminated body, and then the laminated body is wound in the longitudinal direction to form a wound battery element. 10 is formed.

  Next, a recess 18 is formed by deep-drawing the exterior material 19 made of a laminate film, the battery element 10 is inserted into the recess 18, and an unprocessed portion of the exterior material 19 is folded back to the upper portion of the recess 18. The outer peripheral part of is thermally welded and sealed. As described above, the nonaqueous electrolyte secondary battery according to the second example is manufactured.

  In one embodiment, for example, a composite containing a deposition component such as oxo acid is deposited on the surface of the composite oxide particle, the solvent is removed to deposit the deposition component, and then the deposition component is deposited. By heat-treating the oxide particles, it is possible to increase the capacity of the nonaqueous electrolyte secondary battery and improve the charge / discharge efficiency. Therefore, the secondary battery according to the embodiment of the present invention is portable, such as a video camera, a notebook personal computer, a word processor, a radio cassette recorder, a mobile phone, etc. by utilizing the features of light weight, high capacity and high energy density. It can be widely used for small electronic devices.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

<Example 1>
First, nickel sulfate, cobalt sulfate, and sodium aluminate are dissolved in water, a sodium hydroxide solution is added while stirring sufficiently, and nickel (Ni), cobalt (Co), and aluminum (Al) are mixed. A nickel-cobalt-aluminum composite coprecipitated hydroxide was obtained so that the molar ratio was Ni: Co: Al = 77: 20: 3. The produced coprecipitate was washed with water and dried, and then lithium hydroxide monohydrate was added, and the molar ratio was adjusted to Li: (Ni + Co + Al) = 105: 100 to prepare a precursor.

These precursors were calcined at 700 ° C. for 10 hours in an oxygen stream, cooled to room temperature, and then pulverized to be a composite oxidation mainly composed of lithium nickelate represented by the composition formula Li _1.03 Ni _0.77 Co _0.20 Al _0.03 O ₂ Product particles were obtained. In addition, when complex oxide particle | grains were measured by the laser scattering method, the average particle diameter was 13 micrometers.

To 100 parts by weight of the composite oxide particles described above, 1.652 parts by weight of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) was added and sufficiently mixed in a mortar. This mixture was calcined at 400 ° C. for 4 hours in an oxygen stream, cooled to room temperature, then taken out and pulverized to obtain a positive electrode active material of Example 1.

  In addition, when the positive electrode active material was measured by AGK method prescribed | regulated to JISR9101, the carbonic acid content contained was 0.04 weight%.

  The following battery is manufactured using the positive electrode active material described above.

  First, 85 parts by mass of the obtained positive electrode active material, 5 parts by mass of graphite as a conductive agent, and 10 parts by mass of polyvinylidene fluoride as a binder were mixed to prepare a positive electrode mixture. Next, this positive electrode mixture was dispersed in N-methyl-2-pyrrolidone as a dispersion medium to obtain a positive electrode mixture slurry. This positive electrode mixture slurry was uniformly applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 20 μm, dried, and compression molded with a roll press to form a positive electrode active material layer, thereby producing a positive electrode. Subsequently, a positive electrode terminal was attached to the exposed portion of the positive electrode current collector of the positive electrode.

  Next, 90 parts by mass of pulverized graphite powder as a negative electrode active material and 10 parts by mass of polyvinylidene fluoride as a binder are mixed to prepare a negative electrode mixture, which is further dispersed in N-methyl-2 as a dispersion medium. -Dispersed in pyrrolidone to make a negative electrode mixture slurry. Next, the negative electrode mixture slurry is uniformly applied on both sides of a negative electrode current collector made of a copper foil having a thickness of 15 μm, dried, and compression-molded with a roll press to form a negative electrode active material layer. Produced. Then, the negative electrode terminal was attached to the negative electrode current collector exposed portion of $ in the negative electrode.

  Next, the prepared positive electrode and negative electrode are closely adhered via a separator made of a microporous polyethylene film having a thickness of 25 μm, wound in the longitudinal direction, and a protective tape is attached to the outermost peripheral portion, whereby a wound body is obtained. Produced. Subsequently, this wound body was loaded between exterior materials, and three sides of the exterior material were heat-sealed, and one side was not heat-sealed but had an opening. As the exterior material, a moisture-proof aluminum laminate film in which a 25 μm thick nylon film, a 40 μm thick aluminum foil, and a 30 μm thick polypropylene film were laminated in order from the outermost layer was used.

Subsequently, 1 mol / l of lithium hexafluorophosphate (LiPF ₆ ) as an electrolyte salt was added to a solvent mixed so that the mass ratio was ethylene carbonate (EC): ethyl methyl carbonate (EMC) = 5: 5. An electrolytic solution prepared by dissolving was prepared. This electrolyte solution was injected from the opening of the exterior material, and the remaining one side of the exterior material was heat-sealed under reduced pressure and sealed to produce a secondary battery.

<Example 2>
Instead of 1.605 parts by weight of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), 1.600 parts by weight of lithium sulfate (Li ₂ SO ₄ .H ₂ O) is added, and the heat treatment temperature after deposition of the deposition components is 600. A positive electrode active material was produced in the same manner as in Example 1 except that the temperature was changed to ° C. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.04% by weight.

<Example 3>
Instead of 1.652 parts by weight of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), 1.757 parts by weight of cobalt sulfate (CoSO ₄ .7H ₂ O) is added, and the heat treatment temperature after deposition of the deposition components is 700 ° C. A secondary battery was made in the same manner as in Example 1 except that. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.09% by weight.

<Example 4>
1.507 parts by weight of manganese sulfate (MnSO ₄ .5H ₂ O) is added in place of 1.652 parts by weight of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), and the heat treatment temperature after deposition of the deposition components is 700 ° C. A secondary battery was made in the same manner as in Example 1 except that. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.09% by weight.

<Example 5>
Ammonium sulfate _{((NH 4) 2 SO 4} ) 1.652 of ammonium sulfate in place of the parts by weight _{((NH 4) 2 SO 4} ) 1.652 parts by weight of lithium sulfate _{(Li 2 SO 4 · H 2} O) 1.600 Weight A secondary battery was fabricated in the same manner as in Example 1 except that the mixture with the part was added. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.03% by weight.

<Example 6>
A secondary battery was fabricated in the same manner as in Example 1, except that the amount of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) was 0.826 parts by weight and the heat treatment temperature after deposition of ammonium sulfate was 790 ° C. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.01% by weight.

<Example 7>
Add 2.833 parts by weight of ammonium ammonium sulfate (AlNH ₄ (SO ₄ ) ₂ .12H ₂ O) in place of 1.652 parts by weight of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), and heat after deposition of the deposition components A secondary battery was fabricated in the same manner as in Example 1 except that the treatment temperature was 700 ° C. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.04% by weight.

<Example 8>
A secondary battery was fabricated in the same manner as in Example 1, except that the amount of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) was 0.826 parts by weight and the heat treatment time after ammonium sulfate deposition was 1 hour. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.13% by weight.

<Example 9>
A secondary battery was fabricated in the same manner as in Example 1 except that the heat treatment temperature after deposition of ammonium sulfate was 300 ° C. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.12% by weight.

<Example 10>
A secondary battery was fabricated in the same manner as in Example 1 except that the heat treatment temperature after deposition of ammonium sulfate was 500 ° C. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.03% by weight.

<Comparative Example 1>
A secondary battery was fabricated in the same manner as in Example 1 except that ammonium sulfate deposition and heat treatment after ammonium sulfate deposition were not performed. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.24% by weight.

<Comparative example 2>
A secondary battery was fabricated in the same manner as in Example 1 except that ammonium sulfate was not deposited. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.23% by weight.

<Comparative Example 3>
A secondary battery was fabricated in the same manner as in Example 1 except that the heat treatment after deposition of ammonium sulfate was not performed. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.26% by weight.

<Comparative example 4>
A secondary battery was fabricated in the same manner as in Example 1, except that the amount of ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) was 0.826 parts by weight and the heat treatment time after deposition of ammonium sulfate was 0.5 hours. did. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.17% by weight.

<Comparative Example 5>
A secondary battery was fabricated in the same manner as in Example 1 except that the heat treatment temperature after deposition of ammonium sulfate was 140 ° C. The carbonic acid content contained in the positive electrode active material measured by the AGK method was 0.24% by weight.

[Evaluation of secondary battery]
After the secondary battery produced using the positive electrode active material of each Example and Comparative Example was charged at a constant current of 880 mA at a constant current of 880 mA until the battery voltage reached 4.2 V in an environment of 23 ° C., Constant voltage charging was performed until the current value reached 1 mA at a constant voltage of 2V. Thereafter, the fully charged secondary battery was stored in an environment of 80 ° C. for 4 days. The amount of change in the thickness of the secondary battery at this time was defined as the amount of swelling during high temperature storage.

  Table 1 below shows the results of the evaluation.

  As can be seen from Examples 1 to 10 and Comparative Examples 1 and 2, each of the secondary batteries using the positive electrode active material that had been subjected to the heat treatment with the sulfate was deposited. Compared with the secondary battery of Comparative Example 1 in which no heat treatment was performed, the amount of battery swelling decreased. Moreover, the secondary battery of each Example is compared with the secondary battery of Comparative Example 2 in which the heat treatment was performed without performing the sulfate deposition, and the Comparative Example 3 in which the heat treatment was not performed after the sulfate deposition. Even so, the amount of battery swelling decreased.

  Further, as can be seen from Comparative Example 4, when the heat treatment time after the sulfate deposition was too short, the gas generation suppressing effect was not sufficiently obtained. Further, as can be seen from Comparative Example 5, even when the heat treatment temperature after sulfate deposition was too low, the gas generation suppressing effect was not sufficiently obtained.

  The positive electrode active materials prepared in Examples 1 to 10 have a reduced carbonate ion content, and heat treatment after deposition of sulfate replaces carbonate with sulfate, reducing the amount of gas generated. This is probably because

  The present invention is not limited to the above-described embodiment 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, or the like.

  In the first example, a non-aqueous electrolyte secondary battery having an electrolyte as an electrolyte has been described, and 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. Absent.

  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.

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. 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. 3 is an enlarged cross section of a part of the battery element shown in FIG. 2.

Explanation of symbols

2 .... Positive electrode 2A ... Positive electrode current collector 2B ... Positive electrode mixture layer 3 .... Separator 4 ... Negative electrode 4A ... Negative electrode current collector 4B ... Negative electrode mixture layer 5 ... Exterior cup 6 ... Exterior can 7 ... Gasket 10 ... Battery element 11 ... Positive electrode 11A ... Positive electrode current collector 11B ... Positive electrode mixture layer 12 ... Negative electrode 12A ... Negative electrode current collector 12B ... Negative electrode mixture layer 13 ... Gel electrolyte layer 14 ... Separator 15 ... Positive electrode lead 16 ... Negative electrode lead 17 ... Resin piece 18 ... Recess 19 ... Exterior materials

Claims (9)

A deposition step of depositing sulfate on the composite oxide particles containing lithium (Li) and nickel (Ni);
A method for producing a positive electrode active material, comprising: a heating step of heat-treating the composite oxide particles to which the sulfate is deposited. The method for producing a 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 _a Ni _x Co _y Al _z O ₂
(However, Ni, when the total amount of Ni is 1, within the range of 0.1 or less of Ni, manganese (Mn), chromium (Cr), iron (Fe), vanadium (V), magnesium ( Mg), titanium (Ti), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W), copper (Cu), zinc (Zn), gallium (Ga), indium (In), tin ( Sn, lanthanum (La), and cerium (Ce) can be substituted with one or more metal elements selected from the group consisting of a), lanthanum (La), and cerium (Ce), where a, x, y, and z are 0.3 ≦ a ≦ 1.05, 0.60 <x <0.90, 0.10 <y <0.40, 0.01 <z <0.20, values of x, y and z (There is a relationship of x + y + z = 1 between them.) The method for producing a positive electrode active material according to claim 2, wherein the content of carbonate ions is 0.15 wt% or less. The manufacturing method of the positive electrode active material of Claim 3 which heat-processes at the temperature of 150 to 1200 degreeC in the said heating process. 5. The method for producing a positive electrode active material according to claim 4, wherein in the depositing step, 0.01 to 20 parts by weight of sulfate is deposited with respect to 100 parts by weight of the composite oxide particles. The method for producing a positive electrode active material according to claim 5, wherein the sulfate is ammonium sulfate, lithium sulfate, or a mixed salt thereof. The method for producing a positive electrode active material according to claim 1, wherein an average particle diameter of the positive electrode active material is in a range of 2.0 μm or more and 50 μm or less. A positive electrode active material obtained by subjecting composite oxide particles having an average composition represented by chemical formula 1 to sulfate treatment to heat treatment, and having a carbonate ion content of 0.15 wt% or less.
(Chemical formula 1)
Li _a Ni _x Co _y Al _z O ₂
(However, Ni, when the total amount of Ni is 1, within the range of 0.1 or less of Ni, manganese (Mn), chromium (Cr), iron (Fe), vanadium (V), magnesium ( Mg), titanium (Ti), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W), copper (Cu), zinc (Zn), gallium (Ga), indium (In), tin ( Sn, lanthanum (La), and cerium (Ce) can be substituted with one or more metal elements selected from the group consisting of a), lanthanum (La), and cerium (Ce), where a, x, y, and z are 0.3 ≦ a ≦ 1.05, 0.60 <x <0.90, 0.10 <y <0.40, 0.01 <z <0.20, values of x, y and z (There is a relationship of x + y + z = 1 between them.) The positive electrode active material according to claim 8, wherein the positive electrode active material is provided on at least a part of a surface of the composite oxide particle and has a surface layer containing the sulfate or the decomposition product of the sulfate.

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