WO2019087503A1 - Matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux et procédé de production de matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux - Google Patents

Matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux et procédé de production de matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux Download PDF

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WO2019087503A1
WO2019087503A1 PCT/JP2018/029311 JP2018029311W WO2019087503A1 WO 2019087503 A1 WO2019087503 A1 WO 2019087503A1 JP 2018029311 W JP2018029311 W JP 2018029311W WO 2019087503 A1 WO2019087503 A1 WO 2019087503A1
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zirconium
positive electrode
active material
lithium
electrode active
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PCT/JP2018/029311
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English (en)
Japanese (ja)
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小鹿裕希
金田治輝
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住友金属鉱山株式会社
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Priority to JP2019549865A priority Critical patent/JP7052806B2/ja
Publication of WO2019087503A1 publication Critical patent/WO2019087503A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode active material for a non-aqueous electrolyte secondary battery comprising a lithium-nickel-manganese composite oxide, a non-aqueous electrolyte secondary battery, and a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery.
  • lithium nickel cobalt manganese composite oxide As a positive electrode active material of a non-aqueous electrolyte secondary battery, lithium nickel cobalt manganese composite oxide (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) having excellent thermal stability and high capacity in recent years Is being watched.
  • the lithium-nickel-cobalt-manganese composite oxide is a layered compound like the lithium-cobalt composite oxide and the lithium-nickel composite oxide, and the composition ratio of nickel, cobalt and manganese is basically 1: 1 at the transition metal site. Contains at a rate of 1.
  • Patent Document 2 also includes a mixing step of mixing a nickel-containing hydroxide, a lithium compound and a titanium compound to obtain a lithium mixture, and a baking step of firing a lithium mixture to obtain a lithium transition metal composite oxide
  • a positive electrode active material for a non-aqueous electrolyte secondary battery comprising a lithium transition metal composite oxide composed of particles of a polycrystalline structure obtained by a method has been proposed. This positive electrode active material is considered to enable realization of high thermal stability and charge / discharge capacity and excellent cycle characteristics.
  • Patent Document 3 is a positive electrode active material for a non-aqueous electrolyte secondary battery comprising a lithium transition metal composite oxide obtained by a manufacturing method including a niobium coating step and a firing step, and has a porous structure.
  • a positive electrode active material having a specific surface area of 2.0 to 7.0 m 2 / g has been proposed. By using this positive electrode active material, it is believed that a non-aqueous electrolyte secondary battery having high safety, battery capacity and excellent cycle characteristics can be obtained.
  • Patent Document 4 also describes a positive electrode active material for a non-aqueous electrolyte secondary battery having at least a lithium transition metal complex oxide having a layered structure, wherein the lithium transition metal complex oxide is a primary particle and an aggregate thereof.
  • a non-aqueous electrolyte comprising a compound present in the form of a particle comprising one or both of secondary particles and having at least one surface selected from the group consisting of molybdenum, vanadium, tungsten, boron and fluorine on at least the surface of the particle.
  • a positive electrode active material for secondary battery has been proposed. It is said that the conductivity is improved by having the above-described compound on the surface of the particles.
  • Patent Document 5 has a lithium transition metal-based compound having a function capable of inserting and releasing lithium ions as a main component, and contains at least one element selected from B and Bi as a main component material.
  • a lithium transition metal-based compound powder for a lithium secondary battery positive electrode material which is fired after the compound and one or more compounds each containing at least one element selected from Mo, W, Ti, Ta, and Re are added in combination.
  • the body is proposed. By adding and sintering the additive element, it is possible to improve the rate and output characteristics and to obtain a lithium-containing transition metal compound powder that is easy to handle and prepare an electrode.
  • Patent Document 6 proposes a positive electrode composition for a non-aqueous electrolyte secondary battery, which contains a lithium-transition metal composite oxide and a boron compound containing at least a boron element and an oxygen element. Output characteristics and cycle characteristics are improved in a positive electrode composition using a lithium transition metal composite oxide by using a positive electrode composition containing a lithium transition metal composite oxide essentially containing nickel and tungsten and a specific boron compound It can be made to
  • Patent Document 7 discloses a positive electrode active material comprising a lithium-nickel-manganese composite oxide composed of a hexagonal lithium-containing composite oxide having a layered structure, and having an average particle diameter of 2 to 8 ⁇ m, An index showing the spread of distribution [(d90 ⁇ d10) / average particle diameter] is not more than 0.60, and an outer shell portion where the aggregated primary particles are sintered, and a hollow portion existing inside thereof
  • a positive electrode active material for a non-aqueous electrolyte secondary battery is proposed which is characterized in that it has a hollow structure comprising When used in a non-aqueous secondary battery, this positive electrode active material is said to have high capacity, good cycle characteristics, and high output.
  • Patent Document 8 by adding 1 to 10% of zirconium in a molar ratio to cobalt to lithium cobalt composite oxide, the surface of lithium cobalt composite oxide particles becomes a composite oxide of zirconium oxide or lithium and zirconium. By being covered, decomposition reaction and crystal destruction of the electrolytic solution at high potential are suppressed, and it is supposed that a positive electrode active material exhibiting excellent cycle characteristics and storage characteristics can be obtained.
  • the present invention has been made in view of these circumstances, and it is a positive electrode from which a non-aqueous electrolyte secondary battery can be obtained in which the reduction in tap density is suppressed and high thermal stability and excellent battery characteristics are compatible in high dimensions.
  • the purpose is to provide an active material.
  • Another object of the present invention is to provide a method by which such a positive electrode active material can be easily produced in industrial scale production.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery includes lithium (Li), nickel (Ni), manganese (Mn), zirconium (Zr), and optionally, an element M, and
  • the minimum zirconium concentration in the primary particles may be 50% or more with respect to the average zirconium concentration in the primary particles.
  • a compound containing lithium and zirconium may be present in the positive electrode active material for a non-aqueous electrolyte secondary battery.
  • the compound containing lithium and zirconium is also selected as at least one compound selected from Li 2 ZrO 3 , Li 6 Zr 2 O 7 , Li 4 ZrO 4 , Li 8 ZrO 6 Good.
  • the selection of the compound containing lithium and zirconium is the best, the reduction of the tap density can be suppressed, the thermal stability can be further improved, and the excellent battery characteristics can be made compatible with each other in high dimensions.
  • One aspect of the present invention is characterized in that the positive electrode active material for a non-aqueous electrolyte secondary battery is used as a positive electrode.
  • a method of producing a positive electrode active material for a non-aqueous electrolyte secondary battery containing a lithium-nickel-manganese composite oxide wherein crystallization is performed to crystallize nickel-manganese composite hydroxide particles by a continuous crystallization method.
  • the nickel-manganese composite hydroxide particles added in the zirconium mixing step have the general formula (2): Ni 1-a-b Mn a M b (OH) 2 + ⁇ (wherein M in the formula (2) Is at least one element selected from Co, W, Mo, V, Mg, Ca, Al, Ti, Cr, Nb and Ta, and 0.05 ⁇ a ⁇ 0.60, 0 ⁇ b ⁇ 0.60, 0.30 ⁇ (1-ab) ⁇ 0.95, 0 ⁇ ⁇ ⁇ 0.4, and in the above-mentioned firing step, in an oxidizing atmosphere, The lithium-nickel-manganese composite oxide, which is carried out at 750 ° C.
  • the lithium manganese compound hydroxide particles obtained in the crystallization step have an average particle diameter of 0.01 ⁇ m to 10 ⁇ m and an average particle diameter of the lithium compound.
  • a mixture of zirconium compounds may be mixed to obtain a lithium zirconium mixture.
  • a positive electrode active material capable of obtaining a non-aqueous electrolyte secondary battery in which zirconium can be uniformly distributed in the lithium transition metal composite oxide after firing, and high thermal stability and excellent battery characteristics are compatible in high dimensions Can be provided.
  • the zirconium mixing step further includes a slurry step of mixing the nickel-manganese composite hydroxide particles obtained in the crystallization step and water to obtain a slurry, and the slurry A zirconium salt solution and optionally adding an alkali to coat the nickel-manganese composite hydroxide particles with a zirconium compound to obtain a zirconium-coated nickel-manganese composite hydroxide particle, the zirconium-coating process, and the zirconium-coating process It may have a lithium mixing step of mixing the zirconium-coated nickel manganese composite hydroxide particles obtained in the step and the lithium compound.
  • the obtained positive electrode active material can be provided.
  • the lithium zirconium mixing step further includes a heat treatment step of heat treating the nickel manganese composite hydroxide particles or the zirconium-coated nickel manganese composite hydroxide particles, and the heat treatment step It may be performed at a temperature of 105 ° C. or more and 700 ° C. or less.
  • the positive electrode active material which can suppress the fall of a tap density and can obtain the non-aqueous electrolyte secondary battery which made high thermal stability and the outstanding battery characteristic compatible in a high dimension can be provided. Further, the present invention can easily produce such a positive electrode active material in industrial scale production, and the industrial value can be said to be extremely large.
  • FIG. 1 is a view showing an example of a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a view showing an example of a method of producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention.
  • FIG. 3 is a view showing an example of a method of producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention.
  • FIG. 4 is a view showing an example of a method of producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention.
  • FIG. 5 is a schematic cross-sectional view of a coin-type secondary battery used for battery evaluation.
  • FIG. 6 is a diagram showing an example of the Nyquist plot.
  • FIG. 7 is a diagram showing an equivalent circuit used for impedance evaluation.
  • the inventor of the present invention added a specific amount of zirconium to a lithium nickel manganese composite oxide containing a specific amount of manganese while maintaining battery characteristics. It has been found that it is possible to achieve both electron conductivity and high thermal stability due to suppression of oxygen release during overcharge, and the present invention has been completed. Hereinafter, preferred embodiments of the present invention will be described.
  • the present embodiment described below does not unduly limit the contents of the present invention described in the claims, and can be modified without departing from the scope of the present invention. Moreover, not all the configurations described in the present embodiment are essential as the solution means of the present invention.
  • the manufacturing method of a positive electrode active material for non-aqueous electrolyte secondary batteries concerning one embodiment of the present invention, the positive electrode active material for non-aqueous electrolyte secondary batteries, and a non-aqueous electrolyte secondary battery are explained in order of the following. 1.
  • Positive electrode active material for non-aqueous electrolyte secondary battery Method of manufacturing positive electrode active material for non-aqueous electrolyte secondary battery 2-1. Crystallization process 2-2. Zirconium mixing process 2-2-1. Slurry process 2-2-2.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery (hereinafter referred to as "positive electrode active material") according to an embodiment of the present invention is composed of particles of a polycrystalline structure, and secondary particles in which a plurality of primary particles are aggregated. And lithium lithium manganese composite oxide (hereinafter referred to as "lithium metal composite oxide").
  • the above lithium metal complex oxide is generally represented by the general formula (1): Li d Ni 1 -a b c Mn a M b Zr c O 2 + ⁇ (in the general formula (1), M is Co, W, Mo At least one element selected from V, Mg, Ca, Al, Ti, Cr, Nb and Ta, and 0.05 ⁇ a ⁇ 0.60, 0 ⁇ b ⁇ 0.60, 0.0003 ⁇ c ⁇ 0.06, 0.95 ⁇ d ⁇ 1.20, 0.30 ⁇ (1-abc) ⁇ 0.95, ⁇ 0.5 ⁇ ⁇ ⁇ 0.5) Layered compounds.
  • ⁇ may be 0.
  • the zirconium in the lithium-nickel-manganese composite oxide forms a solid solution in the primary particles, and D90 and D10 in the particle size distribution by the laser diffraction scattering method of the secondary particles and the volume average particle diameter (Mv And [(D90 ⁇ D10) / Mv] is 0.80 or more and 1.20 or less, and the Li seat occupancy ratio by the Rietveld analysis is 94% or more and 97 It is characterized by being in the range of% or less.
  • a non-aqueous electrolyte secondary battery uses a flammable non-aqueous electrolyte as a battery material, high thermal stability is required.
  • a lithium ion secondary battery releases oxygen from the crystal of the positive electrode active material by being given heat in a charged state, and causes thermal runaway by reacting with an electrolytic solution.
  • As a method of enhancing the thermal stability during overcharge there is a method of adding a different element to the positive electrode active material to stabilize the crystal structure, or oxidation of the surface of the positive electrode active material such as SiO 2 , Al 2 O 3 or ZrO 2
  • a method of coating with objects has been proposed.
  • the initial decrease in charge and discharge capacity is large, and it is difficult to simultaneously achieve both the battery capacity and the thermal stability.
  • industrial scale production is often difficult because the process is complicated or difficult to scale up.
  • the present invention by adding a specific amount of zirconium to a lithium nickel manganese composite oxide containing a specific amount of manganese, the decrease in tap density is suppressed, and high thermal stability and excellent battery characteristics are achieved. It is possible to be compatible in dimensions and easily manufactured in industrial scale production. Details will be described below.
  • a positive electrode active material according to an embodiment of the present invention is made of a lithium metal composite oxide containing a specific amount of zirconium (Zr), and a non-aqueous electrolyte secondary battery (hereinafter, "secondary battery") using this positive electrode active material
  • the reaction resistance of the positive electrode is low, and the secondary battery has extremely high thermal stability during overcharging of the positive electrode active material as compared to the case where the positive electrode active material containing no zirconium is used.
  • the variation index is 0.80 or more and 1.20 or less and the particle size distribution width is broad, the filling property of the active material is high, and a high volume energy density is obtained when the secondary battery is formed.
  • the positive electrode active material of the present embodiment is characterized in that the Li seat occupancy rate is in the range of 94% to 97%, and the Li seat occupancy rate is lower compared to the case where zirconium is not contained. Since the Li site occupancy rate decreases as the addition amount of zirconium increases, it is considered that the decrease in the Li site occupancy rate is caused by solid solution of the added zirconium in the Li site. Although the details are not clear, the solid solution of zirconium on the Li side makes the crystal structure less likely to be broken even in the overcharged state, and it is considered to exhibit high thermal stability.
  • Patent Document 8 proposes a technique of adding zirconium to a lithium cobalt composite oxide, there is no description regarding Li site occupancy rate, and a composition containing neither nickel nor manganese, and zirconium oxide (ZrO (ZrO) 2 ) or the formation of a lithium zirconium compound (Li 2 ZrO 3 ), which is a technique different from the present invention.
  • the value of a is in the above range, high capacity and excellent reaction resistance can be obtained, and furthermore, high thermal stability can be obtained.
  • the value of a is less than 0.05, the effect of improving the thermal stability can not be obtained.
  • the value of a exceeds 0.60, the capacity decreases.
  • the range of c indicating the content of Zr is 0.0003 ⁇ c ⁇ 0.06, preferably 0.005 ⁇ c ⁇ 0.04.
  • the range of c is the above range, oxygen release can be suppressed when used for the positive electrode of the secondary battery, and high thermal stability can be obtained, and reaction resistance is reduced by zirconium in solid solution, which is excellent Output characteristics can be obtained.
  • the value of c is less than 0.0003, the effect of improving the thermal stability is not obtained because the amount of solid solution of zirconium is not sufficient.
  • the value of c exceeds 0.06, a large amount of lithium zirconium compound is generated, and thus the battery capacity is significantly reduced.
  • the composition of the lithium metal composite oxide can be measured by quantitative analysis by inductively coupled plasma (ICP) emission analysis.
  • M representing an additive element is at least one element selected from Co, W, Mo, V, Mg, Ca, Al, Ti, Cr, Nb and Ta
  • the range of b indicating the content of M is 0 ⁇ b ⁇ 0.60.
  • b is 0 or more, it is possible to improve the thermal stability, the storage characteristics, and the battery characteristics.
  • b exceeds 0.60 the structure becomes unstable and a layered compound is not formed, or the battery capacity may be lowered due to the relative decrease of the ratio of Ni or Mn.
  • M contains Co, the battery capacity and output characteristics are more excellent.
  • M is Co, preferably 0.05 ⁇ b ⁇ 0.5, more preferably 0.05 ⁇ b ⁇ 0.4.
  • the range of d indicating the content of Li is 0.95 ⁇ d ⁇ 1.20.
  • the reaction resistance of the positive electrode is reduced and the output of the battery is improved.
  • the value of d is less than 0.95 or exceeds 1.20, the reaction resistance may be increased, and the output of the battery may be reduced.
  • the Li site occupancy site occupancy of Li ions at 3a site of the layered compound
  • the range is preferably 97% or less, and more preferably 94.5% or more and 97% or less.
  • the thermal stability and reaction resistance improving effect is considered to be due to the solid solution of zirconium in the Li site.
  • zirconium is detected by ICP emission analysis, and by the surface analysis of the primary particle cross section using EDX in a scanning transmission electron microscope (S-TEM), zirconium is It refers to a state detected in the primary particle, and preferably zirconium is detected over the entire surface of the primary particle.
  • the Li site occupancy rate was determined from Rietveld analysis of powder X-ray diffraction pattern using Cu K ⁇ ray. If the Li site occupancy rate exceeds 97%, the thermal stability improvement effect can not be seen because the amount of solid solution of zirconium in the Li site is not sufficient. Furthermore, when the Li seat occupancy rate is less than 94%, the proportion of Li ions contributing to the charge and discharge reaction decreases, so the battery capacity is significantly reduced.
  • the minimum zirconium concentration in the primary particles is equal to the average zirconium concentration in the primary particles.
  • 50% or more is preferable.
  • the minimum zirconium concentration refers to the concentration of the locally lowest concentration of zirconium in primary particles.
  • an average zirconium concentration means the average of the zirconium concentration in primary particles.
  • the fluctuation of the zirconium concentration in the primary particles can be confirmed by analyzing the composition of the primary particle cross section by scanning transmission electron microscopy (S-TEM) EDX analysis.
  • the ratio of the minimum zirconium concentration to the average zirconium concentration in the primary particles is, for example, arbitrarily selected 20 or more primary particles from a plurality of secondary particles, and individual primary particle cross sections
  • the inside can be obtained by analyzing the composition by EDX of S-TEM.
  • the fluctuation of the zirconium concentration is a value in the primary particle, when a zirconium compound is confirmed on the surface of the primary particle by surface analysis etc. in advance, the surface of the primary particle is determined by the presence of the zirconium compound. Measure the fluctuation of zirconium concentration by EDX analysis at a position where the measured value of zirconium concentration in the vicinity is not affected.
  • the crystal structure at the time of overcharge is less likely to be broken by the solid solution of zirconium on the Li site in the primary particles. Thermal stability can be improved. Furthermore, the reaction resistance is reduced by the solid solution zirconium, and excellent output characteristics can be obtained. Therefore, high thermal stability and excellent battery characteristics can be achieved at high level.
  • the compound containing lithium and zirconium is contained in the positive electrode active material according to an embodiment of the present invention.
  • the lithium zirconium compound may be present separately from the positive electrode active material, or may be present on at least a part of the primary particle surface. Also, the entire primary particle surface may be coated. Since the lithium zirconium compound has a relatively high chemical stability with respect to the positive electrode active material, the thermal stability of the obtained secondary battery can be further enhanced by the presence of the lithium zirconium compound.
  • the lithium zirconium compound, Li 2 ZrO 3, Li 6 Zr 2 O 7, Li 4 ZrO 4, Li 8 preferably includes at least one selected from ZrO 6, thermal high stability improvement Li 6 Zr and more preferably 2 O 7.
  • an amorphous phase may be contained in part of the lithium zirconium compound.
  • the positive electrode active material preferably has a volume average particle size (Mv) of 5 ⁇ m to 20 ⁇ m, and more preferably 6 ⁇ m to 15 ⁇ m.
  • Mv volume average particle size
  • the positive electrode active material is used for the positive electrode of the secondary battery, it is possible to achieve both high output characteristics and battery capacity and high filling property to the positive electrode.
  • the average particle size of the secondary particles is less than 5 ⁇ m, high packing properties to the positive electrode may not be obtained, and when the average particle size exceeds 20 ⁇ m, high output characteristics and battery capacity may not be obtained.
  • an average particle diameter can be calculated
  • D90 and D10 particle size at 90% and particle size at 10% in volume integration of particle quantity in particle size distribution curve
  • Mv volume average particle size
  • the positive electrode active material contains many fine particles having a small particle diameter with respect to the average particle diameter and large coarse particles having a large particle diameter with respect to the average particle diameter. It will be. When these fine particles and coarse particles are mixed, the packing density is increased, and the energy density per volume can be increased. Therefore, if the variation index of the particle diameter is less than 0.80, the volumetric energy density may decrease.
  • the upper limit is 1.20 using the manufacturing method described later. When the firing temperature to be described later exceeds 1000 ° C., the dispersion index of the particle size may exceed 1.20, but when the positive electrode active material is formed, the specific surface area decreases and the resistance of the positive electrode increases to increase the battery capacity. It may decrease.
  • the tap density is preferably 2.0 g / cm 3 , more preferably 2.2 g / cm 3 or more. If the tap density is less than 2.0 g / cm 3, the filling ability of the secondary battery may be deteriorated, which may cause a decrease in volumetric energy density.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery according to one embodiment of the present invention, a decrease in tap density (less than 2.0 g / cm 3 ) is suppressed, and high thermal stability and excellent battery characteristics are achieved.
  • the positive electrode active material which can obtain the non-aqueous electrolyte secondary battery made to be compatible in the dimension can be provided.
  • FIG. 1 is a process diagram showing an outline of a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention.
  • the method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to one embodiment of the present invention includes a lithium-nickel-manganese composite oxide, and the crystallization step S10, the zirconium mixing step S20, and the firing step S30 shown in FIG. , And at least a zirconium mixing step S20 and a firing step S30.
  • the following description is an example of the manufacturing method and does not limit the manufacturing method.
  • Crystallization process S10> The method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to one embodiment of the present invention improves the thermal stability by containing manganese and, in addition, contains a combination of manganese and zirconium to obtain a positive electrode active material
  • the present invention relates to a positive electrode active material having a further enhanced thermal stability.
  • the crystallization step S10 can be performed. For example, while stirring a mixed aqueous solution containing at least nickel and manganese at a constant speed in a reaction tank, a neutralizing agent is added to control the pH by neutralization and thereby the composite
  • the hydroxide particles can be produced by coprecipitation.
  • the production method in the crystallization step S10 includes 1) a production method by batch-type crystallization, and 2) a production method by continuous crystallization.
  • a continuous crystallization production method should be used. The method of production by the continuous crystallization method is described below.
  • continuous crystallization is more productive than batch crystallization and is suitable for industrial scale production.
  • the mixed aqueous solution containing nickel and manganese for example, a sulfate solution of nickel and manganese, a nitrate solution, or a chloride solution can be used. Further, as described later, the mixed aqueous solution may contain the additional element M.
  • the composition of the metal element contained in the mixed aqueous solution substantially matches the composition of the metal element contained in the obtained composite hydroxide particles. Therefore, the composition of the metal element of the mixed aqueous solution can be prepared to be the same as the composition of the metal element of the target composite hydroxide particle.
  • the neutralizing agent an aqueous alkaline solution can be used, and for example, sodium hydroxide, potassium hydroxide and the like can be used.
  • a complexing agent to the mixed aqueous solution in combination with the neutralizing agent.
  • the complexing agent is not particularly limited as long as it can form a complex by bonding with nickel ions and other metal ions in an aqueous solution in the reaction tank (hereinafter referred to as "reacted aqueous solution"), and known ones.
  • an ammonium ion donor can be used.
  • the ammonium ion supplier is not particularly limited, and, for example, ammonia, ammonium sulfate, ammonium chloride, ammonium carbonate, ammonium fluoride and the like can be used.
  • the temperature of the reaction aqueous solution is preferably in the range of 60 ° C. to 80 ° C. or less, and the reaction aqueous solution at the above temperature
  • the pH of is preferably 10 or more and 12 or less (25.degree. C. standard).
  • the solubility of Ni increases, and the phenomenon that the precipitation amount of Ni deviates from the target composition and coprecipitation does not occur can be avoided.
  • the temperature of the reaction aqueous solution exceeds 80 ° C., the amount of evaporation of water is large, the slurry concentration (the concentration of the reaction aqueous solution) becomes high, the solubility of Ni decreases, and crystals such as sodium sulfate are generated in the filtrate.
  • the charge / discharge capacity of the positive electrode active material may decrease, for example, the impurity concentration may increase.
  • the temperature of the reaction aqueous solution is preferably 30 ° C. or more and 60 ° C. or less because the solubility of Ni in the reaction aqueous solution increases.
  • the pH of the reaction aqueous solution is preferably 10 or more and 13 or less (based on 25 ° C.), and more preferably 12 or more and 13 or less.
  • the ammonia concentration in the reaction aqueous solution at a constant value in the range of 3 g / L to 25 g / L.
  • the ammonia concentration is less than 3 g / L, the solubility of the metal ion can not be kept constant, and thus primary particles of the composite hydroxide having a uniform shape and particle size may not be formed.
  • the particle size distribution of the obtained composite hydroxide particles is also easily expanded.
  • the composite hydroxide particles are at least one selected from Co, W, Mo, V, Mg, Ca, Al, Ti, Cr, Nb, and Ta as shown in the general formula (2) described later. Elements of the following (hereinafter referred to as "additional element M") may be included.
  • the method for incorporating the additive element M into the composite hydroxide particles is not particularly limited, and any known method can be used.
  • a mixed aqueous solution containing nickel and manganese Preferably, the aqueous solution containing the additive element M is added to coprecipitate the composite hydroxide particles containing the additive element M.
  • aqueous solution containing the additional element M for example, cobalt sulfate, sodium tungstate, tungsten oxide, molybdenum oxide, molybdenum sulfide, vanadium pentoxide, magnesium sulfate, magnesium chloride, calcium chloride, aluminum chloride, aluminum aluminate, titanium sulfate,
  • An aqueous solution containing ammonium peroxotitanate, titanium potassium oxalate, niobium oxide, niobic acid, chromium chloride, sodium tantalate, tantalum acid and the like can be used.
  • a step of further coating M on the obtained composite hydroxide particles You may provide.
  • the method of coating the additive element M is not particularly limited, and a known method can be used.
  • composite hydroxide particles obtained by crystallization are dispersed in pure water to form a slurry.
  • a solution containing M of the target coverage amount is mixed with this slurry, and acid or alkali is dropped to adjust to a predetermined pH.
  • acid for example, sulfuric acid, hydrochloric acid, nitric acid and the like are used.
  • alkali for example, sodium hydroxide, potassium hydroxide or the like is used.
  • the slurry can be filtered and dried to obtain composite hydroxide particles coated with the additional element M.
  • a spray dry method in which a solution containing a compound containing M is sprayed onto composite hydroxide particles and then dried, and a solution containing a compound containing M is impregnated into composite hydroxide particles Methods etc.
  • grains mixes the additional element M to said mixed aqueous solution, and covering the additional element M to composite hydroxide particle
  • the content of M may be adjusted by coating.
  • zirconium mixing step S20 Next, the zirconium mixing step S20 will be described. As shown in FIG. 1, in the zirconium mixing step S20, a mixture containing the nickel manganese composite hydroxide particles obtained in the above crystallization step S10, a zirconium compound, and a lithium compound (hereinafter referred to as "zirconium mixture") Sometimes)).
  • a mixture of a lithium compound and a zirconium compound is added as powder (solid phase) to the composite hydroxide particles and mixed to obtain a zirconium mixture.
  • a mixture of a lithium compound and a zirconium compound is added as powder (solid phase) to the composite hydroxide particles and mixed to obtain a zirconium mixture.
  • the zirconium mixing step S20 will be described in detail with reference to FIGS.
  • the composite hydroxide particles used in the zirconium mixing step S20 have a general formula (2): Ni 1 -ab Mn a M b (OH) 2 + ⁇ (where M is Co, W, Mo, V, Mg, At least one element selected from Ca, Al, Ti, Cr, Nb and Ta, 0.05 ⁇ a ⁇ 0.60, 0 ⁇ b ⁇ 0.60, 0.30 ⁇ (1-a ⁇ b) ⁇ 0.95, 0 ⁇ ⁇ ⁇ 0.4). Since the content (composition) of the metal (Ni, Mn, M) in the composite hydroxide particles is substantially maintained in the lithium metal composite oxide, the content of each metal (Ni, Mn, M) is the same as described above. It is preferable that it is the same range as content in lithium metal complex oxide.
  • the composite hydroxide particles use nickel composite hydroxide particles containing at least manganese in the above range. Thereby, manganese can be uniformly distributed in a plurality of primary particles of the obtained positive electrode active material.
  • the positive electrode active material in which manganese and zirconium are contained (solid solution) in the plurality of primary particles has high thermal stability, and the conductivity decreases.
  • the inclusion of manganese in the primary particles makes it possible to sinter the lithium zirconium mixture at a relatively high temperature. And by baking at high temperature, the zirconium in a zirconium compound can be dissolved in a primary particle more uniformly.
  • the method for producing the composite hydroxide particles is not particularly limited, but it is preferable to use the composite hydroxide particles obtained in the crystallization step S10 as shown in FIGS.
  • the composite hydroxide particles are those in which nickel and manganese are uniformly contained in the particles, and for example, a mixture of nickel hydroxide particles and a manganese compound, or a manganese compound coated In the case of nickel hydroxide particles and the like, the distribution of manganese in the obtained positive electrode active material may become uneven, and the effect obtained by incorporating manganese may not be sufficiently obtained.
  • the zirconium mixing step S20 for example, a mixture of the lithium compound and the zirconium compound is mixed with the nickel manganese composite hydroxide particles obtained in the crystallization step S10 to form a zirconium mixture. It is preferable to obtain. In this way, it is possible to obtain a lithium-nickel-manganese composite oxide in which zirconium forms a solid solution in at least primary particles in the later-described firing step S30.
  • the zirconium compound is preferably mixed in the form of particles (solid phase).
  • the reactivity changes in the subsequent firing step S30 depending on the particle size of the zirconium compound, so the particle size of the zirconium compound used is one of the important factors.
  • the average particle diameter of the zirconium compound is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.05 ⁇ m to 3.0 ⁇ m, and still more preferably 0.08 ⁇ m to 1.0 ⁇ m.
  • an average particle diameter is volume average particle diameter Mv, for example, can be calculated
  • the zirconium compound may be previously ground to a particle size in the above range using various grinders such as a ball mill, a planetary ball mill, a jet mill / nano jet mill, a bead mill, and a pin mill.
  • the zirconium compound may be classified by a dry classifier or a sieve, if necessary. For example, screening can be performed to obtain particles close to 0.01 ⁇ m.
  • zirconium compound mixed in the zirconium mixing step S20 a known compound containing zirconium can be used, and for example, zirconium oxide, zirconium hydroxide, zirconium sulfate, zirconium trichloride, zirconium tetrachloride, etc. can be used. .
  • zirconium oxide, zirconium hydroxide, or a mixture of these is preferable from the viewpoint of easy availability and prevention of mixing of impurities into the lithium metal composite oxide.
  • an impurity mixes in lithium metal complex oxide, the heat stability of the secondary battery obtained, a battery capacity, and the fall of cycling characteristics may be caused.
  • the method of mixing the composite hydroxide particles, the lithium compound and the zirconium compound is not particularly limited, and the composite hydroxide particles, the lithium compound and the zirconium compound are sufficiently sufficient to prevent destruction of the complex such as the composite hydroxide particles. It should just be mixed.
  • mixing can be performed using a common mixer, and for example, mixing can be performed using a shaker mixer, a lodige mixer, a Julia mixer, a V blender, or the like.
  • the atomic% ratio (Li / Me, General Formula (1)) between Li and the metal element Me other than Li (in this embodiment, Me Ni + Mn + additional element M + Zr) between individual particles of the positive electrode active material And the same as d of the general formula (3) described later may vary, and problems such as a failure to obtain sufficient battery characteristics may occur.
  • the lithium compound is mixed such that Li / Me in the lithium zirconium mixture is 0.95 or more and 1.20 or less. That is, Li / Me in the zirconium mixture is mixed to be the same as Li / Me in the obtained positive electrode active material. This is because the molar ratio of Li / Me and each metal element does not change before and after the firing step S30 to be described later, and therefore Li / Me of the lithium zirconium mixture at the time of the mixing becomes Li / Me of the positive electrode active material. It is.
  • the content of zirconium in the lithium-zirconium mixture is 0.03 atomic% or more to the total of metal elements (Ni, Mn, additive elements M, Zr) other than Li in the lithium-zirconium mixture. It mixes so that it may become atomic% or less.
  • a zirconium compound may be coated on the surface of the nickel-manganese composite hydroxide particles to obtain a zirconium mixture.
  • the nickel-manganese composite hydroxide particles obtained in the crystallization process S10 and water are mixed to obtain a slurry.
  • the zirconium compound can be crystallized and easily coated on the surface of the nickel-manganese composite hydroxide particles in the zirconium coating step S22 described later.
  • the mixing method is not particularly limited, and a known method may be used.
  • the coating method of the zirconium compound is not particularly limited, and known methods can be used, but from the viewpoint of being inexpensive and industrially easy to use, for example, the composite hydroxide particles and water are mixed
  • a zirconium salt solution and, if necessary, an alkali are added to the obtained slurry to crystallize a zirconium compound (for example, zirconium hydroxide etc.) on the surface of the composite hydroxide particles.
  • a zirconium compound for example, zirconium hydroxide etc.
  • the slurry obtained by mixing the composite hydroxide particles and water since the slurry obtained by mixing the composite hydroxide particles and water exhibits basicity, it may reach the pH at which the zirconium compound crystallizes when the amount of the zirconium salt solution is small. In some cases, no alkali is added.
  • the mixing method is not particularly limited, and a known method may be used.
  • Heat treatment process S24> In the method of manufacturing a positive electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention, as shown in FIG. 4, heat treatment is further performed to heat the nickel manganese composite hydroxide particles in the zirconium mixing step S20. You may have process S24.
  • the heat treatment step S24 is a step of removing at least a part of the water contained in the composite hydroxide particles by heat treatment. By having the heat treatment step S24, by removing at least a part of the water remaining in the composite hydroxide particles, it is possible to prevent the variation of Li / Me of the positive electrode active material obtained in the baking step S30 described later. Can.
  • the heat treatment in the heat treatment step S24 is preferable to sufficiently oxidize the composite hydroxide particles and convert them to composite oxide particles from the viewpoint of further reducing the variation of Li / Me.
  • it is sufficient if water can be removed to such an extent that variation does not occur in Li / Me of the positive electrode active material it is necessary to convert the hydroxide (composite hydroxide) in all composite hydroxide particles to a composite oxide There is no.
  • the composite hydroxide particles are heat-treated before preparing the zirconium mixture, and then the composite hydroxide particles after the heat treatment
  • a zirconium mixture can be prepared by mixing and / or composite oxide particles, a lithium compound and a zirconium compound.
  • the composite hydroxide particles contain the additional element M
  • heat treatment may be performed, and the composite hydroxide particles and / or after the heat treatment
  • the composite oxide particles may be coated with a compound containing the additive element M.
  • the obtained zirconium-coated composite hydroxide particles may be heat-treated.
  • a heat treatment step S24 is performed after the zirconium covering step S22 to be described with reference to FIG. 3, and a lithium mixing step S23 is performed (not shown).
  • the heat treatment in the heat treatment step S24 may be performed at a temperature at which residual water in the composite hydroxide particles is removed, and for example, the temperature of the heat treatment is preferably 105 ° C. or more and 700 ° C. or less.
  • the temperature of the heat treatment is preferably 105 ° C. or more and 700 ° C. or less.
  • the composite hydroxide particles are heated at 105 ° C. or higher, at least a portion of the residual water can be removed.
  • the temperature of the heat treatment is less than 105 ° C., it takes a long time to remove the residual moisture, which is not industrially suitable.
  • the temperature of the heat treatment exceeds 700 ° C., the particles converted into composite oxide particles may be sintered and agglomerated.
  • the temperature of the heat treatment is preferably 350 ° C. or more and 700 ° C. or less.
  • the atmosphere in which the heat treatment is performed is not particularly limited.
  • the heat treatment is preferably performed in an air stream.
  • the time of the heat treatment is not particularly limited, and may be, for example, one hour or more. If the heat treatment time is less than 1 hour, residual water in the composite hydroxide particles may not be sufficiently removed.
  • the heat treatment time is preferably 5 hours or more and 15 hours or less.
  • the equipment used for the heat treatment is not particularly limited as long as the composite hydroxide particles can be heated in a stream of air, and for example, an air drier, an electric furnace without gas generation, etc. can be suitably used. .
  • Firing step S30> In the firing step S30, the above-mentioned mixture obtained in the zirconium mixing step S20 is fired to obtain the above lithium nickel manganese composite oxide.
  • the firing step S30 is performed at 750 ° C. or more and 1000 ° C. or less in an oxidizing atmosphere.
  • a lithium metal composite oxide composed of particles of a polycrystalline structure is formed.
  • Ru The lithium compound melts at the temperature at the time of firing and penetrates into the composite hydroxide particles to form a lithium metal composite oxide.
  • the zirconium compound penetrates to the inside of the secondary particles together with the molten lithium compound. Also, in the primary particles, if grain boundaries are present, they will penetrate. The permeation promotes diffusion inside the primary particles, and zirconium is uniformly dissolved in the primary particles.
  • zirconium depending on the amount of zirconium, it may exceed the solid solution limit in the primary particle, and the zirconium exceeding the solid solution limit reacts with the excess lithium component, and the lithium zirconium compound is reacted to the primary particle surface or grain boundary, Or it forms alone.
  • the firing temperature is 750 ° C. or more and 1000 ° C. or less in an oxidizing atmosphere, preferably 750 ° C. or more and 950 ° C. or less.
  • the lithium zirconium mixture can increase the firing temperature by containing manganese. Increasing the firing temperature promotes the diffusion of zirconium and promotes the formation of a lithium zirconium compound.
  • the crystallinity of the lithium-nickel-manganese composite oxide is increased, and the battery capacity can be further improved.
  • the firing temperature is less than 750 ° C.
  • the diffusion of lithium and zirconium into the nickel manganese composite hydroxide particles is not sufficiently carried out, excess lithium and unreacted particles remain, and the crystal structure is sufficient. If the battery is not ready, a problem arises that sufficient battery characteristics can not be obtained. In addition, the Li seat occupancy rate may be too high to obtain sufficient thermal stability.
  • the firing temperature exceeds 1000 ° C., severe sintering may occur among the formed lithium transition metal complex oxide particles, and abnormal grain growth may occur.
  • the baking time is preferably at least 3 hours or more, and more preferably 6 hours or more and 24 hours or less. When the firing time is less than 3 hours, the formation of the lithium transition metal complex oxide may not be sufficiently performed.
  • the atmosphere at the time of firing is preferably an oxidation atmosphere, and more preferably an atmosphere having an oxygen concentration of 3 to 100% by volume. That is, the firing is preferably performed in the air or oxygen stream. This is because if the oxygen concentration is less than 3% by volume, the oxygen can not be sufficiently oxidized, and the crystallinity of the lithium transition metal complex oxide may be insufficient. In particular, in consideration of the battery characteristics, it is preferable to carry out in an oxygen stream.
  • the furnace used for the firing is not particularly limited as long as it can bake the lithium-zirconium mixture in an air or oxygen stream, but it is preferable to use an electric furnace without gas generation, and a batch system or a continuous system. Any of the furnaces of
  • the firing step S30 may further include a step of calcining at a temperature lower than the firing temperature before firing at a temperature of 750 ° C. or more and 1000 ° C. or less.
  • the calcination is preferably performed at a temperature at which the lithium compound and / or the zirconium compound in the lithium zirconium mixture melts and can react with the composite hydroxide particles.
  • the calcination temperature may be, for example, 350 ° C. or more and a temperature lower than the firing temperature.
  • the lower limit of the calcination temperature is preferably 400 ° C. or more.
  • the lithium compound and / or the zirconium compound penetrates into the composite hydroxide particles, sufficient diffusion of lithium and zirconium takes place, and uniform lithium is obtained.
  • a metal complex oxide can be obtained.
  • the lithium transition metal complex oxide obtained by firing may form coarse particles due to weak sintering or aggregation.
  • the particle size distribution can be adjusted by eliminating the above-mentioned sintering and aggregation by crushing.
  • the above lithium nickel manganese complex oxide is generally represented by the general formula (3): Li d Ni 1 -a b c Mn a M b Zr c O 2 + ⁇ (in the above formula (3), M is Co, W, At least one element selected from Mo, V, Mg, Ca, Al, Ti, Cr, Nb and Ta, 0.05 ⁇ a ⁇ 0.60, 0 ⁇ b ⁇ 0.60, 0.0003 ⁇ c ⁇ 0.06, 0.95 ⁇ d ⁇ 1.20, 0.30 ⁇ (1-abc) ⁇ 0.95, ⁇ 0.5 ⁇ ⁇ ⁇ 0.5) expressed.
  • the particle size distribution can be adjusted by eliminating the above-mentioned sintering and aggregation by crushing.
  • the reduction in tap density is suppressed, and high thermal stability and excellent battery characteristics are made compatible with each other in high dimensions.
  • the positive electrode active material which can obtain a water-based electrolyte secondary battery can be provided. Further, the present invention can easily produce such a positive electrode active material in industrial scale production, and the industrial value can be said to be extremely large.
  • Non-aqueous electrolyte secondary battery (hereinafter, also referred to as “secondary battery”) according to an embodiment of the present invention uses the above-described positive electrode active material for a positive electrode.
  • a secondary battery according to an embodiment of the present invention will be described for each component.
  • a secondary battery according to an embodiment of the present invention includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and is configured of the same components as a general lithium ion secondary battery.
  • the embodiment described below is merely an example, and the non-aqueous electrolyte secondary battery may be implemented in various modifications and improvements based on the knowledge of those skilled in the art, including the following embodiment. it can. Further, the secondary battery does not particularly limit its use.
  • the positive electrode of a secondary battery is manufactured using the positive electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention described above.
  • An example of a method for producing a positive electrode will be described below. First, the above-mentioned positive electrode active material (powder), a conductive material and a binder (binder) are mixed, and if necessary, activated carbon and a solvent for adjusting viscosity etc. are added, and the mixture is kneaded to obtain a positive electrode. A mixture paste is prepared.
  • the mixing ratio of each material in the positive electrode mixture is a factor that determines the performance of the lithium secondary battery, and can be adjusted according to the application.
  • the mixing ratio of the materials can be the same as that of the positive electrode of a known lithium secondary battery.
  • the positive electrode active material It can contain up to 95% by mass, 1 to 20% by mass of a conductive material, and 1 to 20% by mass of a binder.
  • the obtained positive electrode mixture paste is applied, for example, on the surface of a current collector made of aluminum foil, and dried to disperse the solvent, whereby a sheet-like positive electrode is produced. If necessary, pressure may be applied by a roll press or the like to increase the electrode density.
  • the sheet-like positive electrode obtained in this manner can be cut into an appropriate size according to the target battery, and can be used for battery production.
  • the method of producing the positive electrode is not limited to the one described above, and other methods may be used.
  • the conductive material for example, graphite (natural graphite, artificial graphite, expanded graphite and the like), carbon black-based materials such as acetylene black and ketjen black can be used.
  • the binding agent serves to hold active material particles, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), fluororubber, ethylene propylene diene rubber, styrene butadiene, cellulose type Resin and polyacrylic acid can be used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • fluororubber ethylene propylene diene rubber
  • styrene butadiene cellulose type Resin and polyacrylic acid
  • the positive electrode active material, the conductive material and the activated carbon are dispersed, and a solvent which dissolves the binder is added to the positive electrode mixture.
  • a solvent which dissolves the binder is added to the positive electrode mixture.
  • an organic solvent such as N-methyl-2-pyrrolidone can be used.
  • activated carbon can be added to the positive electrode mixture in order to increase the capacity of the electric double layer.
  • Negative electrode> metal lithium, lithium alloy or the like can be used. Also, for the negative electrode, a negative electrode active material capable of absorbing and desorbing lithium ions is mixed with a binder, and an appropriate solvent is added to form a paste-like negative electrode composite material on the surface of a metal foil current collector such as copper. It may be applied, dried, and compressed as needed to increase the electrode density.
  • the negative electrode active material it is possible to use, for example, a natural graphite, a calcined product of an organic compound such as artificial graphite and a phenol resin, and a powder of a carbon material such as coke.
  • a fluorine-containing resin such as PVDF can be used as in the positive electrode
  • an organic compound such as N-methyl-2-pyrrolidone A solvent can be used.
  • a separator is interposed and disposed between the positive electrode and the negative electrode.
  • a separator separates a positive electrode and a negative electrode and holds an electrolyte, and a known one can be used.
  • a thin film such as polyethylene or polypropylene, which has a large number of fine pores, may be used. it can.
  • Non-aqueous electrolyte is one in which a lithium salt as a support salt is dissolved in an organic solvent.
  • a lithium salt as a support salt is dissolved in an organic solvent.
  • an ionic liquid is comprised from the cation and anions other than lithium ion, and means the salt which shows a liquid form also at normal temperature.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate and trifluoropropylene carbonate
  • linear carbonates such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate and dipropyl carbonate, and further tetrahydrofuran
  • the non-aqueous electrolyte may contain a radical scavenger, a surfactant, a flame retardant, and the like.
  • the solid electrolyte does not decompose even at high potential, it has high thermal stability because there is no gas generation and thermal runaway due to decomposition of the electrolyte during charging as seen in non-aqueous electrolytes. Therefore, when it uses for the lithium ion secondary battery using the positive electrode active material by this invention, the secondary battery with high thermal stability can be obtained.
  • the solid electrolyte include inorganic solid electrolytes and organic solid electrolytes.
  • an oxide-based solid electrolyte As the inorganic solid electrolyte, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, or the like is used.
  • the oxide-based solid electrolyte is not particularly limited, and any oxide-based solid electrolyte containing oxygen (O) and having lithium ion conductivity and electronic insulation can be used.
  • an oxide system solid electrolyte for example, lithium phosphate (Li 3 PO 4 ), Li 3 PO 4 N x , LiBO 2 N x , LiNbO 3 , LiTaO 3 , Li 2 SiO 3 , Li 4 SiO 4 -Li 3 PO 4 , Li 4 SiO 4 -Li 3 VO 4 , Li 2 O-B 2 O 3 -P 2 O 5 , Li 2 O-SiO 2 , Li 2 O-B 2 O 3 -ZnO, Li 1 + X Al X Ti 2-X (PO 4) 3 (0 ⁇ X ⁇ 1), Li 1 + X Al X Ge 2-X (PO 4) 3 (0 ⁇ X ⁇ 1), LiTi 2 (PO 4) 3, Li 3X La 2 / 3-X TiO 3 (0 ⁇ X
  • the sulfide-based solid electrolyte is not particularly limited, and any material containing sulfur (S) and having lithium ion conductivity and electronic insulation can be used.
  • S sulfur
  • the sulfide-based solid electrolyte for example, Li 2 S—P 2 S 5 , Li 2 S—SiS 2 , LiI—Li 2 S—SiS 2 , LiI—Li 2 S—P 2 S 5 , LiI—Li 2 S-B 2 S 3 , Li 3 PO 4 -Li 2 S-Si 2 S, Li 3 PO 4 -Li 2 S-SiS 2 , LiPO 4 -Li 2 S-SiS, LiI-Li 2 S-P 2 O 5 and LiI-Li 3 PO 4 -P 2 S 5 and the like.
  • the inorganic solid electrolyte one other than the above may be used, and for example, Li 3 N, LiI, Li 3 N-LiI-LiOH, etc. may be used.
  • the organic solid electrolyte is not particularly limited as long as it is a polymer compound exhibiting ion conductivity.
  • polyethylene oxide, polypropylene oxide, copolymers of these, and the like can be used.
  • the organic solid electrolyte may also contain a support salt (lithium salt).
  • a solid electrolyte you may mix a solid electrolyte also in positive electrode material, in order to ensure the contact of an electrolyte and a positive electrode active material.
  • the non-aqueous electrolyte secondary battery of the present invention which is composed of the positive electrode, the negative electrode, the separator, and the non-aqueous electrolytic solution described above, can be formed into various shapes such as a cylindrical shape and a laminated shape.
  • the positive electrode and the negative electrode are stacked via a separator to form an electrode body, and the obtained electrode body is impregnated with a non-aqueous electrolytic solution and passed to the positive electrode current collector and the outside. Connection with the positive electrode terminal and between the negative electrode current collector and the negative electrode terminal leading to the outside are connected using a current collection lead etc. and sealed in the battery case to complete the non-aqueous electrolyte secondary battery. .
  • the secondary battery according to an embodiment of the present invention can suppress a decrease in tap density and achieve both high thermal stability and excellent battery characteristics in a high level.
  • the positive electrode active material used for said secondary battery can be obtained by the industrial manufacturing method mentioned above.
  • the secondary battery according to an embodiment of the present invention is suitable as a power source of a small portable electronic device (such as a notebook personal computer or a portable telephone terminal) which always requires a high capacity.
  • the secondary battery according to one embodiment of the present invention has not only the capacity and the electron conductivity but also the comparison with a battery using a conventional lithium cobalt-based oxide or lithium nickel-based oxide positive electrode active material. Excellent in durability and thermal stability during overcharge.
  • the secondary battery according to an embodiment of the present invention is not only a power source for an electric vehicle driven purely by electric energy, but also as a power source for a so-called hybrid vehicle used in combination with a combustion engine such as a gasoline engine or a diesel engine. Can also be used.
  • a method of manufacturing a positive electrode active material for a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery, and a positive electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention will be described in detail by examples.
  • the analysis method of the metal contained in the positive electrode active material in an Example and a comparative example and the various evaluation methods of a positive electrode active material are as follows.
  • Approximately 2 mg of the dried positive electrode was weighed, and the temperature was raised from room temperature to 450 ° C. at a heating rate of 10 ° C./min using a gas chromatograph mass spectrometer (GCMS, Shimadzu Corporation, QP-2010 plus). Helium was used as a carrier gas. The generation behavior of oxygen (m / z 32) generated at the time of heating was measured, and the semiquantitative determination of the amount of oxygen generation was performed from the maximum oxygen generation peak height and peak area obtained, and these were used as the evaluation index of thermal stability. . The semi-quantitative value of the amount of generated oxygen was calculated by injecting pure oxygen gas as a standard sample into GCMS and extrapolating the calibration curve obtained from the measurement result.
  • GCMS gas chromatograph mass spectrometer
  • Example 1 ⁇ Crystallization process> A predetermined amount of pure water was placed in a reaction tank (60 L), and the temperature in the tank was set to 49 ° C. while stirring. At this time, N 2 gas was flowed into the reaction tank so that the concentration of dissolved oxygen in the reaction liquid became 0.8 mg / L.
  • the flow rate was controlled so that the residence time of the mixed aqueous solution was 8 hours, the pH in the reaction tank was adjusted to 12.0-12.6, and the ammonia concentration was adjusted to 10-14 g / L.
  • the slurry containing the nickel-cobalt-manganese composite hydroxide was recovered from the overflow port, and then filtered to obtain a cake of a nickel-cobalt-manganese composite hydroxide (crystallization step). Impurities were washed by passing 1 L of pure water with respect to 140 g of the nickel-cobalt-manganese composite hydroxide present in the Denver subjected to filtration.
  • the powder after filtration was dried to obtain nickel-cobalt-manganese composite hydroxide particles represented by Ni 0.80 Co 0.10 Mn 0.10 (OH) 2 + ⁇ (0 ⁇ ⁇ ⁇ 0.4).
  • the average particle size Mv of the obtained composite hydroxide was 12.6 ⁇ m.
  • Nirconium mixing process The obtained nickel-cobalt-manganese composite hydroxide particles, lithium hydroxide, and zirconium oxide (ZrO 2 ) having an average particle diameter of 1.0 ⁇ m, and the molar ratio of nickel: cobalt: manganese: zirconium are 79.4: The atomic ratio of lithium (Li) to the total metal (Me) of nickel, cobalt, manganese and zirconium (hereinafter referred to as Li / Me) such that 10.0: 9.8: 0.8 The mixture was weighed to obtain 1.01 and thoroughly mixed using a shaker mixer apparatus (TURBULA Type T2C manufactured by Willy-E. Bachkofen (WAB)) to obtain a lithium mixture.
  • TURBULA Type T2C manufactured by Willy-E. Bachkofen (WAB)
  • the obtained lithium mixture is calcined by holding it in a stream of air (oxygen: 21% by volume) at 800 ° C. for 10 hours, and then crushed to obtain a positive electrode active material composed of a lithium nickel cobalt manganese zirconium composite oxide.
  • the volume average particle diameter Mv, the variation index and the tap density of the obtained positive electrode active material are shown in Table 1.
  • Table 1 The volume average particle diameter Mv, the variation index and the tap density of the obtained positive electrode active material.
  • Electrochemical characterization 52.5 mg of the obtained positive electrode active material, 15 mg of acetylene black, and 7.5 mg of polytetrafluoroethylene resin (PTFE) were mixed and press-molded to a diameter of 11 mm and a thickness of 100 ⁇ m under a pressure of 100 MPa.
  • An evaluation electrode 2 was produced. The produced positive electrode 2 was dried in a vacuum drier at 120 ° C. for 12 hours, and then, using this positive electrode 2, a 2032 type coin battery 1 was produced in a glove box under an Ar atmosphere controlled to have a dew point of ⁇ 80 ° C.
  • the negative electrode 3 uses lithium (Li) metal having a diameter of 17 mm and a thickness of 1 mm, and the electrolyte contains an equal mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC) using 1 M LiClO 4 as a supporting electrolyte. Toyama Pharmaceutical Co., Ltd.) was used.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the separator 4 a polyethylene porous film with a film thickness of 25 ⁇ m was used.
  • the coin battery has a gasket 5 and a wave washer 6, and the positive electrode can 7 and the negative electrode can 8 are assembled into a coin-type battery.
  • Table 2 The measurement results of the initial charge / discharge capacity and the positive electrode resistance value of the obtained positive electrode active material are shown in Table 2.
  • Thermal stability evaluation was performed by the procedure as described in the evaluation method (G) of the above-mentioned positive electrode active material. The semi-quantitative value of the amount of generated oxygen was determined from the maximum oxygen evolution peak intensity and the peak area obtained. The results are shown in Table 2.
  • the determination method of the electrochemical characteristic evaluation and thermal stability evaluation of the battery obtained above was determined by the following three-step evaluation (1, 2, 3).
  • Example 2 In the lithium mixing step, the obtained nickel-cobalt-manganese composite hydroxide particles, lithium hydroxide, and zirconium oxide (ZrO 2 ) having an average particle diameter of 1.0 ⁇ m are made of nickel: cobalt: manganese: zirconium in a molar ratio of 78.
  • a positive electrode active material was obtained and evaluated in the same manner as in Example 1 except that measurement was performed so as to be 0: 9.8: 9.6: 2.6. Moreover, as a result of XRD measurement, a peak attributable to Li 6 Zr 2 O 7 was confirmed. The evaluation results are shown in Tables 1 to 3.
  • Example 3 ⁇ Crystallization process>
  • Ni 0.80 Co 0.10 Mn 0.10 (OH) 2 + ⁇ (0 ⁇ ⁇ ⁇ 0.4) are obtained. Obtained.
  • ⁇ Zirconium coating process in zirconium mixing process Next, adjust the concentration of zirconium sulfate (Zr (SO 4 ) 2 ⁇ nH 2 O) powder to 100 g / L in the aqueous solution, keep the solution temperature constant at 50 ° C., and stir for 2 hours. After dissolution, the residue was filtered off to make a zirconium salt solution.
  • a zirconium salt solution and a 25 mass% sodium hydroxide aqueous solution are simultaneously added dropwise to a slurry obtained by mixing the above nickel-cobalt-manganese composite hydroxide with pure water so that the pH becomes 11.0 while maintaining the liquid temperature at 25 ° C.
  • a nickel-cobalt-manganese composite hydroxide coated with a zirconium compound was obtained. The targeted amount of zirconium added was 0.8 (molar ratio).
  • Li / Me The atomic ratio (hereinafter referred to as Li / Me) of the obtained zirconium-coated nickel-cobalt-manganese composite hydroxide particles and lithium hydroxide and the total metal amount of lithium, nickel, cobalt, manganese and zirconium is 1.01.
  • the mixture was sufficiently mixed using a shaker mixer apparatus (TURBULA Type T2C manufactured by Willy-E. Bachopen (WAB)) to obtain a lithium mixture.
  • the firing step and the subsequent steps were the same as in Example 1, and a positive electrode active material was obtained and evaluated.
  • the evaluation results are shown in Tables 1 to 3.
  • Example 4 In the same manner as in the crystallization step of Example 1, nickel-cobalt-manganese composite hydroxide particles represented by Ni 0.80 Co 0.10 Mn 0.10 (OH) 2 + ⁇ (0 ⁇ ⁇ ⁇ 0.4) are obtained. After that, in the zirconium coating step, a positive electrode active material was obtained and evaluated in the same manner as in Example 3 except that the target zirconium addition amount was set to 2.6 (molar ratio). The evaluation results are shown in Tables 1 to 3.
  • Example 5 In the lithium mixing step, the obtained nickel-cobalt-manganese composite hydroxide particles, lithium hydroxide, zirconium oxide (ZrO 2 ) having an average particle diameter of 1.0 ⁇ m, and the molar ratio of nickel: cobalt: manganese: zirconium are 76.
  • the positive electrode active material was obtained and evaluated in the same manner as in Example 1 except that the weight was measured to be 6: 9.7: 9.5: 4.2. The evaluation results are shown in Tables 1 to 3.
  • Example 1 In the lithium mixing step, the positive electrode was activated as in Example 1 except that zirconium oxide was not prepared (the obtained nickel-cobalt-manganese composite hydroxide particles and lithium hydroxide were weighed so that Li / Me would be 1.01). The material was obtained and evaluated. The evaluation results are shown in Tables 1 to 3.
  • Example 2 In the lithium mixing step, the obtained nickel-cobalt-manganese composite hydroxide particles, lithium hydroxide, and zirconium oxide (ZrO 2 ) having an average particle diameter of 1.0 ⁇ m are made of a nickel: cobalt: manganese: zirconium molar ratio of 74.
  • the positive electrode active material was obtained and evaluated in the same manner as in Example 1 except that the weight was measured to be 5: 9.4: 9.1: 7.0. The evaluation results are shown in Tables 1 to 3.
  • the positive electrode active material obtained in the examples has extremely good thermal stability and excellent reaction resistance as compared with Comparative Example 1 in which no zirconium is added. .
  • zirconium is in solid solution in primary particles, and the Li site occupancy rate is lower than that in the case where zirconium is not added. Furthermore, in all the examples, the decrease in tap density was suppressed and the value was high.
  • the solid solution of zirconium on the Li side makes it difficult for the crystal structure to collapse even in an overcharged state, and is considered to exhibit high thermal stability. Further, it is considered that Li ions are easily moved in the crystal by the solid solution zirconium, and the reaction resistance is reduced.
  • the addition method of Zr may be either solid phase addition or coating, and in the case of the coat, the thermal stability improving effect and the resistance reduction effect are higher than that of the solid phase addition. From the viewpoint of productivity etc., solid phase addition is dominant industrially.
  • the positive electrode active material of Comparative Example 1 is inferior in both thermal stability and reaction resistance because Zr is not added.
  • the thermal stability is extremely good because the amount of Zr added is large, but a large amount of Zr compound is precipitated due to the excessive addition of Zr, and the reaction resistance and the initial capacity are significantly deteriorated.
  • the reduction in the amount of Ni contributing to the redox also affects the capacity reduction, and it is presumed that the thermal stability apparently improved due to the low electrochemical characteristics.
  • Comparative Example 5 the composite hydroxide particles are obtained by the batch crystallization method, so that the variation index and the tap density of the active material are low. As in the examples, the high thermal stability and the excellent battery characteristics are shown, but the low tap density is considered to cause the deterioration of the packing property when made into a secondary battery and to cause a decrease in volumetric energy density.
  • the manufacturing method of a positive electrode active material for non-aqueous electrolyte secondary batteries concerning one embodiment of the present invention, the positive electrode active material for non-aqueous electrolyte secondary batteries, and a non-aqueous electrolyte secondary battery suppress the fall of the tap density. It is possible to provide a positive electrode active material from which a non-aqueous electrolyte secondary battery can be obtained in which high thermal stability and excellent battery characteristics are compatible in a high level. Further, the present invention can easily produce such a positive electrode active material in industrial scale production, and the industrial value can be said to be extremely large.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery in which high thermal stability and excellent battery characteristics are compatible in a high level can be obtained by an industrial manufacturing method.
  • This non-aqueous electrolyte secondary battery is suitable as a power source for small portable electronic devices (such as notebook personal computers and mobile phone terminals) which are required to have high capacity and long life at all times.
  • the secondary battery according to one embodiment of the present invention is excellent in safety also in comparison with a battery using a conventional lithium cobalt-based oxide or lithium nickel-based oxide positive electrode active material, and further, Excellent in capacity and durability. Therefore, since miniaturization and long life are possible, it is suitable as a power source for electric vehicles which is restricted in mounting space.
  • the positive electrode active material according to one embodiment of the present invention and the secondary battery using the same are used not only as a power source for an electric vehicle purely driven by electric energy, but also in combination with a combustion engine such as a gasoline engine or a diesel engine. It can also be used as a so-called power supply for hybrid vehicles and stationary storage batteries.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Le but de la présente invention est de fournir un matériau actif d'électrode positive qui permet d'obtenir une batterie secondaire à électrolyte non aqueux qui a atteint un bon équilibre entre une stabilité thermique élevée et d'excellentes caractéristiques de batterie à des niveaux élevés, tout en supprimant une diminution de la densité après tassement. Un matériau actif d'électrode positive pour des batteries secondaires à électrolyte non aqueux, qui contient un oxyde composite de lithium-nickel-manganèse qui contient du lithium (Li), du nickel (Ni), du manganèse (Mn), du zirconium (Zr) et éventuellement un élément M, et qui est constitué de particules secondaires, chacune desdites particules secondaires étant composée d'une pluralité de particules primaires agrégées. Ce matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux est caractérisé en ce que : le rapport de quantité de substance (rapport molaire) des éléments de l'oxyde composite de lithium-nickel-manganèse est représenté par Li : Ni : Mn : M : Zr = d : (1 - a - b - c) : a : b : c (où a satisfait 0,05 ≤ a ≤ 0,60 ; b satisfait 0 ≤ b ≤ 0,60 ; c satisfait 0,0003 ≤ c ≤ 0,06 ; d satisfait 0,95 ≤ d ≤ 1,20 ; (1 - a - b - c) satisfait 0,30 ≤ (1 - a - b - c) ≤ 0,95 ; et M représente au moins un élément choisi parmi Co, W, Mo, V, Mg, Ca, Al, Ti, Cr, Nb et Ta) ; au moins une partie du zirconium dans l'oxyde composite de lithium-nickel-manganèse est solide-résolue dans les particules primaires ; l'indice de variation des diamètres de particule, à savoir (D90-D10)/Mv qui est calculé à partir du diamètre de particule moyen en volume (Mv), et D90 et D10 dans la distribution de taille de particule des particules secondaires telle que déterminée par un procédé de diffraction/diffusion laser est de 0,80 à 1,20 (inclus) ; et l'occupation de Li telle que déterminée par analyse de Rietveld est dans la plage de 94 % à 97 % (inclus).
PCT/JP2018/029311 2017-10-31 2018-08-03 Matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux et procédé de production de matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux WO2019087503A1 (fr)

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WO2020241804A1 (fr) * 2019-05-31 2020-12-03 住友金属鉱山株式会社 Précurseur de matériau actif d'électrode positive destiné à une pile rechargeable au lithium-ion, matériau actif d'électrode positive destiné à une pile rechargeable au lithium-ion, procédé de fabrication d'un précurseur de matériau actif d'électrode positive destiné à une pile rechargeable au lithium-ion, procédé de fabrication d'un matériau actif d'électrode positive destiné à une pile rechargeable au lithium-ion, pile rechargeable au lithium-ion
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JP2021114436A (ja) * 2020-01-21 2021-08-05 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質、リチウムイオン二次電池
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WO2020241804A1 (fr) * 2019-05-31 2020-12-03 住友金属鉱山株式会社 Précurseur de matériau actif d'électrode positive destiné à une pile rechargeable au lithium-ion, matériau actif d'électrode positive destiné à une pile rechargeable au lithium-ion, procédé de fabrication d'un précurseur de matériau actif d'électrode positive destiné à une pile rechargeable au lithium-ion, procédé de fabrication d'un matériau actif d'électrode positive destiné à une pile rechargeable au lithium-ion, pile rechargeable au lithium-ion
JP2020198198A (ja) * 2019-05-31 2020-12-10 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質前駆体、リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極活物質前駆体の製造方法、リチウムイオン二次電池用正極活物質の製造方法、リチウムイオン二次電池
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JP7415336B2 (ja) 2019-05-31 2024-01-17 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質前駆体、リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極活物質前駆体の製造方法、リチウムイオン二次電池用正極活物質の製造方法、リチウムイオン二次電池
JP2021007092A (ja) * 2019-06-27 2021-01-21 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質前駆体、リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極活物質前駆体の製造方法、リチウムイオン二次電池用正極活物質の製造方法、リチウムイオン二次電池
JP7395944B2 (ja) 2019-06-27 2023-12-12 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質前駆体、リチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極活物質前駆体の製造方法、リチウムイオン二次電池用正極活物質の製造方法、リチウムイオン二次電池
JP2021114436A (ja) * 2020-01-21 2021-08-05 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質、リチウムイオン二次電池
JP7413038B2 (ja) 2020-01-21 2024-01-15 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質、リチウムイオン二次電池
JP2022544326A (ja) * 2020-05-25 2022-10-17 スヴォルト エナジー テクノロジー カンパニー リミテッド ニッケルマンガン酸リチウム複合材、その製造方法及びリチウムイオン電池
JP7352727B2 (ja) 2020-05-25 2023-09-28 スヴォルト エナジー テクノロジー カンパニー リミテッド ニッケルマンガン酸リチウム複合材、その製造方法及びリチウムイオン電池

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