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WO2012020768A1 - Procédé de production pour un composé composite comprenant du nickel et du cobalt - Google Patents

Procédé de production pour un composé composite comprenant du nickel et du cobalt Download PDF

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WO2012020768A1
WO2012020768A1 PCT/JP2011/068185 JP2011068185W WO2012020768A1 WO 2012020768 A1 WO2012020768 A1 WO 2012020768A1 JP 2011068185 W JP2011068185 W JP 2011068185W WO 2012020768 A1 WO2012020768 A1 WO 2012020768A1
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Prior art keywords
cobalt
nickel
composite compound
manganese
containing composite
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PCT/JP2011/068185
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English (en)
Japanese (ja)
Inventor
河里　健
卓也 三原
秀人 狩野
絢子 小山
幸満 若杉
巽　功司
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Ａｇｃセイミケミカル株式会社
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Priority to AU2011290195A priority Critical patent/AU2011290195B2/en
Priority to JP2012528688A priority patent/JPWO2012020768A1/ja
Publication of WO2012020768A1 publication Critical patent/WO2012020768A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 method for producing a nickel-cobalt-M element-containing composite compound suitable for a positive electrode active material precursor of a lithium ion secondary battery, and a method for producing a positive electrode material using the nickel-cobalt-M element-containing composite compound. .
  • non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries that are small, lightweight, and have high energy density
  • the positive electrode active material for the non-aqueous electrolyte secondary battery include LiCoO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNiO 2 , LiNi 0.8 Co 0.2 O 2 , LiMn 2.
  • a composite oxide containing lithium and a transition metal element such as O 4 and LiMnO 2 is known.
  • lithium-nickel-cobalt-manganese-containing composite oxides which are cost-effective because they contain inexpensive manganese and have an excellent balance of safety and battery characteristics, are the next-generation cathode materials for lithium-ion secondary batteries. Expected.
  • the lithium-nickel-cobalt-manganese-containing composite oxide obtained by using the conventional solid-phase method in which the powders of the respective metal sources are mixed and fired cannot provide good battery characteristics. It has been proposed to use nickel-cobalt-manganese coprecipitated hydroxide synthesized using a salt as a raw material (see Patent Documents 1 and 2). It has also been proposed to use a nickel-cobalt-manganese coprecipitated carbonate synthesized from a metal sulfate as a raw material in synthesizing a lithium-nickel-cobalt-manganese containing composite oxide (Patent Documents 3 and 4). reference).
  • Patent Document 5 it has been proposed to synthesize a nickel-cobalt-containing composite compound by thermally decomposing a nickel-cobalt ammine complex salt, and further lithiate to synthesize a lithium-nickel-cobalt-containing composite oxide.
  • the present invention can solve such problems, has a uniform composition, has a low impurity content, can be used in a wide voltage range, has a high discharge capacity, high safety, and excellent charge / discharge cycle durability.
  • a method for producing a nickel-cobalt-M element-containing composite compound represented by the following formula (1), the nickel-cobalt-M element obtained by mixing a nickel ammine complex, a cobalt ammine complex and an M element source Production of a nickel-cobalt-M element-containing composite compound comprising heating an aqueous solution or dispersion containing water to thermally decompose the nickel ammine complex and cobalt ammine complex to form a nickel-cobalt-M element-containing composite compound Method.
  • Ni x Co y M z C p O q H r Formula (1)
  • M is at least one selected from the group consisting of transition metal elements other than Co and Ni, alkaline earth metal elements, and aluminum.
  • 0.1 ⁇ x ⁇ 0.85, 0.05 ⁇ y ⁇ 0. .85, 0.03 ⁇ z ⁇ 0.8, x + y + z 1, 0 ⁇ p ⁇ 1.6, 0.9 ⁇ q ⁇ 3.1, and 0 ⁇ r ⁇ 3.1.
  • (2) The method for producing a nickel-cobalt-M element-containing composite compound as described in (1) above, wherein the nickel ammine complex and the cobalt ammine complex are carbonate ammine complexes.
  • M element source metal manganese, manganese oxide, triiron tetraoxide, manganese, basic manganese carbonate, having an average particle diameter D 50 of less 5 ⁇ m comprising at least one selected from the group consisting of manganese carbonate and manganese oxyhydroxide
  • the nickel-cobalt-M element-containing composite compound obtained by the production method described in any one of (1) to (10) above and a lithium compound are mixed and fired at 700 to 1000 ° C. in an oxygen-containing atmosphere.
  • a method for producing a positive electrode active material for a lithium secondary battery is described in any one of (1) to (10) above and a lithium compound.
  • a lithium ion secondary battery having a uniform composition, low impurity content, usable in a wide voltage range, high discharge capacity, high safety, and excellent charge / discharge cycle durability.
  • An inexpensive method for producing a precursor containing nickel-cobalt and M element used for producing a positive electrode active material for a battery and a method for producing a positive electrode active material for a lithium ion secondary battery using the same are provided. *
  • the nickel-cobalt-M element-containing composite compound represented by the formula (1) provided by the present invention exhibits excellent characteristics as a precursor for a positive electrode active material for a lithium ion secondary battery as described above. Although it is not necessarily clear as to whether to do it, it can be considered as follows.
  • the nickel-cobalt-M element-containing composite compound provided by the present invention has a very low content of impurities such as sulfate radicals, chlorine, sodium, iron, etc., so that the positive electrode active material obtained using this composite compound is It is considered that excellent battery performance is exhibited.
  • an ammine complex refers to a complex having an amine such as ammonia as a ligand, and an amine having various organic amines as ligands is also referred to as an ammine complex.
  • the ligand of the ammine complex is preferably at least one selected from the group consisting of ammonia (NH 3 ), an aliphatic derivative of ammonia, diamine, pyridine, aniline, dipyridyl, and phenanthroline.
  • ammonia (NH 3 ) is particularly preferable.
  • the ligand may include ligands other than ammine complexes such as aco (OH 2 ), carbonato (CO 3 2 ⁇ ), acid (CN ⁇ ), hydroxo (OH ⁇ ).
  • the number of coordinated ammonia should just contain at least one, and may be two or more.
  • the central metal is +3 valent, it is preferable that the number of ammonia coordinated to the central metal is small and carbonato is used as a ligand. Specifically, [Me III (NH 3 ) 5 (CO 3 )] + , [Me III (NH 3 ) 4 (CO 2 ) 2 ] ⁇ , [Me III (NH 3 ) 3 (CO 3 ) 3 ] 3- is more preferred. In this case, the solubility of Co which is stable at +3 valence is increased, but Me is unstable, which is not preferable. Therefore, an inert atmosphere that suppresses oxidation of the central metal Me is preferable. Specifically, a nitrogen gas atmosphere is preferable, and it is more preferable to use water in which nitrogen gas is bubbled and oxygen and carbon dioxide are degassed.
  • the raw materials for the nickel ammine complex and cobalt ammine complex used in the present invention are not particularly limited, and among these, metals, hydroxides, carbonates, oxyhydroxides, or oxides are preferable, and metals, hydroxides, carbonates are preferred. Or oxyhydroxide is more preferred.
  • the nickel source is preferably metallic nickel, nickel oxide, nickel hydroxide, nickel carbonate, basic nickel carbonate, or nickel oxyhydroxide.
  • the cobalt source is preferably metallic cobalt, cobalt oxide, cobalt hydroxide, cobalt carbonate, or cobalt oxyhydroxide.
  • Ammonia water and the like are added to these nickel source and cobalt source and stirred, and further ammonium carbonate and the like are added, followed by stirring at 20 to 60 ° C. for 30 minutes to 12 hours to obtain a nickel ammine complex and cobalt ammine complex-containing aqueous solution. Can be synthesized.
  • Ammine complex, a metal, a hydroxide, carbonate, oxyhydroxide, or an oxide is preferable, Ammine complex, a metal, carbonate, An oxyhydroxide or an oxide is more preferable, and an ammine complex is particularly preferable.
  • the nickel-cobalt-M element-containing aqueous solution or aqueous dispersion does not necessarily need to dissolve all of the components, and some of the components may be dispersed. Including.
  • the M element source is a metal, hydroxide, carbonate, oxyhydroxide or oxide that is sparingly soluble in water
  • an aqueous solution in which the M element source is dispersed using a finely divided M element source it is preferable to heat the dispersion to thermally decompose the nickel ammine complex and the cobalt ammine complex.
  • the M element source is preferably water-soluble.
  • the M element source is a solution, there is a tendency that nickel, cobalt, and the M element are dispersed very uniformly and the battery characteristics are improved.
  • the M element source is insoluble or hardly soluble in water, the nickel-cobalt-M element-containing aqueous dispersion containing the M element source as fine particles is heated to thermally decompose the nickel ammine complex and cobalt ammine complex to obtain nickel- A cobalt-M element-containing composite compound can be synthesized.
  • the water-soluble M element source is prepared by adding ammonia water, ammonium carbamate, triethanolamine, etc. to the M element raw material, stirring at 0-60 ° C. for 30 minutes-12 hours, and adding ammonium carbonate, for example, to an ammine complex It is obtained by preparing an aqueous solution consisting of It is preferable that the M element source is an ammine complex because nickel, cobalt, and the M element are dispersed very uniformly and the battery performance tends to be improved.
  • liquid ammonia As the amine source used for forming the ammine complex, liquid ammonia, aqueous ammonia, ammonium carbonate, or ammonium bicarbonate is used. Furthermore, at least one selected from the group consisting of aliphatic derivatives of ammonia, diamine, pyridine, aniline, dipyridyl and phenanthroline can also be preferably used. Among these, ammonia water is preferable when cost is taken into consideration.
  • Carbonate (CO 3 ) is preferably included as a ligand of the ammine complex, and the carbonic acid source is not particularly limited, but liquid carbon dioxide is particularly preferable.
  • ammonium carbonate is a compound whose form is represented by the chemical formula (NH 4 ) 2 CO 3 , but usually available reagents include ammonium hydrogen carbonate (NH 4 .HCO 3 ) and ammonium carbamate (NH 2 COONH 4 ).
  • the M element is at least one element selected from transition metal elements other than Co and Ni, alkaline earth metal elements, and aluminum.
  • the transition metal element represents a transition metal element of Group 3, Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 10, Group 11 or Group 12 of the Periodic Table.
  • the M element is preferably selected from the group consisting of Mn, Al, Mg, Zr, Ti, and Hf.
  • the M element is more preferably at least one element selected from the group consisting of Mn, Al, and Mg. More preferably, Mn is particularly preferable.
  • iron (Fe) which is an impurity contained in a large amount in manganese
  • Fe is an impurity that adversely affects battery characteristics.
  • iron is contained in a large amount in the manganese raw material and is difficult to purify.
  • trivalent iron Fe (III) hardly forms an ammine complex and can be removed by filtering an aqueous solution of the ammine complex.
  • Manganese raw materials used when the M element contains Mn include metal manganese, manganese oxide (MnO), manganese dioxide (MnO 2 ), dimanganese trioxide (Mn 2 O 3 ), and trimanganese tetroxide (Mn 3 O 4).
  • solubility a combination of a nickel source as basic nickel carbonate, a cobalt source as cobalt hydroxide, and a manganese source as metal manganese is particularly preferable.
  • a raw material does not contain an impurity and a highly soluble raw material is preferable.
  • manganese ammine complex when the M element contains Mn, it is preferable to use a manganese ammine complex in order to improve the stability of manganese ions, and as the manganese ammine complex, it is more preferable to use manganese carbamate, which is a complex of ammonium manganate.
  • Manganese carbamate can be prepared by dissolving manganese metal or manganese oxide (MnO) in a solution of ammonium carbonate in concentrated aqueous ammonia.
  • [CO 3 ] / [NH 3 ] (moles) is the ratio of the number of moles of [CO 3 ] to the number of moles of [NH 3 ] in the nickel-cobalt-M element-containing aqueous solution. Ratio) is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.09. The value of [CO 3 ] / [NH 3 ] can be obtained by calculating from the charged amount.
  • the stability of the ammine complex decreases in the order of nickel, cobalt, and manganese
  • the element M contains manganese
  • a process of synthesizing the manganese ammine complex and mixing the separately synthesized nickel ammine complex and cobalt ammine complex is performed. It is preferable to go through.
  • Preferable ligands for stabilizing manganese to form an ammine complex include pyridine-2-methanol, ethanediamine, ethylenediamine, and the like.
  • the raw material of Al is not particularly limited, but metallic aluminum or aluminum hydroxide is particularly preferable. Since aluminum is difficult to dissolve in excess ammonia, it is preferable to prepare a triethanolamine complex aqueous solution that forms a stable complex in an aqueous solution and then mix it with a nickel ammine complex solution and a cobalt ammine complex solution.
  • the M element is Al, it is preferable to form an ammine complex of [M III (NH 3 ) 6 ] 3+ .
  • the M element is Mg, it is preferable to form an ammine complex of [M II (NH 3 ) 6 ] 2+ because it exists stably and a decomposition product having a uniform composition can be obtained.
  • Ammonia and carbon dioxide desorbed when the nickel-cobalt-M element-containing aqueous solution or aqueous dispersion is heated can be easily recovered and used.
  • ammonia and carbon dioxide are basically the only impurities remaining in the crystallized product, a simple solid-liquid separation process is sufficient, and a careful washing process such as a coprecipitation method using metal sulfate as a raw material. Is not necessary.
  • a coprecipitation method using metal sulfate as a raw material NaSO 4 and (NH 4 ) 2 SO 4 which are neutralized and by-produced and water necessary for washing are consumed, and it is necessary to make the waste liquid harmless. It takes.
  • the production method of the present invention can recycle raw materials such as ammonia without any by-products and does not require waste liquid treatment, so it is environmentally friendly, inexpensive and extremely efficient. Is a process.
  • the molar ratio of the elements nickel (x) -cobalt (y) -M (z) contained in the nickel-cobalt-M element-containing aqueous solution or aqueous dispersion is expressed as x, y, and z contained in the formula (1).
  • the molar ratio is preferably.
  • the concentration of the nickel ammine complex contained in the nickel-cobalt-M element-containing aqueous solution or aqueous dispersion is preferably 2 to 7%, more preferably 3 to 6% by mass.
  • the concentration of the cobalt ammine complex is preferably 2 to 7%, more preferably 3 to 6%, by mass.
  • the concentration of the M element source is preferably 1 to 6%, more preferably 2 to 5% by mass.
  • the total mass% of the nickel ammine complex, the cobalt ammine complex and the M element source contained in the nickel-cobalt-M element-containing aqueous solution or aqueous dispersion is preferably 5 to 10%. Further, the concentration of the metal element contained in the nickel-cobalt-M element-containing aqueous solution or aqueous dispersion is preferably 1 to 10% by mass, more preferably 3 to 6% by mass.
  • the average particle diameter D 50 of the M element source contained in the nickel-cobalt-M element-containing aqueous dispersion is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and 5 ⁇ m or less. Is more preferable, and 2 ⁇ m or less is particularly preferable.
  • D 50 exceeds 10 ⁇ m the particles obtained after heating tend to have a core-shell structure with a concentration gradient in the composition of the particles, and a nickel-cobalt-M element-containing composite compound in which M elements are not uniform tends to be obtained. is there.
  • the smaller the D 50 the more uniform the composition can be obtained.
  • the smaller the D 50 the higher the production cost. Therefore, considering the balance with the battery characteristics, the average particle size D 50 of the M element compound is preferably 0.01 ⁇ m or more. .1 ⁇ m or more is more preferable, and 0.5 ⁇ m or more is more preferable.
  • the average particle size D 50 in the present invention determine the particle size distribution on a volume basis, the cumulative curve the total volume was 100%, a particle diameter of the point where the cumulative curve becomes 50%, volume-reduced cumulative 50% diameter (D 50 ) is meant. In the present invention, it may be referred to an average particle size D 50 or D 50. Further, the D 10 of the volume-reduced cumulative 10% diameter means a volume-reduced cumulative 90% diameter and the D 90.
  • the particle size distribution is obtained from a frequency distribution and a cumulative volume distribution curve measured with a laser scattering particle size distribution measuring apparatus.
  • the particle size is measured by sufficiently dispersing the particles in an aqueous medium by ultrasonic treatment or the like and measuring the particle size distribution (for example, using Nikkiso Microtrac HRA (X-100)). .
  • the average particle diameter D 50 if the particles to be measured is a secondary particle, it is the volume average particle diameter of the secondary particle diameter of primary particles formed by agglomerating one another, when the particles consisting only of primary particles Is the average particle size for the primary particles.
  • nickel-cobalt-M element-containing composite compound obtained in the present invention a compound containing at least one selected from the group consisting of a hydroxyl group, a carbonate group and an OOH group is preferred, and a compound containing both a hydroxyl group and a carbonate group or A compound containing an OOH group is more preferable.
  • the composition of the nickel-cobalt-M element-containing composite compound obtained by the present invention is represented by the following formula (1).
  • x, y and z are preferably 0.3 ⁇ x ⁇ 0.85, 0.05 ⁇ y ⁇ 0.5 and 0.03 ⁇ z ⁇ 0.7, respectively, and 0.3 ⁇ x ⁇ 0.75.
  • 0.05 ⁇ y ⁇ 0.3 and 0.03 ⁇ z ⁇ 0.6 are more preferable.
  • Ni x Co y M z C p O q H r is preferably Ni x Co y M z (CO 3 ) a (OH) b or Ni x Co y M z OOH.
  • Ni x Co y M z OOH is one embodiment where the average valence of Ni, Co and Mn is 3.
  • the numerical values of a and b or the composition of Ni x Co y M z OOH are determined.
  • the pyrolysis conditions are severe, for example, when pyrolysis is performed at a higher temperature, the proportion of carbonic acid groups decreases and hydroxyl groups increase.
  • M is contained in a large amount and M is easily oxidized, the average valences of Ni, Co, and Mn take any valence greater than 2 and less than or equal to 3.
  • the lithium-nickel-cobalt-M element-containing composite oxide obtained by reacting with a lithium compound is used as a positive electrode active material, it is inexpensive, highly safe, and has a high discharge capacity. It is preferable that there are many.
  • provisional firing may be necessary in the firing step for obtaining a lithium-nickel-cobalt-M element-containing composite oxide, but when x is 0.62 or less, provisional firing is required. Is preferably unnecessary, and 0.42 ⁇ x ⁇ 0.62, 0.1 ⁇ y ⁇ 0.2, and 0.2 ⁇ z ⁇ 0.6 are preferable.
  • generated by thermal decomposition changes a form according to the conditions of thermal decomposition, and becomes a hydroxide, an oxyhydroxide, an oxide, carbonate, or these mixtures.
  • the composite compound represented by the above formula (1) include Ni 0.5 Co 0.2 M 0.3 (OH) 2 or Ni 0.6 Co 0.2 M 0.2 (OH) 2 . Hydroxide represented by Ni 0.5 Co 0.2 M 0.3 OOH or Ni 0.6 Co 0.2 M 0.2 OOH, Ni 0.5 Co 0.
  • the content of the M element is large, and x, y, and z are each 0.1%. ⁇ x ⁇ 0.3, 0.05 ⁇ y ⁇ 0.2, and 0.5 ⁇ z ⁇ 0.7 are preferable.
  • Examples of the composite compound represented by the above formula (1) include a hydroxide represented by Ni 1/6 Co 1/6 M 4/6 (OH) 2 , Ni 1/6 Co 1/6 M 4 / Oxyhydroxide represented by 6 OOH, Ni 1/6 Co 1/6 M 4/6 (CO 3 ) (OH) or Ni 1/6 Co 1/6 M 4/6 (CO 3 ) 0.5
  • Examples thereof include at least one selected from the group consisting of a basic carbonate represented by (OH) and a carbonate represented by Ni 1/6 Co 1/6 M 4/6 (CO 3 ).
  • the amount of elements contained in the particles can be analyzed with an ICP analysis (high frequency inductively coupled plasma emission spectroscopy) apparatus.
  • M element is Mn
  • x, y, and z in z C p O q H r are 0.46 ⁇ x ⁇ 0.62, 0.15 ⁇ y ⁇ 0.22, and 0.16 ⁇ z ⁇ 0.33, respectively.
  • a hydroxide represented by Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 or Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 Ni An oxyhydroxide represented by 0.5 Co 0.2 M 0.3 OOH or Ni 0.6 Co 0.2 Mn 0.2 OOH, Ni 0.5 Co 0.2 Mn 0.3 (CO 3 ) 0.5 (OH) or Ni 0.6 Co 0.2 Mn 0.2 (CO 3 ) 0.5 (OH), Ni 0.5 Co 0.2 Mn 0.3 (CO 3 ) (OH) Or a basic carbonate represented by Ni 0.6 Co 0.2 Mn 0.2 (CO 3 ) (OH), and Ni 0.5 Co 0.2 Mn 0.3 (CO 3 ) or Ni 0.
  • the M element is Mn
  • x, y in Ni x Co y M z C p O q H r , Z are preferably 0.1 ⁇ x ⁇ 0.3, 0.05 ⁇ y ⁇ 0.2, and 0.5 ⁇ z ⁇ 0.7, respectively.
  • More specific compositions include a hydroxide represented by Ni 1/6 Co 1/6 Mn 4/6 (OH) 2 and an oxy represented by Ni 1/6 Co 1/6 Mn 4/6 OOH.
  • Examples thereof include at least one selected from the group consisting of basic carbonates and carbonates represented by Ni 1/6 Co 1/6 Mn 4/6 (CO 3 ).
  • the M element is Al and Ni x Co y X, y and z in M z C p O q H r are 0.7 ⁇ x ⁇ 0.82, 0.05 ⁇ y ⁇ 0.2 and 0.03 ⁇ z ⁇ 0.13, respectively. preferable. Moreover, it is more preferable that 0.03 ⁇ z ⁇ 0.05. In this case, 20 to 80 mol% of Al may be substituted with Mn. More specific composition is represented by, for example, Ni 0.8 Co 0.15 Al 0.05 (OH) 2 or Ni 0.8 Co 0.15 Al 0.03 Mn 0.02 (OH) 2 . Hydroxides that can be used.
  • Mg is preferably 3 mol% or less, more preferably 1 mol% in all metal elements. It is preferable that Al or Mg contained in the M element is in the above-described range since the discharge capacity tends to be improved.
  • the M element source contained in the nickel-cobalt-M element-containing aqueous solution is an M-element ammine complex
  • all the elements contained in the nickel-cobalt-M element-containing aqueous solution are dissolved.
  • impurities such as Fe that are difficult to form an ammine complex can be removed.
  • M element is Mn
  • a nickel-cobalt-M element-containing composite compound containing much less impurities than conventional ones is preferable.
  • the M element contains Mn or Mg, it is preferable to form an ammine complex of [M II (NH 3 ) 6 ] 2+ because a stable product is obtained because a stable product is obtained.
  • the method for heating the nickel-cobalt-M element-containing aqueous solution or aqueous dispersion is not particularly limited, but it is preferably heated at 80 to 250 ° C., more preferably 100 to 250 ° C.
  • the temperature of the steam to be introduced is preferably 100 to 250 ° C., more preferably 120 to 180 ° C., and further preferably 150 to 180 ° C. to complete the reaction uniformly in a short time.
  • the steam temperature is 130 ° C. or higher, it is necessary to prepare equipment that can withstand high pressure.
  • the pressure in the reaction vessel may be under reduced pressure or high pressure, and in particular, the reactivity is improved, so 0.03 to 2 MPa is preferable, 0.1 to 2 MPa is more preferable, and pressure of 0.2 to 1 MPa is preferable. It is particularly preferred to heat under.
  • the heating time is preferably 0.1 to 12 hours, and more preferably 0.5 to 10 hours.
  • the obtained lithium-nickel-cobalt-M element-containing composite oxide is obtained by firing a mixture of a nickel-cobalt-M element-containing composite compound and a lithium compound. There is a tendency to be affected. For this reason, when used as a positive electrode active material, the balance between safety and discharge rate characteristics is improved, so the average particle diameter D 50 of the nickel-cobalt-M element-containing composite compound is in the range of 2 to 25 ⁇ m. The range of 5 to 15 ⁇ m is more preferable, and the range of 8 to 12 ⁇ m is more preferable.
  • the specific surface area of the nickel-cobalt-M element-containing composite compound is preferably large in order to increase the reactivity with the lithium compound.
  • the nickel-cobalt-M element-containing composite compound crystallized in the aqueous solution by heating is separated from the aqueous solution, it is not particularly limited because there is no need to clean and remove impurities, but suction filtration, filter press, belt filter, Examples include centrifugation.
  • the adsorbed water may be removed by using a compressed air blowing method utilizing a capillary phenomenon in order to reduce the drying load.
  • the content of the metal contained in the composite compound can be measured, and if handling is possible, drying is not necessary, but drying may be performed as necessary. .
  • drying it is preferable to dry at 80 to 150 ° C., more preferably 100 to 150 ° C., and the composite compound is preferably a highly reactive oxyhydroxide.
  • the amount of impurities contained in the nickel-cobalt-M element-containing composite compound obtained in the present invention is small.
  • Elements that affect battery performance include sodium (Na), sulfur (S) and iron (Fe).
  • the content of sodium is preferably 0.01% by mass or less, and more preferably 0.008% by mass or less.
  • the content of sodium may be 0.0001% by mass or more.
  • the content of sulfur is preferably 0.07% by mass or less, and more preferably 0.04% by mass or less.
  • 0.0001 mass% or more may be sufficient as content of sulfur.
  • the iron content is preferably 0.002% by mass or less, and more preferably 0.001% by mass or less.
  • 0.0001 mass% or more of iron content may be sufficient.
  • the chromium content is preferably 0.0005% by mass or less.
  • 0.00001 mass% or more may be sufficient as content of chromium.
  • the obtained nickel-cobalt-M element-containing composite compound and a lithium compound are mixed and then fired to make a lithium-nickel-cobalt-M element-containing composite oxide useful as a positive electrode material for a lithium ion secondary battery Is obtained.
  • the lithium compound to be used is not particularly limited, lithium hydroxide or lithium carbonate is preferable because it is inexpensive, and lithium carbonate is more preferable.
  • firing conditions an oxygen-containing atmosphere is preferable. Further, firing is preferably performed under conditions of 700 to 1000 ° C. When the firing temperature is lower than 700 ° C., the formation of the lithium-nickel-cobalt-M element-containing composite oxide is insufficient and results in containing impurities.
  • the firing temperature exceeds 1000 ° C.
  • the charge / discharge cycle durability and the discharge capacity tend to decrease.
  • a minimum is 850 degreeC and an upper limit is 970 degreeC.
  • the oxygen-containing atmosphere is preferably in the air, and more specifically, the oxygen content contained in the atmosphere is more preferably 10 to 40% by volume.
  • the firing time is preferably 1 to 24 hours, more preferably 2 to 18 hours, and particularly preferably 4 to 14 hours.
  • the average particle size D 50 is preferably 2 to 25 ⁇ m, more preferably 5 to 15 ⁇ m, and even more preferably 8 to 12 ⁇ m.
  • the specific surface area is preferably from 0.1 to 1.0 m 2 / g, more preferably from 0.3 to 0.8 m 2 / g. In the present invention, the specific surface area was all measured using the BET method.
  • Press density is preferably 2.9 ⁇ 3.4g / cm 3, more preferably 3.0 ⁇ 3.4g / cm 3, particularly preferably 3.2 ⁇ 3.4g / cm 3.
  • the press density means the apparent density of the powder when the lithium-nickel-cobalt-M element-containing composite oxide powder is pressed at a pressure of 1.0 ton / cm 2 .
  • the amount of free alkali is determined by dispersing 5 g of lithium-nickel-cobalt-M element-containing composite oxide powder in 50 g of pure water, stirring for 30 minutes, and then filtering the filtrate. Neutralization titration with a 0.02 mol% / liter hydrochloric acid aqueous solution is carried out from the amount of the hydrochloric acid aqueous solution used until the pH reaches 4.0.
  • a carbon-based conductive material such as acetylene black, graphite, or ketjen black is added to the composite oxide powder. It is formed by mixing a material and a binder.
  • a binder polyvinylidene fluoride, polytetrafluoroethylene, polyamide, carboxymethyl cellulose, acrylic resin, or the like is preferably used.
  • the lithium-nickel-cobalt-M element-containing composite oxide powder, conductive material and binder of the present invention are made into a slurry or a kneaded product using a solvent or a dispersion medium. This is supported on a positive electrode current collector such as an aluminum foil or a stainless steel foil by coating or the like to produce a positive electrode for a lithium secondary battery of the present invention.
  • a porous polyethylene film, a porous polypropylene film, or the like is used as the separator.
  • Various solvents can be used as the solvent for the electrolyte solution of the battery, and among them, carbonate ester is preferable.
  • the carbonate ester can be either cyclic or chain. Examples of the cyclic carbonate include propylene carbonate and ethylene carbonate (EC). Examples of the chain carbonate include dimethyl carbonate, diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate, methyl isopropyl carbonate, and the like.
  • the carbonate ester can be used alone or in admixture of two or more. Moreover, you may mix and use with another solvent. Further, depending on the material of the negative electrode active material, the combined use of a chain carbonate ester and a cyclic carbonate ester may improve the discharge capacity, cycle characteristics, and charge / discharge efficiency.
  • a vinylidene fluoride-hexafluoropropylene copolymer for example, trade name Kyner manufactured by Atchem Co., Ltd.
  • a gel polymer electrolyte containing a vinylidene fluoride-perfluoropropyl vinyl ether copolymer may be used.
  • Solutes added to the electrolyte solvent or polymer electrolyte include ClO 4 ⁇ , CF 3 SO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , CF 3 CO 2 ⁇ , (CF 3 Any one or more of lithium salts having SO 2 ) 2 N — or the like as an anion is preferably used. It is preferable to add at a concentration of 0.2 to 2.0 mol / L with respect to the electrolyte solvent or polymer electrolyte comprising the lithium salt. If it deviates from this range, the ionic conductivity is lowered and the electrical conductivity of the electrolyte is lowered. Of these, 0.5 to 1.5 mol / L is particularly preferable.
  • a material capable of inserting and extracting lithium ions is used as the negative electrode active material.
  • the material for forming the negative electrode active material is not particularly limited.
  • the carbon material those obtained by pyrolyzing an organic substance under various pyrolysis conditions, artificial graphite, natural graphite, soil graphite, expanded graphite, flake graphite, and the like can be used.
  • the oxide a compound mainly composed of tin oxide can be used.
  • the negative electrode current collector a copper foil, a nickel foil, or the like is used. Such a negative electrode is preferably produced by kneading the active material with an organic solvent to form a slurry, and applying the slurry to a metal foil current collector, drying, and pressing.
  • the shape of the lithium secondary battery using the lithium-nickel-cobalt-M element-containing composite oxide of the present invention as the positive electrode active material is not particularly limited.
  • a sheet shape, a film shape, a folded shape, a wound-type bottomed cylindrical shape, a button shape, or the like is selected depending on the application.
  • Example 1 A basic nickel carbonate (66.70 g), cobalt hydroxide (18.59 g), metal manganese powder (average particle size 5 ⁇ m) (16.48 g) was added with 25% aqueous ammonia (1062.71 g), and degassed by bubbling with nitrogen gas for 2 hours. While adding 193.37 g of ion-exchanged water and stirring, 81.68 g of ammonium carbonate was added, and the mixture was stirred at 25 ° C. for 2 hours under a flow of nitrogen gas.
  • the obtained nickel-cobalt-manganese ammine aqueous solution was filtered to remove undissolved components, and then 0.3 MPa of steam at about 135 ° C. was directly introduced into the ammine aqueous solution and reacted for 30 minutes to react with the nickel- A cobalt-manganese-containing composite compound was obtained.
  • the nickel-cobalt-manganese-containing composite compound was filtered and dried at 100 ° C. for 2 hours to obtain a nickel-cobalt-manganese-containing composite compound powder.
  • the total amount of nickel, cobalt and manganese contained in this composite compound was 42.8% by mass.
  • the composition of this composite compound was Ni 0.5 Co 0.2 Mn 0.3 (CO 3 ) (OH).
  • the obtained nickel-cobalt-manganese-containing composite compound was analyzed for the amount of impurities by ICP analysis and summarized in Table 1.
  • a scanning electron microscope (hereinafter referred to as SEM) image of this composite compound is shown in FIG.
  • a powder X-ray diffraction spectrum (sometimes referred to as an XRD spectrum in the present invention) was measured under the conditions of an acceleration voltage of 40 KV and an acceleration current of 40 mA using RINT2200V manufactured by Rigaku Corporation.
  • a Cu—K ⁇ ray was used as the radiation source.
  • the spectrum chart is shown in FIG.
  • Li 1.015 [Ni 0.5 Co 0.2 Mn 0.3 ] 0.985 O 2 was obtained as a lithium-nickel-cobalt-manganese-containing composite oxide powder.
  • the resulting average particle size D 50 of the composite oxide is 11.9, D 10 is 4.1 .mu.m, D 90 is 19.7Myuemu, the specific surface area was 0.35 m 2 / g.
  • the press density of this composite oxide was 2.99 g / cm 3 , and the amount of free alkali was 0.43 mol%.
  • the obtained lithium-nickel-cobalt-manganese-containing composite oxide, acetylene black, and polyvinylidene fluoride powder were mixed at a mass ratio of 90/5/5, and N-methylpyrrolidone was added to prepare a slurry.
  • One-side coating was performed on a 20 ⁇ m thick aluminum foil using a doctor blade, dried, and roll press rolling was performed twice to produce a positive electrode sheet for a lithium battery.
  • the positive electrode sheet is punched out as a positive electrode, a metal lithium foil having a thickness of 500 ⁇ m is used as a negative electrode, a nickel foil of 20 ⁇ m is used as a negative electrode current collector, and a porous polypropylene having a thickness of 25 ⁇ m is used as a separator.
  • the electrolytic solution used is a LiPF 6 / EC + DEC (1: 1) solution having a concentration of 1 M (meaning a mixed solution of EC and DEC in a weight ratio (1: 1) containing LiPF 6 as a solute. Solvent described later) Were also used to assemble two stainless steel simple sealed cell type lithium batteries in an argon glove box.
  • the one battery is charged at a load current of 75 mA per gram of the positive electrode active material at 25 ° C. to 4.3 V, discharged to 2.5 V at a load current of 75 mA per gram of the positive electrode active material, and The charge / discharge capacity density (sometimes referred to as initial weight capacity density in the present specification) was determined.
  • the battery was charged to 4.3 V with a load current of 75 mA, and the discharge capacity when discharged to 2.5 V with a load current of 113 mA was determined.
  • the initial weight capacity density of the positive electrode active material at 25 ° C.
  • Example 2 219 g of ion-exchanged water was added to 182 g of 28% ammonia water, and further 78.5 g of ammonium bicarbonate was added and dissolved while stirring. To this solution, 50.0 g of basic nickel carbonate and 14.2 g of cobalt hydroxide were added at room temperature and stirred for 2 hours. After dissolution, insoluble components were removed by pressure filtration to obtain a nickel-cobalt ammine solution. To the obtained aqueous solution of nickel-cobalt ammine, 26.5 g of finely divided manganese carbonate having an average particle size of 0.8 ⁇ m was added and stirred to prepare a nickel-cobalt-manganese carbonate suspension.
  • the press density of this composite oxide was 2.90 g / cm 3 , and the amount of free alkali was 0.58 mol%.
  • An electrode and a battery were produced and evaluated in the same manner as in Example 1 except that the positive electrode sheet was produced using the lithium-nickel-cobalt-manganese-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 174 mAh / g.
  • the high load capacity retention rate obtained from the discharge capacity when discharged at a high load of 113 mA related to the discharge rate characteristics was 93.2%.
  • the capacity retention rate after 30 charge / discharge cycles was 95.6%.
  • Example 3 219 g of ion-exchanged water was added to 182 g of 28% ammonia water, and further 78.5 g of ammonium bicarbonate was added and dissolved while stirring. To this solution, 50.0 g of basic nickel carbonate and 14.2 g of cobalt hydroxide were added at room temperature and stirred for 2 hours. After dissolution, insoluble components were removed by pressure filtration to obtain a nickel-cobalt ammine solution. On the other hand, 34.9 g of ammonium carbonate was added to 268 g of 28% aqueous ammonia, and the mixture was cooled to 15 ° C. while stirring.
  • the obtained lithium-nickel-cobalt-manganese-containing composite compound was analyzed for the amount of impurities by ICP analysis and summarized in Table 1.
  • nickel, cobalt, and manganese contained in this composite compound are 47.0 mass% in total, and the composition ratio of this composite compound is Ni 0.5 Co 0.2 Mn 0.3 (CO 3 ) (OH) It was 0.29 .
  • This composite oxide had a press density of 3.18 g / cm 3 and a free alkali amount of 0.40 mol%.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the lithium-nickel-cobalt-manganese-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 173 mAh / g.
  • the high load capacity retention rate obtained from the discharge capacity when discharged at a high load of 113 mA related to the discharge rate characteristics was 90.2%.
  • the capacity retention rate after 30 charge / discharge cycles was 96.5%.
  • Example 4 219 g of ion-exchanged water was added to 182 g of 28% ammonia water, and further 78.5 g of ammonium bicarbonate was added and dissolved while stirring. To this solution, 50.0 g of basic nickel carbonate and 14.2 g of cobalt hydroxide were added at room temperature and stirred for 2 hours. After dissolution, insoluble components were removed by pressure filtration to obtain a nickel-cobalt ammine solution.
  • the obtained lithium-nickel-cobalt-manganese-containing composite compound was analyzed for the amount of impurities by ICP analysis and summarized in Table 1.
  • nickel, cobalt, and manganese contained in this composite compound are 53.1% by mass in total, and the composition ratio of this composite compound is Ni 0.5 Co 0.2 Mn 0.3 (CO 3 ) 0.7 O. 0.4 (OH) 0.15 .
  • This composite oxide had a press density of 2.92 g / cm 3 and a free alkali amount of 0.55 mol%.
  • An electrode and a battery were produced and evaluated in the same manner as in Example 1 except that the positive electrode sheet was produced using the lithium-nickel-cobalt-manganese-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 174 mAh / g.
  • the high load capacity retention rate obtained from the discharge capacity when discharged at a high load of 113 mA related to the discharge rate characteristics was 92.8%.
  • the capacity retention rate after 30 charge / discharge cycles was 95.8%.
  • Example 5 A sulfate aqueous solution containing 2.5 mol / L nickel sulfate, 1.0 mol / L cobalt sulfate and 1.5 mol / L manganese sulfate was prepared and filtered to obtain a nickel-cobalt-manganese-containing sulfate aqueous solution. Obtained. Next, 500 g of ion-exchanged water was added to the reaction vessel, and the mixture was stirred at 400 rpm while being kept at 50 ° C. while bubbling with nitrogen gas.
  • the obtained nickel-cobalt-manganese-containing composite hydroxide was analyzed for the amount of impurities by ICP analysis and summarized in Table 1.
  • the particles of the obtained nickel-cobalt-manganese-containing composite hydroxide are spherical, and the average particle diameter is 12.7 ⁇ m.
  • the composition of this composite hydroxide was Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 .
  • nickel, cobalt, and manganese contained in this composite compound were 61.5 mass% in total.
  • the XRD spectrum was measured on the measurement conditions similar to Example 1 using RINT2200V by Rigaku Corporation. A chart of the spectrum is shown in FIG.
  • the press density of this powder was 2.97 g / cm 3 , and the amount of free alkali was 0.48 mol%.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the lithium-nickel-cobalt-manganese-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 169 mAh / g.
  • required from the discharge capacity when discharging with a high load of 113 mA related to the discharge rate characteristic was 87.5%.
  • the capacity retention rate after 30 charge / discharge cycles was 92.8%.
  • a lithium ion secondary battery having a uniform composition, low impurity content, usable in a wide voltage range, high discharge capacity, high safety, and excellent charge / discharge cycle durability.
  • a precursor for a positive electrode active material is provided at low cost.
  • the manufacturing method of the positive electrode active material for lithium ion secondary batteries which uses this precursor is provided. They are useful in the field of lithium ion secondary batteries, and their applicability in this field is extremely high.

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Abstract

Le procédé de production produit de façon économique un composé composite qui comprend du nickel et du cobalt avec quelques impuretés, et sert de précurseur pour le matériau d'électrode positive d'une batterie secondaire lithium-ion. La composé composite est sûr, a une capacité de service élevée, a une durabilité de cycle de charge/décharge supérieure et peut être utilisé avec une large plage de tensions. Le procédé de production pour un composé composite comprenant du nickel, du cobalt et un élément M est caractérisé en ce qu'une solution ou dispersion aqueuse comprenant du nickel, du cobalt et un élément M est obtenu par mélange d'un complexe nickel-amine, un complexe cobalt-amine et une source d'élément M, et la solution aqueuse ou dispersion est chauffée de manière à décomposer de façon thermique le complexe nickel-amine et le complexe cobalt-amine et produire ainsi un composé composite contenant du nickel, du cobalt et un élément M.
PCT/JP2011/068185 2010-08-10 2011-08-09 Procédé de production pour un composé composite comprenant du nickel et du cobalt WO2012020768A1 (fr)

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