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WO2016013674A1 - Particules d'hydroxyde d'un composé de nickel et de manganèse et procédé de production associé - Google Patents

Particules d'hydroxyde d'un composé de nickel et de manganèse et procédé de production associé Download PDF

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Publication number
WO2016013674A1
WO2016013674A1 PCT/JP2015/071163 JP2015071163W WO2016013674A1 WO 2016013674 A1 WO2016013674 A1 WO 2016013674A1 JP 2015071163 W JP2015071163 W JP 2015071163W WO 2016013674 A1 WO2016013674 A1 WO 2016013674A1
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WIPO (PCT)
Prior art keywords
composite hydroxide
hydroxide particles
particles
manganese composite
nickel manganese
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PCT/JP2015/071163
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English (en)
Japanese (ja)
Inventor
巧也 山内
勝哉 井之上
充 山内
小向　哲史
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Priority to JP2016536005A priority Critical patent/JP6747291B2/ja
Publication of WO2016013674A1 publication Critical patent/WO2016013674A1/fr
Anticipated expiration legal-status Critical
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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
    • 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 nickel manganese composite hydroxide particles, which are precursors of a positive electrode active material for a non-aqueous electrolyte secondary battery, and a method for producing the same.
  • lithium ion secondary battery that is a kind of non-aqueous electrolyte secondary battery.
  • This lithium ion secondary battery is composed of a negative electrode, a positive electrode, an electrolytic solution, and the like, and a material capable of desorbing and inserting lithium is used as an active material used as a material for the negative electrode and the positive electrode.
  • lithium-ion secondary batteries are being actively carried out.
  • lithium using a positive electrode active material composed of layered or spinel type lithium transition metal composite oxide particles as a positive electrode material. Since an ion secondary battery can obtain a high voltage of 4 V class, it is being put to practical use as a material having a high energy density.
  • lithium cobalt composite oxide (LiCoO 2 ), which is currently relatively easy to synthesize, lithium nickel composite oxide (LiNiO 2 ) using nickel which is cheaper than cobalt with a small amount of reserves, Lithium manganese composite oxide (LiMn 2 O 4 ), lithium nickel manganese composite oxide (LiNi 0.5 Mn 0.5 O 2 ), lithium nickel cobalt manganese composite oxide (LiNi 1 / Lithium transition metal composite oxides such as 3 Co 1/3 Mn 1/3 O 2 ) have been proposed.
  • lithium nickel manganese composite oxide having excellent thermal stability and high capacity without using cobalt, or good cycle characteristics, low resistance and high output can be obtained.
  • Lithium nickel manganese cobalt composite oxide which can be used, is currently attracting attention.
  • a lithium transition metal composite oxide used as a positive electrode active material It is required to strictly control the powder properties such as the average particle size, particle size distribution, specific surface area, and crystallite size, and the crystallinity thereof.
  • the method of using the transition metal composite hydroxide particles obtained by the crystallization reaction as the precursor of the positive electrode active material has a uniform composition at the atomic level by appropriately controlling the crystallization conditions, and There is an advantage that a positive electrode active material excellent in powder characteristics can be obtained.
  • the impurity component contained in the lithium transition metal composite oxide particles may cause a decrease in battery characteristics, it becomes an important management item in production, as with the above-described powder characteristics and crystallinity. . That is, it is necessary to reduce the amount of impurities contained in the transition metal composite hydroxide particles that are precursors of the positive electrode active material and to optimize the impurities.
  • transition metal composite hydroxide particles are obtained by crystallization reaction, and the obtained transition metal composite hydroxide particles are filtered or filtered. Prior to this, it is described that excess base and ammonia contained in the transition metal composite hydroxide particles are removed by washing with a centrifugal separator, a suction filter, or the like.
  • the aqueous solution for nucleation is controlled so that the pH value on the basis of the liquid temperature of 25 ° C. is 12.0 to 14.0, and the oxygen concentration is 1% by volume.
  • a nucleation step in which nucleation is performed in an oxidizing atmosphere that exceeds the above, and an aqueous solution for particle growth containing nuclei formed in the nucleation step, having a pH value of 10.5 to 12.0 at a liquid temperature of 25 ° C.
  • a mixed atmosphere of oxygen and inert gas having an oxygen concentration of 1% by volume or less from an oxidizing atmosphere in the range of 0% to 40% with respect to the whole particle growing process from the beginning of the particle growing process.
  • a crystallization step comprising a particle growth step for growing the nuclei, and having a central portion made of fine primary particles and comprising plate-like primary particles larger than the fine primary particles outside the central portion. Having an outer shell, The Kkerumangan composite hydroxide particles, it is disclosed that obtained by industrial-scale mass production.
  • nickel-manganese composite hydroxide particles having such a structure as a precursor, a hollow structure comprising an outer shell portion in which aggregated primary particles are sintered and a hollow portion existing inside thereof is provided.
  • a positive electrode active material having excellent powder characteristics can be obtained.
  • nickel-manganese composite hydroxide particles having such a structure sodium contained in the central part consisting of fine primary particles, particularly by simply washing the obtained nickel-manganese composite hydroxide particles. Is extremely difficult to remove.
  • the present invention is a positive electrode active material capable of producing a non-aqueous electrolyte secondary battery in which deterioration and variation in battery characteristics are suppressed, particularly in mass production on an industrial scale, and transition metal composite hydroxide particles that are precursors thereof, particularly
  • An object of the present invention is to provide nickel manganese composite hydroxide particles.
  • the slurry is held in a non-oxidizing atmosphere in which the oxygen partial pressure is controlled to 10 Pa or less from the end of the crystallization process to the start of the cleaning process.
  • the slurry is controlled to have a pH value in the range of 10.5 to 13.0 based on a liquid temperature of 25 ° C. from the end of the crystallization step to the start of the washing step. It is preferable to hold at.
  • the holding time is preferably 10 hours or less.
  • the method for producing nickel manganese composite hydroxide particles of the present invention is for producing nickel manganese composite hydroxide particles composed of secondary particles formed by agglomeration of a plurality of primary particles obtained by a crystallization reaction.
  • the nickel manganese composite hydroxide particles have a central portion made of fine primary particles, and are made of plate-like primary particles larger than the fine primary particles outside the central portion. It is suitably applied to the production of nickel manganese composite hydroxide particles composed of secondary particles having an outer shell portion.
  • the aqueous solution for nucleation is controlled so that the pH value on the basis of the liquid temperature of 25 ° C. is 12.0 to 14.0, and the oxygen concentration is 1 volume.
  • the nickel manganese composite hydroxide particles of the present invention have a central portion made of fine primary particles, and an outer shell portion made of plate-like primary particles larger than the fine primary particles outside the central portion. It is preferably composed of secondary particles.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery of the present invention is characterized by comprising lithium nickel manganese composite oxide particles having the nickel manganese composite hydroxide particles as precursors.
  • the present invention particularly in mass production on an industrial scale, when nickel manganese composite hydroxide particles containing manganese as a constituent metal element are obtained by a crystallization reaction using inexpensive sodium hydroxide as a neutralizing agent
  • the alkali metal content particularly the sodium content
  • the positive electrode active material for a non-aqueous electrolyte secondary battery obtained using such nickel manganese composite hydroxide particles as a precursor the positive electrode active material is used as the positive electrode in order to inherit the powder characteristics of low alkali metal content.
  • a non-aqueous electrolyte secondary battery in which deterioration and variation in battery characteristics due to the presence of alkali metal are suppressed is provided. For this reason, the industrial significance of the present invention is extremely large.
  • the present inventors have used a transition metal composite hydroxide particle, in particular, a positive electrode active material containing nickel manganese composite hydroxide particles as a precursor, containing manganese as a constituent metal element.
  • a transition metal composite hydroxide particle in particular, a positive electrode active material containing nickel manganese composite hydroxide particles as a precursor, containing manganese as a constituent metal element.
  • the inventors have obtained knowledge that the oxidation state of nickel manganese composite hydroxide particles during washing affects the removal of alkali metals, particularly sodium, and have reached the present invention.
  • the method for producing nickel manganese composite hydroxide particles of the present invention comprises a general formula (A): Ni x M y y by a crystallization reaction using sodium hydroxide as a neutralizing agent.
  • M is one or more elements selected from Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W)
  • Nickel-manganese composite hydroxide particles obtained by crystallization reaction are usually composed of secondary particles formed by aggregation of a plurality of primary particles. Most of the alkali metal salt adhering to the primary particle surface during crystallization is removed by washing with water after crystallization. However, the alkali metal contained as an impurity exists not only in the alkali metal salt adhering to the surface of the primary particle, but also in a state in which a part is incorporated in the crystal of the composite hydroxide particle. Such an alkali metal is difficult to remove by washing with water after crystallization, and when the alkali metal taken into the crystal increases, the content of the alkali metal as an impurity increases.
  • an alkali metal particularly sodium
  • an alkali metal is taken into the crystals of the composite hydroxide particles with the oxidation of manganese in the composite hydroxide particles. That is, manganese in the composite hydroxide particles is easily oxidized, and when the composite hydroxide particles obtained by the crystallization reaction are placed in an atmosphere in which oxygen is present, the composite hydroxide particles are oxidized.
  • the degree to which manganese is oxidized increases. As the degree of oxidation of manganese increases in this way, the content of alkali metal taken into the crystal increases accordingly. Thus, even if it wash
  • the degree of oxidation of the composite hydroxide particles in advance specifically, the average valence of the metal element in the composite hydroxide particles at the start of the cleaning process is controlled to 2.4 or less. By this, it becomes possible to suppress the alkali metal taken into the crystal.
  • the method for producing composite hydroxide particles of the present invention is divided into (1) a crystallization step, (2) from the end of the crystallization step to the start of the cleaning step, and (3) the cleaning step. explain.
  • the crystallization step is a step of obtaining composite hydroxide particles by a crystallization reaction. More specifically, nickel (Ni) and manganese (Mn), which are main metal elements, or a mixed aqueous solution containing nickel, manganese, and cobalt (Co) and an additive element M, water as a neutralizing agent.
  • This is a step of forming a reaction aqueous solution by supplying an aqueous solution of sodium oxide and a complexing agent such as aqueous ammonia, crystallizing the composite hydroxide particles, and obtaining a slurry containing the composite hydroxide particles.
  • the conditions in the crystallization step are not particularly limited, and are appropriately selected according to the composition, particle structure or powder characteristics of the target composite hydroxide particles.
  • M is selected from Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W
  • the ratio of the metal compounds is adjusted so that the composition is the same as the composition of the composite hydroxide particles, and these metal compounds are dissolved in water. To produce a mixed aqueous solution.
  • the crystallization process grows mainly from the nucleation process in which nucleation occurs and the nuclei generated in the nucleation process as particles. It is preferable to divide into the particle growth process to be performed.
  • the composite hydroxide has a uniform composition at the atomic level and is composed of secondary particles obtained by agglomeration of primary particles, and has excellent powder characteristics such as a narrow particle size distribution. Particles are obtained.
  • a composite hydroxide particle having a particle structure composed of a central part composed of fine primary particles and an outer shell part formed outside the central part and composed of plate-like primary particles larger than the fine primary particles.
  • the aqueous solution for nucleation has a pH value of 12.0 to 14.0 based on a liquid temperature of 25 ° C.
  • the pH value is controlled to be 10.5 to 12.0, and the oxygen concentration is 1 volume from the oxidizing atmosphere in the range of 0% to 40% with respect to the whole particle growth process from the start of the particle growth process.
  • % Oxygen and inert Switch to scan a mixed atmosphere of, by the particle growth step of growing the nucleus to form a crystallization step.
  • reaction atmosphere the atmosphere in the reaction vessel including the reaction field (in the reaction aqueous solution) during the crystallization reaction
  • reaction atmosphere an oxidizing atmosphere needs to be selected.
  • a non-oxidizing atmosphere is preferable, and a nitrogen atmosphere is more preferable.
  • the oxygen partial pressure in the reaction atmosphere is preferably 1013 Pa or less, more preferably 1000 Pa or less, and even more preferably 990 Pa or less.
  • the non-oxidizing atmosphere in the crystallization process can also be adjusted so that the oxygen partial pressure is 10 Pa or less.
  • the crystallization step in such a reaction atmosphere it is possible to suppress the oxidation of manganese during the crystallization reaction and further reduce the alkali metal, particularly sodium, taken into the crystal.
  • the average valence of the metal elements constituting the composite hydroxide particles obtained by the crystallization reaction is generally in the range of 2.00 to 2.15.
  • the composite hydroxide particles are held in a slurry state, usually in an air atmosphere.
  • this slurry is held while being stirred from the viewpoint of preventing aggregation of the composite hydroxide particles.
  • the composite hydroxide particles are easily oxidized, and this is affected by the degree of stirring of the slurry and the contact state with the air atmosphere. Average valence increases.
  • the alkali metal incorporated in the crystal is suppressed, and the primary particles are mainly washed by washing after crystallization.
  • the alkali metal existing on the surface is removed.
  • the content of alkali metal remaining in the composite hydroxide particles, particularly the content of sodium can be reduced to 500 ppm by mass or less.
  • the average valence of the metal element in the composite hydroxide particles means the arithmetic average value of the valences of nickel, cobalt, manganese, and additive element M contained in the composite hydroxide particles, and the composite hydroxide It can be obtained by redox titration of a solution obtained by dissolving particles in hydrochloric acid.
  • the average valence of the metal element in the composite hydroxide particles is preferably controlled to 2.2 or less, more preferably 2.15 or less.
  • the atmosphere from the end of the crystallization process to the start of the cleaning process (hereinafter referred to as “holding atmosphere”) is preferably a non-oxidizing atmosphere, and more preferably a nitrogen atmosphere. That is, it is preferable to control the oxygen partial pressure in the holding atmosphere to 10 Pa or less, preferably 5 Pa or less.
  • the holding atmosphere in such a range, even if the time from the end of the crystallization reaction to the start of the washing process is a long time, for example, 12 hours or more, the average of the main metal element M The valence can be kept below 2.4.
  • the oxygen partial pressure in the holding atmosphere exceeds 10 Pa
  • the time from the completion of the crystallization reaction to the start of the washing step is long, for example, 12 hours or more
  • the average valence of the metal element may exceed 2.4.
  • an inert gas preferably nitrogen gas
  • the oxygen partial pressure may be 10 Pa or less from the oxygen partial pressure (for example, 1013 Pa or less) at the end of the crystallization reaction.
  • the atmosphere during the crystallization reaction may be set as a non-oxidizing atmosphere in advance so that the non-oxidizing atmosphere is maintained even after the crystallization process is completed. Furthermore, even when the composite hydroxide particles are continuously separated by solid-liquid separation due to overflow, the composite hydroxide particles directly come into contact with the atmosphere. It is effective to maintain an atmosphere of 10 Pa or less.
  • an air atmosphere oxygen partial pressure: 21273 Pa
  • the average valence of the metal element in the composite hydroxide particles is 2.4 or less.
  • the time from the end of the crystallization process to the start of the washing process is within 12 hours, preferably within 10 hours, More preferably, it must be within 8 hours.
  • Stirring involving air atmosphere promotes oxidation of metal elements, so it is necessary to further reduce the retention time in the slurry state, and the average valence of metal elements depending on stirring conditions can be controlled to 2.4 or less. It is sufficient to confirm the appropriate holding time by a preliminary test.
  • the pH value based on the liquid temperature of the slurry at 25 ° C. is preferably 13.0 or less, more preferably 12.5 or less, and even more preferably 12.0 or less.
  • the pH value of the slurry is preferably 10.5 or more, more preferably 11.0 or more, based on the liquid temperature of 25 ° C.
  • the oxidation of manganese in the composite hydroxide particles subjected to the washing process is suppressed, the amount of alkali metal taken into the crystal along with the oxidation of manganese is reduced, and the alkali metal is on the surface of the primary particles. Stays present.
  • the alkali metal remaining on the surface of the primary particles of such composite hydroxide particles can be removed sufficiently and easily by washing.
  • the method for cleaning the composite hydroxide particles is not particularly limited, and for example, a method of adding an appropriate amount of cleaning water to the slurry containing the composite hydroxide particles and stirring the slurry can be employed.
  • washing water it is preferable to use pure water such as ion-exchanged water or distilled water having as little impurity content as possible from the viewpoint of preventing contamination of impurities. Further, it is preferable to perform the cleaning in a plurality of times rather than only once.
  • the composite hydroxide particles can be washed using a filter press or the like.
  • the slurry is filtered or before it is filtered, it can be washed using a centrifugal separator, a suction filter, or the like. In any case, it is necessary to appropriately adjust the cleaning conditions according to the characteristics of the apparatus to be used, the amount of composite hydroxide particles to be cleaned, and the like.
  • the average valence of the metal element is in the range of 2.4 or less at the end of the washing step, but thereafter, the oxidation proceeds with time, so that the average valence is not necessarily limited.
  • the numbers are not in this range.
  • the composite hydroxide particles of the present invention contain at least nickel (Ni) and manganese (Mn) as main metal elements, and preferably contain nickel, manganese, and cobalt (Co).
  • the present invention can be suitably applied to composite hydroxide particles containing manganese in which y in general formula (A) is 0.1 or more and 0.55 or less, indicating the composition of manganese. .
  • Nickel is an element that contributes to improving battery capacity. Therefore, the ratio of the number of nickel atoms to the total number of atoms of the metal element (Ni / total metal elements) is preferably 0.3 to 0.7, more preferably 0.3 to 0.6, and even more preferably 0. 3 to 0.5.
  • Ni / total metal elements is preferably 0.3 to 0.7, more preferably 0.3 to 0.6, and even more preferably 0. 3 to 0.5.
  • the value of Ni / all metal elements is less than 0.3, a secondary battery using a positive electrode active material having the composite hydroxide particles as a precursor does not have a high capacity.
  • the Ni / M ratio exceeds 0.7, the content of cobalt and manganese decreases, and the effect of addition cannot be sufficiently obtained.
  • Manganese is an element that contributes to improved thermal stability. Therefore, the ratio of the number of manganese atoms to the total number of atoms of metal elements (Mn / total metal elements) is preferably 0.1 to 0.55, more preferably 0.2 to 0.4, and even more preferably. 0.2 to 0.35. If the value of Mn / all metal elements is less than 0.1, the thermal stability cannot be sufficiently improved. On the other hand, if the value of Mn / all metal elements exceeds 0.55, the elution amount of manganese increases at high temperature operation, and the cycle characteristics may be deteriorated.
  • Cobalt is an element that contributes to improved cycle characteristics.
  • addition of cobalt is optional, but when cobalt is added, the ratio of the number of cobalt atoms to the total number of atoms of the metal element (Co / total metal elements) is preferably 0.05 to 0.00. 4, more preferably 0.1 to 0.4, and still more preferably 0.2 to 0.35.
  • the value of Co / all metal elements is less than 0.05, the effect of addition cannot be sufficiently obtained.
  • the value of Co / all metal elements exceeds 0.4, the initial discharge capacity may be reduced.
  • the composite hydroxide particles of the present invention can contain an additive element M in addition to the main metal element.
  • the additive element M include magnesium (Mg), calcium (Ca), aluminum (Al), titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), and molybdenum.
  • At least one selected from the group consisting of (Mo), hafnium (Hf), tantalum (Ta), and tungsten (W) can be used.
  • the value of t in the general formula (A) indicating the content of the additive element M is 0.1 or less, preferably 0.05 or less, more preferably 0.02 or less. If the value of t exceeds 0.1, the metal element that contributes to the Redox reaction decreases, and the battery capacity decreases.
  • a in the general formula (A) indicating the content of the hydroxyl group (OH) contained in the composite hydroxide particles of the present invention is the average value of the metal elements in the composite hydroxide at the end of the crystallization process. Controlled by number. That is, a is expressed as 1 ⁇ average valence of metal element ⁇ 2. When the average valence of metal element at the end of the crystallization process is 2.1, a is 0.1.
  • composition when used as a positive electrode active material, it can function as a positive electrode material with better cycle characteristics, low resistance and high output when used as a positive electrode active material. Further, in such a composition, the effect of the production method of the present invention is sufficiently exerted, and the improvement of the characteristics is sufficiently achieved while suppressing the deterioration of the characteristics as the positive electrode material due to the suppression of the alkali metal content. Can do.
  • the content of alkali metal contained in the composite hydroxide particles of the present invention is 500 ppm by mass or less, preferably 400 ppm by mass or less, more preferably 270 ppm by mass or less. is there.
  • Alkali metal is used as a neutralizing agent in the crystallization process, and industrially, sodium (Na), potassium (K) or the like is used and contained as an impurity in the obtained composite hydroxide particles. Is done.
  • the positive electrode active material obtained using such composite hydroxide particles as a precursor When the content of alkali metal in the composite hydroxide particles increases, in the positive electrode active material obtained using such composite hydroxide particles as a precursor, the output characteristics deteriorate due to a decrease in battery capacity or an increase in reaction resistance. Will result. Therefore, by making the content of the alkali metal contained in the composite hydroxide particles 500 mass ppm or less, the positive electrode active material obtained using this as a precursor can function as a positive electrode material having excellent battery characteristics. It becomes possible.
  • the sodium content is 500 mass ppm or less. And is preferably 400 mass ppm or less, and more preferably 250 mass ppm or less.
  • the potassium content is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, and further preferably 20 ppm by mass or less. preferable.
  • the particle structure of the composite hydroxide particle of the present invention is not limited as long as it is composed of secondary particles formed by aggregation of a plurality of primary particles.
  • the composite hydroxide particles have a central portion constituted by fine primary particles and It is preferable that a particle structure including an outer shell portion composed of plate-like primary particles larger than the fine primary particles is provided outside the center portion.
  • the positive electrode active material having a composite hydroxide particle having such a particle structure as a precursor has a hollow structure, and a sufficient contact area with the electrolyte is ensured when a secondary battery is configured. Therefore, the output characteristics can be greatly improved.
  • the powder characteristics of the composite hydroxide particles can be adjusted according to the conditions in the crystallization process described above.
  • the powder characteristics are inherited by the positive electrode active material having the composite hydroxide particles as a precursor. That is, the powder characteristics of the composite hydroxide particles can be controlled by adjusting the conditions in the crystallization process according to the powder characteristics required for the target positive electrode active material.
  • the average particle size means an average particle diameter based on volume, and can be determined by, for example, a laser diffraction scattering method.
  • Positive electrode active material for non-aqueous electrolyte secondary battery (1) Positive electrode active material for non-aqueous electrolyte secondary battery
  • the positive electrode active material for non-aqueous electrolyte secondary battery of the present invention (hereinafter referred to as “positive electrode active material”) is the present invention. It is characterized by comprising lithium nickel manganese composite oxide particles obtained by the production method of the present invention and using the nickel manganese composite hydroxide particles of the present invention as a precursor.
  • the value of u indicating the content of lithium (Li) is 0.95 to 1.50, preferably 1.00 to 1.35, more preferably 1.00 to 1. It is controlled in the range of 20. If the value of u is less than 0.95, the positive electrode resistance of the secondary battery using this positive electrode active material will increase, and the output of the battery will decrease. On the other hand, when the value of u exceeds 1.50, the initial discharge capacity of the secondary battery using this positive electrode active material is lowered.
  • the particle structure and powder characteristics of the present invention basically inherit the particle structure and powder characteristics of the composite oxide particles of the present invention. That is, the positive electrode active material of the present invention is not limited in its particle structure as long as it is composed of secondary particles formed by aggregating a plurality of primary particles. However, when a secondary battery having excellent output characteristics is to be obtained, the positive electrode active material preferably has a hollow particle structure. The powder characteristics of the positive electrode active material of the present invention are adjusted according to the intended use of the secondary battery and the required performance, and are not particularly limited.
  • the average particle diameter of the positive electrode active material is preferably adjusted to a volume-based average particle diameter of 3 ⁇ m to 20 ⁇ m by the laser diffraction scattering method. It is preferable to adjust to a range of ⁇ 15 ⁇ m.
  • the method for producing the positive electrode active material of the present invention is the same as that of the prior art, except that the composite hydroxide particles of the present invention described above are used as a precursor. That is, the non-aqueous electrolyte secondary battery of the present invention is obtained by firing the obtained lithium mixture (firing step) after mixing the composite hydroxide particles and the lithium compound described above (mixing step) (firing step). Process).
  • a heat treatment step, a calcination step, a crushing step, and the like can be appropriately performed as necessary.
  • the heat treatment step is a step of heating the composite hydroxide particles at 105 ° C. to 750 ° C. in an oxidizing atmosphere to remove moisture contained in the composite hydroxide particles to obtain heat treated particles.
  • the heat treated particles include not only the composite hydroxide particles from which excess moisture has been removed in the heat treatment step, but also transition metal composite oxide particles converted by the heat treatment step (hereinafter referred to as “composite oxide particles”), Alternatively, a mixture thereof is also included.
  • the mixing step is a step of mixing the lithium compound with the composite hydroxide particles or the heat-treated particles to obtain a lithium mixture.
  • the lithium compound is not particularly limited, but lithium hydroxide, lithium nitrate, lithium carbonate, or a mixture thereof can be used in consideration of availability. Among these, it is preferable to use lithium hydroxide, lithium carbonate, or a mixture thereof in consideration of ease of handling and quality stability.
  • the lithium mixture is sufficiently mixed before firing.
  • mixing is insufficient, Li / Me varies among individual particles, and sufficient battery characteristics may not be obtained.
  • a general mixer can be used for mixing, for example, a shaker mixer, a V blender, a ribbon mixer, a Julia mixer, a Ladige mixer, or the like can be used.
  • the composite hydroxide particles or the heat-treated particles and the lithium compound may be sufficiently mixed so that the shape of the composite hydroxide particles or the heat-treated particles is not destroyed.
  • the lithium mixture is lower than the firing temperature and is 350 ° C. to 800 ° C., preferably 450 ° C. to 780 ° C. after the mixing step and before the firing step. That is, calcination may be performed at a reaction temperature (calcination temperature) between lithium hydroxide or lithium carbonate and the composite oxide particles. Thereby, the diffusion of lithium into the composite hydroxide particles is promoted, and more uniform lithium composite oxide particles can be obtained.
  • the firing step is a step in which the lithium mixture obtained in the mixing step is fired at a predetermined temperature to synthesize a positive electrode active material composed of lithium transition metal composite oxide particles (hereinafter referred to as “lithium composite oxide particles”). .
  • the atmosphere in the firing step is an oxidizing atmosphere, but it is preferably performed in an atmosphere having an oxygen concentration of 18% by volume to 100% by volume, that is, in the air to an oxygen stream. Is more preferable. If the oxygen concentration is less than 18% by volume, the oxidation reaction does not proceed sufficiently, and the crystallinity of the positive electrode active material may not be sufficient.
  • the firing temperature needs to be appropriately adjusted depending on the composition of the composite hydroxide particles or heat-treated particles in the lithium mixture, particularly the composition ratio of the main metal element M.
  • the firing temperature is preferably 800 ° C. to 1100 ° C., more preferably 800 ° C. to 950 ° C.
  • baking time shall be 3 hours or more.
  • the aggregate or sintered body can be crushed to adjust the powder characteristics of the positive electrode active material to a suitable range.
  • pulverization means that mechanical energy is applied to an aggregate composed of a plurality of secondary particles generated by sintering necking between secondary particles during firing, and the secondary particles themselves are hardly destroyed. An operation of separating secondary particles and loosening aggregates.
  • known means can be used, for example, a pin mill or a hammer mill can be used. At this time, it is preferable to adjust the crushing force to an appropriate range so as not to destroy the secondary particles.
  • Non-aqueous electrolyte secondary battery to which the positive electrode active material of the present invention is applied as a positive electrode material is a general non-aqueous electrolyte secondary battery such as a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte solution. It is comprised by the same component.
  • the positive electrode active material of the present invention is applied as a positive electrode material
  • the content of sodium in the positive electrode active material constituting the positive electrode material is reduced, and the thermal stability, charge / discharge capacity, and output characteristics are reduced.
  • the battery characteristics are prevented from being deteriorated, and the variation is small.
  • the reaction aqueous solution is formed by supplying the above-described mixed aqueous solution, 20% by mass sodium hydroxide aqueous solution, and 25% by mass ammonia water into the reaction vessel.
  • the composite hydroxide particles were crystallized.
  • the supply amounts of the mixed aqueous solution, the aqueous sodium hydroxide solution, and the aqueous ammonia were adjusted so that the pH value on the basis of the liquid temperature of 25 ° C. was maintained at 11.5 and the ammonia concentration was maintained at 10 g / L.
  • the reaction atmosphere was maintained in a nitrogen atmosphere having an oxygen partial pressure of 5 Pa and the temperature of the reaction aqueous solution was maintained at 50 ° C. through the crystallization reaction.
  • the slurry containing the composite hydroxide particles obtained as described above was dispensed in a separately prepared container in an air atmosphere (oxygen partial pressure: 21273 Pa), and then washed without being retained. Specifically, the operation of solid-liquid separation of the slurry containing the composite hydroxide particles was repeated twice while being washed with pure water (ion exchange water) using 5C quantitative filter paper. The composite hydroxide particles thus washed and solid-liquid separated were subjected to a vacuum drying treatment at 120 ° C. for 12 hours to obtain powdered composite hydroxide particles.
  • Example 2 From the end of the crystallization process to the start of the washing process, the slurry containing the composite hydroxide particles is stirred for 2 hours in an atmospheric atmosphere (oxygen partial pressure: 21273 Pa). Using a magnetic stirrer HSD-6), composite hydroxide particles were obtained in the same manner as in Example 1 except that the atmospheric atmosphere was not entangled and maintained while stirring at a rotation speed of 500 rpm. The same measurement was performed.
  • Example 3 The composite hydroxide particles are obtained in the same manner as in Example 2 except that the slurry containing the composite hydroxide particles is held with stirring for 4 hours from the end of the crystallization process to the start of the washing process. At the same time, the same measurement was performed.
  • the average valence of the metal element constituting the composite hydroxide particles is 2.15, and the sodium content in the composite hydroxide particles after washing is 260 mass ppm, The potassium content was less than 20 ppm by mass.
  • Example 4 The composite hydroxide particles are obtained in the same manner as in Example 2 except that the slurry containing the composite hydroxide particles is held with stirring for 8 hours from the end of the crystallization process to the start of the washing process. At the same time, the same measurement was performed. As a result of the oxidation-reduction titration after the holding, the average valence of the metal element constituting the composite hydroxide particles is 2.22, and the sodium content in the composite hydroxide particles after washing is 280 mass ppm, The potassium content was less than 20 ppm by mass.
  • Example 1 The composite hydroxide particles are obtained in the same manner as in Example 2 except that the slurry containing the composite hydroxide particles is maintained with stirring for 16 hours from the end of the crystallization process to the start of the washing process. At the same time, the same measurement was performed.
  • the average valence of the metal element constituting the composite hydroxide particles is 2.41
  • the sodium content in the composite hydroxide particles after washing is 510 mass ppm
  • the potassium content was less than 20 ppm by mass, and the potassium content was less than 20 ppm by mass.
  • Example 2 The composite hydroxide particles are obtained in the same manner as in Example 2 except that the slurry containing the composite hydroxide particles is maintained with stirring for 24 hours from the end of the crystallization process to the start of the washing process. At the same time, the same measurement was performed.
  • the average valence of the metal element constituting the composite hydroxide particles is 2.44
  • the sodium content in the composite hydroxide particles after washing is 520 mass ppm
  • the potassium content was less than 20 ppm by mass.
  • Example 3 The composite hydroxide particles are obtained in the same manner as in Example 2 except that the slurry containing the composite hydroxide particles is held with stirring for 32 hours from the end of the crystallization step to the start of the washing step. At the same time, the same measurement was performed. As a result of the oxidation-reduction titration after the holding, the average valence of the metal element constituting the composite hydroxide particles is 2.51, and the sodium content in the composite hydroxide particles after washing is 520 mass ppm. The potassium content was less than 20 ppm by mass.
  • Example 4 The composite hydroxide particles are obtained in the same manner as in Example 2 except that the slurry containing the composite hydroxide particles is maintained with stirring for 96 hours from the end of the crystallization process to the start of the washing process. At the same time, the same measurement was performed.
  • the average valence of the metal element constituting the composite hydroxide particles is 2.66, and the sodium content in the composite hydroxide particles after washing is 980 mass ppm, Potassium content was less than 20 ppm by weight (Example 5) From the end of the crystallization process to the start of the washing process, except that the slurry containing the composite hydroxide particles was maintained with stirring for 4 hours while maintaining the nitrogen atmosphere (oxygen partial pressure: 5 Pa). In the same manner as in Example 2, composite hydroxide particles were obtained and the same measurement was performed.
  • the average valence of the metal element constituting the composite hydroxide particles is 2.08, and the sodium content in the composite hydroxide particles after washing is 210 mass ppm, The potassium content was less than 20 ppm by mass.
  • Example 6 The composite hydroxide particles are obtained in the same manner as in Example 5 except that the slurry containing the composite hydroxide particles is maintained with stirring for 24 hours from the end of the crystallization process to the start of the washing process. At the same time, the same measurement was performed. As a result of the oxidation-reduction titration after the holding, the average valence of the metal element constituting the composite hydroxide particles is 2.07, and the sodium content in the composite hydroxide particles after washing is 220 mass ppm, The potassium content was less than 20 ppm by mass.
  • Example 7 The composite hydroxide particles are obtained in the same manner as in Example 5 except that the slurry containing the composite hydroxide particles is maintained with stirring for 32 hours from the end of the crystallization step to the start of the washing step. At the same time, the same measurement was performed. As a result of the oxidation-reduction titration after the holding, the average valence of the metal element constituting the composite hydroxide particles is 2.08, and the sodium content in the composite hydroxide particles after washing is 220 mass ppm, The potassium content was less than 20 ppm by mass.
  • Example 8 The composite hydroxide particles are obtained in the same manner as in Example 5 except that the slurry containing the composite hydroxide particles is maintained with stirring for 96 hours from the end of the crystallization process to the start of the washing process. At the same time, the same measurement was performed. As a result of the oxidation-reduction titration after the holding, the average valence of the metal element constituting the composite hydroxide particles is 2.08, and the sodium content in the composite hydroxide particles after washing is 240 mass ppm, The potassium content was less than 20 ppm by mass.
  • Example 9 to 12 Comparative Examples 5 to 8, Examples 13 to 16
  • the atmosphere in the reaction vessel was an atmospheric atmosphere (oxygen partial pressure: 21273 Pa)
  • the pH value of the aqueous reaction solution was maintained at 13.0 on the basis of the liquid temperature of 25 ° C.
  • the ammonia concentration was maintained at 15 g / L for 2 minutes and 30 seconds.
  • the supply of 25% by mass aqueous sodium hydroxide is stopped until the pH value of the reaction aqueous solution becomes 11.6 based on the liquid temperature of 25 ° C.
  • alkali metal particularly sodium
  • composite hydroxide It is understood that the content of alkali metal remaining in the product particles can be reduced.
  • composite hydroxide particles are provided as a precursor for obtaining a positive electrode active material with a small content of alkali metal remaining in the crystal, and the composite hydroxide of the present invention It is understood that by using a positive electrode active material having a product particle as a precursor as a positive electrode material, it is possible to manufacture a secondary battery in which deterioration and variation in battery characteristics are suppressed.

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

Abstract

La présente invention concerne des particules d'hydroxyde d'un composé de nickel et de manganèse qui peuvent être utilisées comme précurseur d'un matériau actif cathodique dans lequel la teneur en sodium est réduite et pour lequel la diminution et la variation des caractéristiques de batterie sont évitées. L'invention concerne une suspension comprenant des particules d'hydroxyde de composé de nickel et de manganèse obtenue par une réaction de cristallisation à l'aide d'hydroxyde de sodium comme neutralisant, les particules d'hydroxyde de composé de nickel et de manganèse étant représenté par la formule générale (A) : NixMnyCozMt(OH)2+a (x + y + z + t = 1, 0,3 ≤ x ≤ 0,7, 0,1 ≤ y ≤ 0,55, 0 ≤ z ≤ 0,4, 0 ≤ t ≤ 0,1, 0 ≤ a ≤ 0,5, où M est un ou plusieurs éléments choisis parmi Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta et W). Les particules d'hydroxyde de composé de nickel et de manganèse sont lavées dans un état dans lequel une valence moyenne des éléments métalliques dans les particules d'hydroxyde de composé de nickel et de manganèse est contrôlée à 2,4 ou moins.
PCT/JP2015/071163 2014-07-25 2015-07-24 Particules d'hydroxyde d'un composé de nickel et de manganèse et procédé de production associé Ceased WO2016013674A1 (fr)

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