Classifications

• • 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
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a positive electrode active material for lithium ion batteries, a positive electrode for lithium ion batteries, and a lithium ion battery.
• lithium-containing transition metal oxides are used for a positive electrode active material for lithium ion batteries.
• they are lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganite (LiMn 2 O 4 ) and the like.
• a conjugation of the lithium-containing transition metal oxides is proceeding in order to improve properties such as high volume, cycle characteristic, storage characteristic, decreased internal resistance, rate performance, and safety.
• Lithium ion batteries, for large-size equipment use such as automobile use and load leveling use, require properties different from those of the past mobile phone use and personal computer use.
• patent document 1 discloses a manufacturing method of a positive electrode material for a lithium secondary battery characterized in that a lithium-nickel composite oxide having a composition of Li x Ni 1-y M y O 2 ⁇ (0.8 ⁇ x ⁇ 1.3, 0 ⁇ y ⁇ 0.5, M is at least one element selected from a group consisting of Co, Mn, Fe, Cr, V, Ti, Cu, Al, Ga, Bi, Sn, Zn, Mg, Ge, Nb, Ta, Be, B, Ca, Sc and Zr.
• ⁇ oxygen loss or oxygen excess
• the lithium-nickel composite oxide disclosed in Patent document 1 has excess oxygen in the composition formula, and there is still room for improvement as high-quality positive electrode active material for lithium ion batteries.
• the present invention aims to provide a positive electrode active material for lithium ion batteries having excellent battery property.
• the inventors have diligently studied and eventually have found out, there is a close correlation between amount of oxygen in the positive electrode active material and battery property. That is, they found out that excellent battery property can be provided especially when the amount of oxygen in the positive electrode active material is a certain value or more, and more excellent battery property can be provided by controlling average particle sizes of powder in the positive electrode active material having amount of oxygen, being a certain value or more.
• the present invention produced on the basis of the above findings, in one aspect, is a positive electrode active material for lithium ion batteries, represented by composition formula: Li x Ni 1-y M y O 2+ ⁇ , wherein M is Co as an essential component and at least one species selected from a group consisting of Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B and Zr, 0.9 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.7, ⁇ >0.05, and an average particle size (D50) is 5 ⁇ m to 15 ⁇ m. “D50” means a particle size corresponding to 50% in volume-based cumulative fractions.
• the present invention is, in one embodiment, the positive electrode active material for lithium ion batteries where the average particle size (D50) is 7 ⁇ m to 13 ⁇ m.
• the present invention is, in yet another embodiment, the positive electrode active material for lithium ion batteries, where M is at least one species selected from a group consisting of Mn and Co.
• the present invention is, in yet another embodiment, the positive electrode active material for lithium ion batteries, where ⁇ >0.15.
• the present invention is, in yet another embodiment, the positive electrode active material for lithium ion batteries, where ⁇ >0.20.
• the present invention is, in yet another embodiment, the positive electrode active material for lithium ion batteries, where D90 is 20 ⁇ m or less in particle size distribution.
• D90 means a particle size corresponding to 90% in volume-based cumulative fractions.
• the present invention in another aspect, is a positive electrode for lithium ion batteries using the positive electrode active material for lithium ion batteries of the present invention.
• the present invention in yet another aspect, is a lithium ion battery using the positive electrode for lithium ion batteries of the present invention.
• the present invention can provide a positive electrode active material for lithium ion batteries having excellent battery property.
• lithium-containing transition metal oxides such as lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ) and lithium manganite (LiMn 2 O4).
• the positive electrode active material for lithium ion batteries of the present invention is represented by composition formula: Li x Ni 1-y M y O 2+ ⁇ , where M is Co as an essential component and at least one species selected from a group consisting of Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B and Zr, 0.9 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.7, ⁇ >0.05.
• the lithium ratio to all metal amount in the positive electrode active material for lithium ion batteries is 0.9 to 1.2. This is because it is difficult to maintain stable crystal structure if the ratio is less than 0.9, and high volume of the battery cannot be secured if the ratio is more than 1.2.
• the positive electrode active material for lithium ion batteries consists of primary particles, secondary particles formed by aggregation of the primary particles or mixture of the primary particles and the secondary particles.
• An average particle size (D50) of primary particles, secondary particles formed by aggregation of the primary particles or mixture of the primary particles and the secondary particles is 5 ⁇ m to 15 ⁇ m.
• the average particle size (D50) is preferably 13 ⁇ m or less, more preferably 7 ⁇ m to 13 ⁇ m.
• D90 is 20 ⁇ m or less in particle size distribution. When D90 is 20 ⁇ m or less, reaction variability among the particles decreases and then rate performance and cycle performance become more excellent. D90 is preferably 13 ⁇ m to 20 ⁇ m.
• the positive electrode for lithium ion batteries of the present invention has a structure, for example, where positive electrode combination agent, prepared by mixing the positive electrode active material for lithium ion batteries having the above described structure, conductivity auxiliary agent and binder, is applied on one surface or both surfaces of a current collector made of aluminum foil and the like.
• the lithium ion battery of the embodiment of the present invention has the positive electrode for lithium ion batteries having the above described structure.
• metal salt solution is produced.
• the metal is Ni and at least one species selected from a group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B and Zr.
• the metal salt is sulfate, chloride, nitrate, acetate and the like.
• nitrate is preferable because nitrate can be directly calcined and therefore cleaning process can be omitted when nitrate is mixed in raw material for calcination as impurities, and nitrate acts as an oxidant to promote oxidation of metals in the raw material for calcination.
• Each metal contained in the metal salt is prepared such that it has a desired molar ratio. In this way, molar ratio of each metal in the positive electrode active material is determined.
• lithium carbonate is suspended in pure water, and then metal salt solution of the above metal is poured to produce metal carbonate solution slurry. At this time, microparticles of lithium-containing carbonate precipitate in the slurry.
• the lithium compounds do not react at heat treatment as with sulfate, chloride and the like as metal salt, they are cleaned by saturated lithium carbonate solution and then filtered.
• the lithium compounds react at heat treatment as with nitrate and acetate, as the lithium raw material, they are not cleaned but directly filtered. Then they are dried and then they can be used as precursor of calcination.
• the filtered lithium-containing carbonate is dried and then powder of lithium salt complex (precursor for positive electrode active material for lithium ion batteries) is provided.
• the powder of the precursor for positive electrode active material for lithium ion batteries, provided by drying, is classified to provide only powder having the particle size of 1 ⁇ m to 30 ⁇ m, by using a sifter or a commercially available classification apparatus and the like.
• a calcination holder having a predetermined content, is prepared.
• Precursor for positive electrode active material for lithium ion batteries having the particle size of 1 ⁇ m to 30 ⁇ m, is filled in the calcination holder.
• the calcination holder filled with powder of precursor for positive electrode active material for lithium ion batteries, is moved to a calcination furnace and then calcined.
• the calcination is conducted by heat preservation for predetermined time under oxygen atmosphere. Further, it is preferable to conduct the calcination under increased pressure of 101 KPa to 202 KPa because amount of oxygen in the composition increases.
• the powder is taken from the calcination holder and then powder of positive electrode active material is provided by pulverization with commercially available pulverization apparatus and the like.
• the pulverization is conducted by controlling pulverization power and pulverization time accordingly, to provide desired median diameter and repose angle.
• lithium carbonate the amount of which is described in Table 1
• metal salt solution was prepared such that the composition ratio of each metal became the value described in Table 1 with regard to each hydrate of nitrate and all molar number of the metals became 14 mol.
• Suspension amount of lithium carbonate was such that a product (positive electrode material for lithium ion batteries, that is, positive electrode active material) was Li x (Ni 1-y M y )O 2+ ⁇ , where x is described in Table 1, and each of the amount was respectively calculated by the following formula.
• “A” is a value to be multiplied in order to subtract the amount of lithium in lithium compound other than lithium carbonate remaining in raw materials after filtration, in addition to needed volume for precipitation reaction, from the suspension amount beforehand.
• “A” is 0.9 when lithium salt reacts as raw material of calcination as with nitrate and acetate.
• “A” is 1.0 when lithium salt does not react as raw material of calcination as with sulfate and chloride.
• Microparticles of lithium-containing carbonate precipitated in the solution by the treatment Then the precipitate was filtered by using a filter press. Next, the precipitate was dried and then the lithium-containing carbonate (precursor for positive electrode active material for lithium ion batteries) was produced.
• the lithium-containing carbonate, provided by drying, was classified to provide powder having the particle size of 1 ⁇ m to 30 ⁇ m by using a sifter.
• a calcination holder was prepared and then filled with the lithium-containing carbonate. Then the calcination holder was set in an oxygen atmosphere furnace at atmospheric pressure, heat preservation was conducted for 10 hours at the calcination temperature described in Table 1, and then oxides were provided by cooling.
• the provided oxides were pulverized to 5 ⁇ m to 15 ⁇ m of the average particle size with a compact pulverization apparatus (HOSOKAWA MICRON ACM-2EC), and then powder of positive electrode active materials for lithium ion batteries were provided.
• a compact pulverization apparatus HOSOKAWA MICRON ACM-2EC
• composition of each metal of raw materials is shown in Table 1, metal salt was chloride. After precipitating lithium-containing carbonate, washing treatment was conducted by saturated lithium carbonate solution and then filtration treatment was conducted. Other than that, treatments similar to working examples 1 to 15 were conducted.
• composition of each metal of raw materials is shown in Table 1, metal salt was sulfate. After precipitating lithium-containing carbonate, washing treatment was conducted by saturated lithium carbonate solution and then filtration treatment was conducted. Other than that, treatments similar to working examples 1 to 15 were conducted.
• composition of each metal of raw materials is shown in Table 1. Calcination treatment was conducted under increased pressure of 120 KPa instead of conducting under atmosphere pressure. Other than that, treatments similar to working examples 1 to 15 were conducted.
• composition of each metal of raw materials is shown in Table 1, classification after drying the precursor was not conducted, and the last pulverization of oxides was conducted such that the average particle size became 5 ⁇ m or less, or 20 ⁇ m or more. Other than that, treatments similar to working examples 1 to 15 were conducted.
• composition of each metal of raw materials is shown in Table 1. Calcination treatment was conducted in an air atmosphere furnace instead of conducting in an oxygen atmosphere furnace. Other than that, treatments similar to comparative example 1 were conducted.
• Powders of each positive electrode material were taken and D50 and D90 were measured by Laser Diffraction Particle Size Analyzer (SHIMADZU: SALD-3000).
• the positive electrode active material, an electrical conducting material and a binder were weighed in a proportion of 85:8:7. Next, the positive electrode active material and the electrical conducting material were mixed in an organic solvent (N-methylpyrrolidone) where the binder dissolved, and then slurry was produced. Next, the slurry was applied to aluminum foil, and then a positive electrode was produced by pressing after drying the slurry.
• organic solvent N-methylpyrrolidone

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• Inorganic Compounds Of Heavy Metals (AREA)

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• 2011
  • 2011-07-22 CN CN201510940247.6A patent/CN105514420A/zh active Pending
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