WO2014061653A1 - Li-Ni複合酸化物粒子粉末及びその製造方法、並びに非水電解質二次電池 - Google Patents
Li-Ni複合酸化物粒子粉末及びその製造方法、並びに非水電解質二次電池 Download PDFInfo
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- WO2014061653A1 WO2014061653A1 PCT/JP2013/077951 JP2013077951W WO2014061653A1 WO 2014061653 A1 WO2014061653 A1 WO 2014061653A1 JP 2013077951 W JP2013077951 W JP 2013077951W WO 2014061653 A1 WO2014061653 A1 WO 2014061653A1
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- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- 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
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- 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
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- 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
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Definitions
- the present invention relates to a Li—Ni composite oxide particle powder having a high initial discharge capacity and excellent thermal stability when used as a positive electrode active material of a non-aqueous electrolyte secondary battery, and a method for producing the same.
- LiMn 2 O 4 of spinel structure LiMnO 2 having a zigzag layer structure, LiCoO 2 of layered rock-salt structure, LiNiO 2 and the like are generally known, and lithium ion secondary batteries using LiNiO 2 have attracted attention as batteries having a high charge / discharge capacity.
- this material is inferior in thermal stability during charging and charge / discharge cycle durability, further improvement in characteristics is required.
- the primary particle diameter of the Li—Ni composite oxide is small, in order to obtain a Li—Ni composite oxide having a high packing density, the physical properties must be set so that they form densely aggregated secondary particles. Need to control.
- the Li—Ni composite oxide in which secondary particles are formed increases the surface area due to secondary particle destruction due to compression during electrode preparation, and the reaction with the electrolyte is promoted during storage at a high temperature charged state.
- the non-conductive film formed at the interface is characterized in that the resistance as a secondary battery increases.
- the Li—Ni composite oxide starts a decomposition reaction with oxygen release from a lower temperature than the Li—Co composite oxide, and the released oxygen causes the electrolyte to burn and the temperature of the battery rapidly increases.
- the crystallite size (primary particle diameter) is effectively increased to the extent that the discharge capacity does not decrease, and the reaction with the electrolyte is suppressed, or the crystal structure Need to be stabilized.
- Li—Ni composite oxide having a high discharge capacity and excellent thermal stability is required as a positive electrode active material for a non-aqueous electrolyte secondary battery.
- LiNiO 2 powder in order to improve various characteristics such as higher capacity, control of crystallite size, stabilization of crystal structure, and thermal stability.
- a composition is controlled so that the amount of tetravalent Ni is 60% or less to improve thermal stability (Patent Document 1), Li—Ni Cycle characteristics and thermal stability by replacing part of Ni in the composite oxide with at least one element selected from metal species including Co, Al and Mn, and removing excess Li after firing , Technology for improving storage characteristics (Patent Document 2), Technology for improving the thermal stability by controlling the crystallite size by incorporating an oxide of at least one element of B and P into a Li—Ni composite oxide (Patent Document 3), a technique of stabilizing a crystal structure by replacing a part of Ni in a Li—Ni composite oxide with Co and Al (Patent Document 4), and the like are known.
- Li—Ni composite oxide having a high discharge capacity and excellent thermal stability is currently most demanded, but has not yet been obtained.
- Patent Document 1 is based on the composition of the original Li—Ni composite oxide so that the amount of tetravalent Ni is 60% or less in the Li—Ni composite oxide from which 75% of Li is extracted by charging. Is a technology that improves heat stability.
- the amount of tetravalent Ni is 60% or less, a large amount of Ni is substituted with Co and Mn. Therefore, it is necessary to increase the charging voltage to achieve high capacity, and the thermal stability is reduced. You have to sacrifice. Therefore, it is difficult to say that controlling the composition alone can achieve both high capacity and thermal stability, and it is not sufficient as a method for obtaining a Li—Ni composite oxide with improved thermal stability.
- Patent Document 2 replaces a part of Ni in the Li—Ni composite oxide with at least one element selected from metal species including Co, Al, and Mn, and an excessive amount after firing.
- This is a technique for improving cycle characteristics, thermal stability, and storage characteristics by removing Li.
- the Li removal treatment causes a reduction in capacity and is not sufficient as a method for obtaining a Li—Ni composite oxide having a high discharge capacity.
- Li removal treatment by washing increases the specific surface area of the Li—Ni composite oxide and promotes reaction with the electrolyte during high-temperature charging, thus improving the thermal stability of the Li—Ni composite oxidation. It's not enough as a way to get things.
- Patent Document 3 is a technique for improving the thermal stability by adding an oxide of at least one element of B and P to a Li—Ni composite oxide.
- the addition of an element that does not participate in the charge / discharge reaction causes disorder of the crystal structure and a decrease in capacity, and thus is not sufficient as a method for obtaining a high discharge capacity.
- the firing temperature is low, the crystallite size is small and the exothermic peak is located at a low temperature. Further, when the crystallite size is small, the specific surface area of the Li—Ni composite oxide increases, resulting in a high temperature. Since the reaction with the electrolytic solution is promoted during charging, it is not sufficient as a method for obtaining a Li—Ni composite oxide with improved thermal stability.
- Patent Document 4 is a technique that stabilizes the crystal structure by replacing part of Ni in the Li—Ni composite oxide with Co and Al, thereby enabling high capacity and high output. is there.
- the Li site occupancy of the Li site in the crystal by the Rietveld analysis is 98.5% or more and the metal site occupancy of the metal site is 95% or more and 98% or less, the purpose is to improve battery capacity and output characteristics. It is not intended to improve thermal stability.
- a technical problem of the present invention is to obtain Li—Ni composite oxide particle powder having a high discharge capacity and excellent thermal stability when used as a positive electrode active material of a non-aqueous electrolyte secondary battery.
- the present invention is a composition of Li x Ni 1-y-a -b Co y M1 a M2 b O 2 (1.00 ⁇ x ⁇ 1.10,0 ⁇ y ⁇ 0.25,0 ⁇ a ⁇ 0 .25, 0 ⁇ b ⁇ 0.10, M1 is at least one element selected from Al and Mn, and M2 is at least one element selected from Zr and Mg).
- Li-Ni characterized by the product of the metal site occupancy (%) of lithium sites obtained from Rietveld analysis of line diffraction and the crystallite size (nm) obtained from Rietveld analysis being 700 or more and 1400 or less This is a composite oxide particle powder (Invention 1).
- the present invention also provides the Li—Ni composite oxide particles according to the present invention, wherein the lithium site has a metal site occupancy of 2% or more and 7% or less obtained from a Rietveld analysis of the Li—Ni composite oxide. It is a powder (Invention 2).
- the present invention is the Li—Ni composite oxide particle powder according to the first or second aspect of the present invention, wherein the crystallite size obtained from Rietveld analysis of the Li—Ni composite oxide is 500 nm or less (Invention 3). ).
- the present invention also provides the Li—Ni composite oxide particles according to any one of the present inventions 1 to 3, which have an average particle diameter of 1 to 20 ⁇ m and a BET specific surface area of 0.1 to 1.6 m 2 / g. It is a powder (Invention 4).
- the present invention also relates to a method for producing a Li—Ni composite oxide particle powder in which a lithium compound powder and a Ni—Co hydroxide particle powder are mixed, and the resulting mixture is fired.
- the hydroxide particle powder is prepared by mixing an aqueous sulfate solution of a metal element, an aqueous ammonia solution, and an aqueous sodium hydroxide solution so that the ammonia concentration in the reaction vessel is 1.4 mol / l or less (the ammonia concentration in the reaction vessel). ) / (Excess hydroxyl group concentration in the reaction vessel) is controlled to be 6 or more to obtain a Ni—Co hydroxide powder according to any one of the present inventions 1 to 4 (Invention 5).
- the present invention also provides a Li—Ni composite oxide in which a lithium compound powder, a Ni—Co hydroxide particle powder, an aluminum compound powder and / or a zirconium compound powder are mixed, and the resulting mixture is fired.
- a method for producing particle powder in which Ni—Co hydroxide particle powder is prepared by mixing an aqueous sulfate solution of a metal element, an aqueous ammonia solution, and an aqueous sodium hydroxide solution so that the ammonia concentration in the reaction vessel is 1.4 mol.
- This is a method for producing the Li—Ni composite oxide particle powder according to the present invention (Invention 6).
- the present invention is a nonaqueous electrolyte secondary battery using a positive electrode containing a positive electrode active material comprising the Li—Ni composite oxide particle powder according to any one of the present inventions 1 to 4 (Invention 7). .
- the Li—Ni composite oxide particle powder according to the present invention has a high charge / discharge capacity by securing a lithium diffusion path by controlling the metal site occupancy ratio mixed in the lithium site to 2% or more and 7% or less. Since it can be obtained and the crystal structure is stabilized, the thermal stability is also good.
- the Li—Ni composite oxide particle powder according to the present invention has a controlled crystallite size and a small specific surface area, so that the reaction with the electrolytic solution is suppressed and the thermal stability is good.
- the Li—Ni composite oxide particle powder according to the present invention can achieve high capacity and improved thermal stability at the same time, and is suitable as a positive electrode active material for a non-aqueous electrolyte secondary battery.
- FIG. 3 is a SEM image of Li—Ni composite oxide particles obtained in Example 1.
- FIG. 2 is a SEM image of Li—Ni composite oxide particles obtained in Comparative Example 1.
- FIG. 3 is a SEM image of Li—Ni composite oxide particles obtained in Example 1.
- Li—Ni composite oxide particle powder for a non-aqueous electrolyte secondary battery according to the present invention will be described.
- the composition of the Li—Ni composite oxide particles according to the present invention is Li x Ni 1- yab Co y M1 a M2 b O 2 (1.00 ⁇ x ⁇ 1.10, 0 ⁇ y ⁇ 0 .25, 0 ⁇ a ⁇ 0.25, 0 ⁇ b ⁇ 0.10, M1 is at least one element selected from Al and Mn, and M2 is at least one element selected from Zr and Mg).
- x is smaller than 1.00, Ni is likely to be mixed into the Li phase, the metal site occupation ratio of the lithium site is increased, and a Li—Ni composite oxide having a high battery capacity cannot be obtained.
- x is larger than 1.10, the amount of Li mixed into the metal site is increased, so that the Ni knocked out from the metal site is mixed into the Li phase and the metal site occupation ratio of the lithium site is increased.
- x is preferably 1.00 ⁇ x ⁇ 1.05, more preferably 1.01 ⁇ x ⁇ 1.04.
- y is preferably 0.03 ⁇ y ⁇ 0.20, more preferably 0.05 ⁇ y ⁇ 0.15.
- a is larger than 0.25, the true density of the positive electrode active material is lowered, so that it is difficult to obtain a material with high filling properties, the charge / discharge capacity is remarkably lowered, and the charge / discharge capacity is high.
- the merit of the Li—Ni composite oxide is reduced.
- a is preferably 0.01 ⁇ a ⁇ 0.20, more preferably 0.02 ⁇ a ⁇ 0.15.
- b is larger than 0.10, the true density of the positive electrode active material is lowered, so that it is difficult to obtain a material with high filling property, and the charge / discharge capacity is remarkably lowered, and the charge / discharge capacity is high.
- the merit of the Li—Ni composite oxide is reduced.
- b is preferably 0.001 ⁇ b ⁇ 0.05, more preferably 0.002 ⁇ b ⁇ 0.02.
- the crystal structure of the Li—Ni composite oxide according to the present invention belongs to the space group R-3m and is mainly a lithium site (3a site) occupied by lithium, a metal site occupied mainly by Ni, Co, M1, and M2 ( 3b site), mainly oxygen sites occupied by oxygen (6c sites).
- R-3m is officially written with a bar on 3 of R3m, but here it is represented as R-3m for convenience.
- the crystal structure of the Li—Ni composite oxide according to the present invention was analyzed by Rietveld analysis.
- a peak shape function of X-ray diffraction of the Li—Ni composite oxide particle powder a modified TCH pseudo-voigt function represented by superposition of a Gaussian function and a Lorentz function was used.
- the crystallite size was calculated by using the Scherrer equation from the coefficient of (cos ⁇ ) ⁇ 1 of the half-value width of the Lorentz function when the Gaussian function was regarded as an almost device-dependent function and ⁇ was the diffraction angle.
- the seat occupancy rate at each site can be calculated by the same analysis.
- the metal seat occupation ratio of the lithium site is a ratio of the lithium site occupied by atoms of Ni, Co, M1, and M2.
- the product of the lithium site metal site occupancy (%) obtained from the X-ray diffraction Rietveld analysis of the Li—Ni composite oxide particles according to the present invention and the crystallite size (nm) obtained from the Rietveld analysis is 700.
- the above is 1400 or less.
- the product of the lithium-site metal seat occupancy (%) and the crystallite size (nm) obtained from the lead belt analysis is considered to be related to the durability of the Li-Ni composite oxide particles in the de-Li process. It is done.
- the metal site occupancy of the lithium site represents the completeness of the R-3m structure of the Li—Ni composite oxide particle powder
- the crystallite size means the size of the R-3m structure.
- the electrochemical characteristics of the Li—Ni composite oxide particle powder can be controlled.
- the product of the lithium site metal seat occupancy and the crystallite size is smaller than 700, the reactivity with the electrolytic solution is promoted and the thermal stability is deteriorated, which is not preferable.
- the product of the metal site occupation ratio of the lithium site and the crystallite size is larger than 1400, the diffusion resistance of lithium ions becomes high and the initial discharge capacity is lowered, which is not preferable.
- the product of the metal site occupation ratio and the crystallite size of the lithium site is preferably 900 or more and 1300 or less, and more preferably 1000 or more and 1200 or less.
- the metal site occupancy of lithium sites obtained from the Rietveld analysis of the X-ray diffraction of the Li—Ni composite oxide particles according to the present invention is preferably 2% or more and 7% or less.
- the metal seat occupation ratio of the lithium site is larger than 7%, sufficient charge / discharge capacity cannot be obtained.
- the metal seat occupation ratio of the lithium site is 2% or more and 6% or less.
- the metal site occupancy of the lithium site is small.
- a sufficient charge / discharge capacity can be obtained even if the metal site occupation ratio of the lithium site is 2% or more.
- the crystallite size obtained from the Rietveld analysis of the X-ray diffraction of the Li—Ni composite oxide particle powder according to the present invention is preferably 500 nm or less.
- the lower limit of the crystallite size is usually 100 nm.
- the crystallite size is preferably 100 nm or more and 450 nm or less, more preferably 200 nm or more and 400 nm or less.
- the BET specific surface area of the Li—Ni composite oxide particle powder according to the present invention is preferably 0.1 to 1.6 m 2 / g.
- the BET specific surface area value is smaller than 0.1 m 2 / g, it is difficult to produce industrially.
- the BET specific surface area value is larger than 1.6 m 2 / g, it is not preferable because the filling density is lowered and the reactivity with the electrolytic solution is increased.
- the BET specific surface area value is more preferably 0.1 to 1.0 m 2 / g, and still more preferably 0.15 to 0.6 m 2 / g.
- the average particle size of the Li—Ni composite oxide particles according to the present invention is preferably 1 to 20 ⁇ m.
- the average particle size is smaller than 1 ⁇ m, it is not preferable because the packing density is lowered and the reactivity with the electrolyte is increased.
- it exceeds 20 ⁇ m it is difficult to produce industrially. More preferably, it is 3 to 17 ⁇ m.
- the particle shape of the Li—Ni composite oxide particles according to the present invention is preferably spherical and has few acute angles.
- the Li—Ni composite oxide particle powder according to the present invention can be obtained by mixing a lithium compound powder and a Ni—Co hydroxide particle powder and firing the resulting mixture.
- the Li—Ni composite oxide particle powder according to the present invention is obtained by mixing a lithium compound powder, a Ni—Co hydroxide particle powder, an aluminum compound powder and / or a zirconium compound powder.
- the obtained mixture can be obtained by firing.
- the lithium compound used in the present invention is preferably lithium hydroxide, and the lithium carbonate content is particularly preferably less than 5%.
- the content of lithium carbonate is 5% or more, lithium carbonate remains in the produced Li—Ni composite oxide as an impurity, reducing the initial charge / discharge capacity and decomposing lithium carbonate during charging, It causes a decrease in thermal stability.
- the lithium compound powder to be used preferably has an average particle size of 50 ⁇ m or less. More preferably, it is 30 ⁇ m or less. When the average particle size of the lithium compound powder exceeds 50 ⁇ m, the mixing of the Ni—Co hydroxide particle powder with the aluminum compound powder and / or the zirconium compound powder becomes non-uniform and the crystallinity is good. It becomes difficult to obtain a Li—Ni composite oxide.
- Ni—Co hydroxide in the present invention includes Ni—Co—Mn hydroxide and Ni—Co—Mn—Mg hydroxide.
- Ni—Co hydroxide particles in the present invention preferably have an average particle size of 2 to 30 ⁇ m and a BET specific surface area of 1 to 20 m 2 / g.
- the Ni—Co hydroxide particle powder is prepared by mixing a metal element with a predetermined molar amount of an aqueous solution of a sulfate of a metal element such as 0.1 to 2.0 mol / l nickel sulfate and cobalt sulfate, manganese sulfate, and magnesium sulfate.
- a mixed aqueous solution, an aqueous ammonia solution, and an aqueous sodium hydroxide solution are mixed so that the ammonia concentration in the reaction vessel is 1.4 mol / l or less, and (ammonia concentration in the reaction vessel) / (in the reaction vessel)
- 1.0 to 15.0 mol / l aqueous ammonia solution and 0.1 to 2.0 mol / l sodium hydroxide solution were continuously fed to the reaction vessel so that the excess hydroxyl concentration of
- the Ni—Co hydroxide suspension overflowing from the reaction tank is seeded and circulated to the reaction tank while adjusting the concentration rate in the concentration tank connected to the overflow pipe.
- the concentration of i-Co hydroxide was reacted until 2 ⁇ 10mol / l, can be obtained by performing a particle control by mechanical impact.
- the ammonia concentration in the reaction tank is preferably 1.4 mol / l or less.
- the ammonia concentration in the reaction tank exceeds 1.4 mol / l, the primary particles of Ni—Co hydroxide increase, the reactivity with the lithium compound during firing decreases, and the crystallite size control during firing can be controlled. It becomes difficult.
- Ni—Co hydroxide is produced based on the following formula (1). Me 2 + SO 4 + 2NaOH ⁇ Me 2 + (OH) 2 + Na 2 SO 4 (1) At this time, the molar ratio of Me 2 + SO 4 and NaOH is 1: 2, which is a theoretical raw material ratio. However, the reaction in the present invention is performed by supplying NaOH more than the theoretical molar ratio. The desired Ni—Co hydroxide was obtained by controlling the excess hydroxyl group concentration at that time.
- the surplus hydroxyl group concentration in the reaction vessel is preferably 0.005 mol / l or more and 0.04 mol / l or less.
- the excess hydroxyl group concentration in the reaction tank is less than 0.005 mol / l, the density of secondary particles of Ni—Co hydroxide is lowered and the bulk density of Ni—Co hydroxide is lowered.
- the excess hydroxyl group concentration in the reaction vessel exceeds 0.04 mol / l, the primary particle size of Ni—Co hydroxide increases and the reactivity with the Li compound during firing decreases.
- (Ammonia concentration in reaction tank) / (excess hydroxyl group concentration in reaction tank) is preferably 6 or more.
- (ammonia concentration in the reaction vessel) / (excess hydroxyl group concentration in the reaction vessel) is less than 6, the primary particles of Ni—Co hydroxide increase, and the reactivity with the lithium compound during firing decreases. It becomes difficult to control the crystallite size during firing.
- the Ni—Co hydroxide particle powder is used against the Ni—Co hydroxide slurry weight by using a filter press, vacuum filter, filter thickener or the like. It can be obtained by washing with 1 to 10 times as much water and drying.
- an aluminum hydroxide is preferably used as the aluminum compound used in the present invention.
- the average particle size of the aluminum compound powder is preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less.
- the primary particle diameter of the aluminum compound powder is preferably 1 ⁇ m or less.
- the addition amount of the aluminum compound is preferably 2 to 5% in terms of elemental molar ratio with respect to Ni—Co hydroxide.
- the addition amount of the aluminum compound is less than 2%, the thermal stability is lowered, and when it exceeds 5%, the discharge capacity is lowered.
- the zirconium compound used in the present invention is preferably a zirconium oxide.
- the average particle size of the zirconium compound powder is preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less.
- the amount of zirconium compound added is preferably 2% or less in terms of elemental molar ratio with respect to Ni—Co hydroxide. When the amount of the zirconium compound exceeds 2%, the discharge capacity decreases.
- the mixing treatment of the lithium compound powder, the Ni—Co hydroxide particle powder, the aluminum compound powder and / or the zirconium compound powder may be either dry or wet as long as they can be uniformly mixed.
- the mixing ratio of the lithium compound powder, the Ni—Co hydroxide particle powder, the aluminum compound powder, and / or the zirconium compound powder is 1.00 to 1.10.
- the molar ratio is Li / (Ni + Co + M1 + M2). It is preferable.
- the firing temperature is preferably 650 ° C. to 950 ° C.
- the firing temperature is less than 650 ° C., the reaction between Li and Ni does not proceed sufficiently, and the primary particle growth of Li—Ni composite oxide particles becomes insufficient.
- the firing temperature exceeds 950 ° C., Ni 3+ It is reduced to Ni 2+ and mixed into the Li phase, and the metal site occupation ratio of the lithium site increases.
- a more preferable firing temperature is 700 ° C. to 900 ° C.
- the atmosphere during firing is preferably an oxidizing gas atmosphere, and more preferably the oxygen concentration in the atmosphere is 70% or more.
- the firing time is preferably 5 to 30 hours.
- a non-aqueous electrolyte secondary battery using a positive electrode containing a positive electrode active material made of Li—Ni composite oxide particles according to the present invention is composed of the positive electrode, the negative electrode, and an electrolyte.
- a positive electrode mixture in which a conductive agent and a binder are added and mixed in accordance with a conventional method. Is applied to the current collector.
- a conductive agent acetylene black, carbon black, graphite and the like are preferable
- the binder polytetrafluoroethylene, polyvinylidene fluoride and the like are preferable.
- an electrode containing a negative electrode active material such as lithium metal, lithium / aluminum alloy, lithium / tin alloy, graphite, or graphite can be used.
- At least one lithium salt such as lithium perchlorate and lithium tetrafluoroborate can be dissolved in a solvent and used.
- an organic solvent containing at least one of carbonates such as propylene carbonate and dimethyl carbonate and ethers such as dimethoxyethane can be used as the electrolyte solvent.
- the nonaqueous electrolyte secondary battery manufactured using the positive electrode active material comprising the Li—Ni composite oxide particles according to the present invention has an initial discharge capacity of about 185 to 210 mAh / g, and was measured by an evaluation method described later.
- Excellent heat release rate is 0.15 W / g ⁇ s or less.
- the heat generation rate is preferably 0.15 W / g ⁇ s or less, more preferably closer to 0 W / g ⁇ s.
- both the metal site occupancy and the crystallite size in the lithium site It is important to control. Therefore, in the present invention, the metal site occupation ratio (%) of the lithium site obtained from the Rietveld analysis of the X-ray diffraction of the Li—Ni composite oxide particle powder and the crystallite size (nm) obtained from the Rietveld analysis.
- the product was 700 or more and 1400 or less.
- the metal seat occupation ratio mixed in the lithium site to 2% or more and 7% or less, it is possible to secure a lithium diffusion path and obtain a high charge / discharge capacity, and to stabilize the crystal structure. It becomes possible to improve the thermal stability.
- the Li—Ni composite oxide particle powder according to the present invention has a large crystallite size and a small specific surface area, the reaction with the electrolytic solution is suppressed and the thermal stability can be improved.
- a typical embodiment of the present invention is as follows.
- the ammonia concentration in the reaction vessel when producing the Ni—Co hydroxide according to the present invention is determined by collecting a predetermined amount of the supernatant of the reaction slurry containing hydroxide and subjecting the ammonia component in the supernatant to distillation extraction.
- the ammonia concentration in the extract was titrated with a 0.5N hydrochloric acid solution, and the titration amount at which the pH was 5.2 was determined as the end point.
- the excess hydroxyl group concentration in the reaction tank was obtained by collecting a predetermined amount of the supernatant of the reaction slurry containing hydroxide, titrating with a 0.5N hydrochloric acid solution as it was, and setting the titer at which the pH was 5.2 as the end point. The sum of ammonia and excess hydroxyl group concentration was determined from the titration amount, and the ammonia concentration was subtracted from that value.
- composition of the Li—Ni composite oxide particles according to the present invention was determined by dissolving the powder with an acid and measuring with a plasma emission spectroscopic analyzer ICPS-7500 [manufactured by Shimadzu Corporation].
- the average particle size is a volume-based average particle size measured using a laser type particle size distribution analyzer LMS-30 [manufactured by Seishin Enterprise Co., Ltd.].
- the average particle size of the lithium compound was measured by a dry laser method, and the average particle size of other powders was measured by a wet laser method.
- the primary particle size of the aluminum compound powder is the size of the primary particles constituting the secondary particles when observed using a scanning electron microscope SEM-EDX with an energy dispersive X-ray analyzer [manufactured by Hitachi High-Technologies Corporation]. That's it.
- the specific surface area was determined by a BET one-point continuous method using MONOSORB [manufactured by Yuasa Ionics Co., Ltd.] after drying and degassing the sample at 250 ° C. for 15 minutes under a mixed gas of 30% nitrogen and 70% helium. Surface area.
- the metal seat occupation ratio of the lithium site was obtained from the Rietveld analysis of X-ray diffraction performed under the conditions of Cu-K ⁇ , 45 kV, 200 mA using an X-ray diffractometer SmartLab [manufactured by Rigaku Corporation].
- the crystallite size was determined from Rietveld analysis of X-ray diffraction performed under the conditions of Cu-K ⁇ , 45 kV, and 200 mA using an X-ray diffractometer SmartLab (manufactured by Rigaku Corporation).
- the initial charge / discharge characteristics and thermal stability were evaluated by a coin cell using a positive electrode active material made of Li—Ni composite oxide particle powder.
- the initial charge / discharge characteristics were evaluated by the initial discharge capacity of a coin cell using a positive electrode active material made of Li—Ni composite oxide particle powder. Using the above coin cell, charging at room temperature was performed at 0.1 C up to 4.3 V, then discharging was performed at 0.1 C up to 3.0 V, and the initial discharge capacity at that time was measured.
- the above-described coin cell is used, and after the initial charge / discharge, the second charge is performed up to 4.25 V in 15 hours, and the coin cell is disassembled and taken out in that state.
- the positive electrode was sealed in a SUS pressure cell in the presence of an electrolyte solution, differential thermal analysis was performed at a scanning rate of 50 ° C./min from room temperature to 400 ° C., and the calorific value was determined by differentiating the calorific value with time. evaluated.
- the reaction tank is always stirred with a blade-type stirrer.
- the aqueous ammonia solution and the aqueous sodium hydroxide solution always have an ammonia concentration of 0.4 mol / l in the reaction vessel and an excess hydroxyl group concentration in the reaction vessel of 0.01 mol / l.
- the obtained Li—Ni composite oxide particle powder has a chemical composition of Li 1.01 Ni 0.80 Co 0.15 Al 0.05 O 2 , an average particle size of 5.7 ⁇ m, and a BET specific surface area of 0.00. 36m 2 / g, metal seat occupancy rate of lithium site is 2.9%, the crystallite size is 334nm, the product of the metal site occupancy and the crystallite size of the lithium site was 968.6.
- An SEM photograph of this Li—Ni composite oxide particle is shown in FIG. Further, the discharge capacity of this Li—Ni composite oxide particle powder was 192 mAh / g, and as a result of conducting differential thermal analysis in the 4.25 V charged state, the heat generation rate was 0.06 W / g ⁇ s.
- Ni—Co hydroxide particle powder was obtained.
- the obtained Ni—Co hydroxide particle powder, aluminum hydroxide powder having a primary particle size of 0.5 ⁇ m and an average particle size of 1.5 ⁇ m, and a lithium carbonate content of which particle size was adjusted by a pulverizer in advance were 0.
- Li / (Ni + Co + Al) 1.00, 1.02, 1.03, 1.05, and 1.08 in terms of a molar ratio of 3 wt% lithium hydroxide monohydrate powder having an average particle diameter of 10 ⁇ m
- Li-Ni composite oxide particles having different chemical compositions were obtained in the same manner as in Example 1.
- Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials.
- Ni—Co—Mn hydroxide suspension was washed with water 10 times the weight of the Ni—Co—Mn hydroxide using a filter press, and then dried.
- Ni—Co—Mn hydroxide particles of Ni: Co: Mn 80: 10: 10.
- the obtained Li—Ni composite oxide particles had a chemical composition of Li 1.02 Ni 0.80 Co 0.10 Mn 0.10 O 2 , an average particle size of 12.5 ⁇ m, and a BET specific surface area of 0. .23m 2 / g, metal seat occupancy rate of lithium site is 4.7%, the crystallite size is 200nm, the product of the metal site occupancy and the crystallite size of the lithium site was 940.0. Further, the discharge capacity of this Li—Ni composite oxide particle powder was 206 mAh / g, and as a result of conducting differential thermal analysis in a 4.25 V charged state, the heat generation rate was 0.12 W / g ⁇ s.
- Example 8 to 9 The same operation as in Example 7 was performed to obtain Ni—Co—Mn hydroxide particles.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- Ni—Co—Mn hydroxide particle powder and a lithium hydroxide monohydrate powder having a lithium carbonate content of 0.3 wt% and an average particle size of 10 ⁇ m, the particle size of which was adjusted by a pulverizer in advance. It mixed so that it might become Li / (Ni + Co + Mn) 1.04 by molar ratio. This mixture was calcined at 820 ° C. for 10 hours in an oxygen atmosphere and crushed to obtain Li—Ni composite oxide particle powder.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- the reaction tank is always stirred with a blade-type stirrer.
- the aqueous ammonia solution and the aqueous sodium hydroxide solution always have an ammonia concentration of 0.4 mol / l in the reaction vessel and an excess hydroxyl group concentration in the reaction vessel of 0.06 mol / l.
- Ni—Co—Mn hydroxide particle powder and a lithium hydroxide monohydrate powder having a lithium carbonate content of 0.3 wt% and an average particle size of 10 ⁇ m, the particle size of which was adjusted by a pulverizer in advance. It mixed so that it might become Li / (Ni + Co + Mn) 1.02 by molar ratio. This mixture was calcined at 780 ° C. for 10 hours in an oxygen atmosphere and pulverized to obtain Li—Ni composite oxide particle powder.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- the obtained Ni—Co—Mn hydroxide particle powder and a lithium hydroxide monohydrate powder having a lithium carbonate content of 0.3 wt% and an average particle size of 10 ⁇ m, the particle size of which was adjusted by a pulverizer in advance. It mixed so that it might become Li / (Ni + Co + Mn) 1.02 by molar ratio.
- This mixture was calcined at 780 ° C. for 10 hours in an oxygen atmosphere and pulverized to obtain Li—Ni composite oxide particle powder.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- An aqueous sodium hydroxide solution was supplied.
- the reaction tank is always stirred with a blade-type stirrer.
- the aqueous ammonia solution and the aqueous sodium hydroxide solution always have an ammonia concentration of 1.2 mol / l in the reaction vessel and an excess hydroxyl group concentration in the reaction vessel of 0.04 mol / l.
- Ni—Co—Mn hydroxide particle powder and a lithium hydroxide monohydrate powder having a lithium carbonate content of 0.3 wt% and an average particle size of 10 ⁇ m, the particle size of which was adjusted by a pulverizer in advance. It mixed so that it might become Li / (Ni + Co + Mn) 1.04 by molar ratio. This mixture was calcined at 780 ° C. for 10 hours in an oxygen atmosphere and pulverized to obtain Li—Ni composite oxide particle powder.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- the obtained Ni—Co—Mn hydroxide particle powder and a lithium hydroxide monohydrate powder having a lithium carbonate content of 0.3 wt% and an average particle size of 10 ⁇ m, the particle size of which was adjusted by a pulverizer in advance. It mixed so that it might become Li / (Ni + Co + Mn) 1.04 by molar ratio.
- This mixture was calcined in an oxygen atmosphere at 890 ° C. for 3.33 hours and crushed to obtain Li—Ni composite oxide particle powder.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- Example 22 5.
- a reaction vessel containing an aqueous solution in which 2 mol / l of nickel sulfate, cobalt sulfate, manganese sulfate, and magnesium sulfate are mixed so that Ni: Co: Mn: Mg 90.9: 5.1: 2: 2.
- a 0 mol / l aqueous ammonia solution and a 2 mol / l aqueous sodium hydroxide solution were supplied.
- the reaction tank is always stirred with a blade-type stirrer.
- the aqueous ammonia solution and the aqueous sodium hydroxide solution always have an ammonia concentration of 0.4 mol / l in the reaction vessel and an excess hydroxyl group concentration in the reaction vessel of 0.01 mol / l.
- (Ammonia concentration in the reaction vessel) / (excess hydroxyl group concentration in the reaction vessel) was kept at 40.
- the Ni—Co—Mn—Mg hydroxide produced in the reaction tank overflowed, was concentrated in a concentration tank connected to the overflow pipe, and was circulated to the reaction tank. The reaction was carried out for 40 hours until the Ni—Co—Mn—Mg hydroxide concentration in the reaction tank and the sedimentation tank reached 4 mol / l.
- Ni—Co—Mn—Mg hydroxide particle powder, aluminum hydroxide powder having a primary particle size of 0.5 ⁇ m and an average particle size of 1.5 ⁇ m, and lithium carbonate whose particle size was adjusted beforehand by a pulverizer Lithium hydroxide / monohydrate powder having a content of 0.3 wt% and an average particle diameter of 10 ⁇ m was mixed so that the molar ratio was Li / (Ni + Co + Mn + Mg + Al) 1.04.
- This mixture was calcined at 750 ° C. for 10 hours in an oxygen atmosphere and crushed to obtain Li—Ni composite oxide particle powder.
- the composition of this material was Li 1.04 Ni 0.90 Co 0.05 Mn 0.02 Mg 0.02 Al 0.01 O 2 .
- Table 1 shows the average particle diameter and BET specific surface area
- Table 2 shows the lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate.
- the obtained Ni—Co—Mn hydroxide particle powder, the zirconium oxide powder having an average particle size of 0.4 ⁇ m, the lithium carbonate content that was adjusted in advance by a pulverizer, the content was 0.3 wt%, the average particle size 10 ⁇ m of lithium hydroxide monohydrate powder was mixed at a molar ratio of Li / (Ni + Co + Mn + Zr) 1.04. This mixture was calcined in an oxygen atmosphere at 890 ° C.
- Li—Ni composite oxide particle powder The composition of this material was Li 1.040 Ni 0.600 Co 0.200 Mn 0.198 Zr 0.002 O 2 .
- Table 1 shows the average particle diameter and BET specific surface area
- Table 2 shows the lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate.
- Example 1 The same operation as in Example 1 was performed to obtain Ni—Co hydroxide particles.
- Li—Ni composite oxide particle powders having different compositions were obtained. Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials.
- the lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate Is shown in Table 2.
- An SEM photograph of the Li—Ni composite oxide particles is shown in FIG. Thus, when x is smaller than 1.00, a Li—Ni composite oxide having a high battery capacity cannot be obtained.
- Example 2 The same operation as in Example 1 was performed to obtain Ni—Co hydroxide particles.
- Li—Ni composite oxide particle powders having different compositions were obtained.
- Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials.
- Example 3 (Ammonia concentration in the reaction tank) / (excess hydroxyl group concentration in the reaction tank) was continued in the same manner as in Example 3, except that the Li—Ni composite having a different chemical composition was used. Oxide particle powder was obtained. Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials. The lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate. Is shown in Table 2.
- Example 3 (Ammonia concentration in the reaction vessel) / (excess hydroxyl group concentration in the reaction vessel) was continued in the same manner as in Example 3, except that the Li—Ni composite having a different chemical composition was used. Oxide particle powder was obtained. Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials. The lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate. Is shown in Table 2.
- Example 7 The same operation as in Example 7 was performed to obtain Ni—Co—Mn hydroxide particles.
- Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials.
- Example 7 (Ammonia concentration in the reaction vessel) / (excess hydroxyl group concentration in the reaction vessel) was continued in the same manner as in Example 7 except that the Li—Ni composite having a different chemical composition was used. Oxide particle powder was obtained. Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials. The lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate. Is shown in Table 2.
- Example 7 (Ammonia concentration in the reaction vessel) / (excess hydroxyl group concentration in the reaction vessel) was continued in the same manner as in Example 7 except that the Li—Ni composite having a different chemical composition was used. Oxide particle powder was obtained. Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials. The lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate. Is shown in Table 2.
- Example 11 The same procedure as in Example 11 was performed to obtain Ni—Co—Mn hydroxide particles.
- Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials.
- Ni—Co—Mn hydroxide particles were obtained.
- the obtained Ni—Co—Mn hydroxide particle powder was mixed with a lithium hydroxide monohydrate powder having a lithium carbonate content of 0.3 wt% and an average particle size of 10 ⁇ m, which had been previously adjusted by a pulverizer.
- Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials. The lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate. Is shown in Table 2.
- Example 13 (Ammonia concentration in the reaction vessel) / (excess hydroxyl group concentration in the reaction vessel) was continued in the same manner as in Example 13 except that the Li—Ni composite having a different chemical composition was used. Oxide particle powder was obtained. Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials. The lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate. Is shown in Table 2.
- Example 13 (Ammonia concentration in the reaction vessel) / (excess hydroxyl group concentration in the reaction vessel) was continued in the same manner as in Example 13 except that the Li—Ni composite having a different chemical composition was used. Oxide particle powder was obtained. Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials. The lithium site metal site occupancy, crystallite size, the product of lithium site metal site occupancy and crystallite size, initial discharge capacity, and heat generation rate. Is shown in Table 2.
- Ni—Co—Mn hydroxide particles were obtained.
- Table 1 shows the composition, average particle diameter, and BET specific surface area of these materials.
- This mixture was calcined at 950 ° C. for 3.67 hours in an air atmosphere and crushed to obtain Li—Ni composite oxide particle powder.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- Table 2 shows that when a is larger than 0.25, the initial charge / discharge capacity is significantly reduced.
- This mixture was calcined at 930 ° C. for 10 hours in an air atmosphere and crushed to obtain Li—Ni composite oxide particle powder.
- the composition, average particle diameter and BET specific surface area of this material are shown in Table 1, and the metal site occupation ratio, crystallite size, product of lithium site metal site occupation ratio and crystallite size, initial discharge capacity, and heat generation rate are shown. It shows in Table 2.
- Table 2 shows that when y is larger than 0.25, the initial charge / discharge capacity is significantly reduced.
- the Li—Ni composite oxides obtained in Examples 1 to 23 have a metal seat occupation ratio of 2% or more and 7% or less mixed in the lithium site, and the crystal structure is stabilized. As a result, it is an excellent positive electrode material that can secure a diffusion path of lithium and obtain a high discharge capacity of 185 mAh / g or more, and can simultaneously achieve high capacity and improved thermal stability.
- the Li—Ni composite oxide according to the present invention has a controlled crystallite size and a small specific surface area, the reaction with the electrolyte solution at the particle interface can be suppressed, and the thermal stability is improved. Excellent positive electrode material.
- the heat generation rate determined by differential thermal analysis in a 4.25 V charged state is 0.15 W / g ⁇ s or less, and it is an excellent positive electrode material with improved thermal stability.
- the Li—Ni composite oxide according to the present invention has a high initial discharge capacity and is effective as an active material for a non-aqueous electrolyte secondary battery excellent in thermal stability.
- Li—Ni composite oxide particle powder according to the present invention is used as a positive electrode active material of a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery having a high initial discharge capacity and excellent thermal stability is obtained. be able to.
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Abstract
Description
Me2+SO4 + 2NaOH → Me2+(OH)2 + Na2SO4 (1)
この時の、Me2+SO4とNaOHのモル比は1:2が理論的な原料比率となるが、本発明における反応は、NaOHを理論的なモル比よりも、余剰に供給して行い、その時の余剰な水酸基濃度を制御することにより、目的とするNi-Co水酸化物を得た。
非水電解質二次電池の高容量化と熱安定性を両立するには正極活物質を構成するLi-Ni複合酸化物粒子粉末において、リチウムサイトへのメタル席占有率と結晶子サイズの両方を制御することが重要である。そこで、本発明においては、Li-Ni複合酸化物粒子粉末のX線回折のリートベルト解析から得られるリチウムサイトのメタル席占有率(%)とリートベルト解析から得られる結晶子サイズ(nm)の積を700以上、1400以下とした。
2mol/lの硫酸ニッケルと硫酸コバルトをNi:Co=84:16になるように混合した水溶液の入った反応槽に6.0mol/lのアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が0.4mol/l、反応槽中の余剰の水酸基濃度が0.01mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が40となるように供給し続けた。反応槽中に生成したNi-Co水酸化物はオーバーフローされ、オーバーフロー管に連結された濃縮槽で濃縮し、反応槽へ循環を行った。反応槽と沈降槽中のNi-Co水酸化物濃度が4mol/lになるまで40時間反応を行った。
実施例1と同様に行ってNi-Co水酸化物粒子粉末を得た。得られたNi-Co水酸化物粒子粉末と、一次粒子径が0.5μmで平均粒子径1.5μmの水酸化アルミニウムの粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Al)=1.00、1.02、1.03、1.05及び1.08になるように混合した以外は、実施例1と同様に行い、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルト及び硫酸マンガンをNi:Co:Mn=80:10:10になるように混合した水溶液の入った反応槽に6.0mol/lアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が0.4mol/l、反応槽中の余剰の水酸基濃度が0.01mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が40となるように供給し続けた。反応槽中に生成したNi-Co-Mn水酸化物はオーバーフローされ、オーバーフロー管に連結された濃縮槽で濃縮し、反応槽へ循環を行った。反応槽と沈降槽中のNi-Co-Mn水酸化物濃度が4mol/lになるまで40時間反応を行った。
実施例7と同様に行ってNi-Co-Mn水酸化物粒子を得た。得られたNi-Co-Mn水酸化物粒子粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Mn)=1.04または1.08になるように混合した以外は、実施例7と同様に行い、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルト及び硫酸マンガンをNi:Co:Mn=80:10:10になるように混合した水溶液の入った反応槽に6.0mol/lアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が0.4mol/l、反応槽中の余剰の水酸基濃度が0.02mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が20となるように供給し続けた。反応槽中に生成したNi-Co-Mn水酸化物はオーバーフローされ、オーバーフロー管に連結された濃縮槽で濃縮し、反応槽へ循環を行った。反応槽と沈降槽中のNi-Co-Mn水酸化物濃度が4mol/lになるまで40時間反応を行った。
2mol/lの硫酸ニッケルと硫酸コバルト及び硫酸マンガンをNi:Co:Mn=80:15:5になるように混合した水溶液の入った反応槽に、6.0mol/lアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が0.4mol/l、反応槽中の余剰の水酸基濃度が0.06mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が6.7となるように供給し続けた。反応槽中に生成したNi-Co-Mn水酸化物はオーバーフローされ、オーバーフロー管に連結された濃縮槽で濃縮し、反応槽へ循環を行った。反応槽と沈降槽中のNi-Co-Mn水酸化物濃度が4mol/lになるまで40時間反応を行った。
組成をNi:Co:Mn=80:5:15になるように行った以外は、実施例7と同様に行ってNi-Co-Mn水酸化物粒子粉末を得た。得られたNi-Co-Mn水酸化物粒子粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Mn)=1.02になるように混合した。この混合物を酸素雰囲気下、780℃にて10時間焼成し、解砕し、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
組成をNi:Co:Mn=75:10:15になるように行った以外は、実施例7と同様に行ってNi-Co-Mn水酸化物粒子粉末を得た。得られたNi-Co-Mn水酸化物粒子粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Mn)=1.02、1.04、1.08になるように混合した以外は、実施例12と同様に行い、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルト及び硫酸マンガンをNi:Co:Mn=75:10:15になるように混合した水溶液の入った反応槽に6.0mol/lのアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が1.2mol/l、反応槽中の余剰の水酸基濃度が0.04mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が30となるように供給し続けた。反応槽中に生成したNi-Co-Mn水酸化物はオーバーフローされ、オーバーフロー管に連結された濃縮槽で濃縮し、反応槽へ循環を行った。反応槽と沈降槽中のNi-Co水酸化物濃度が4mol/lになるまで40時間反応を行った。
Ni-Co-Mn水酸化物の組成をNi:Co:Mn=75:15:10になるように行った以外は、実施例12と同様に行い、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
Ni-Co-Mn水酸化物の組成をNi:Co:Mn=75:5:20になるように行った以外は、実施例12と同様に行い、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
Ni-Co-Mn水酸化物の組成をNi:Co:Mn=85:10:5になるように行った以外は、実施例12と同様に行い、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
Ni-Co-Mn水酸化物の組成をNi:Co:Mn=85:5:10になるように行った以外は、実施例12と同様に行い、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
組成をNi:Co:Mn=60:20:20になるように行った以外は、実施例7と同様に行ってNi-Co-Mn水酸化物粒子粉末を得た。得られたNi-Co-Mn水酸化物粒子粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Mn)=1.04になるように混合した。この混合物を酸素雰囲気下、890℃にて3.33時間焼成し、解砕し、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルト、硫酸マンガン及び硫酸マグネシウムをNi:Co:Mn:Mg=90.9:5.1:2:2になるように混合した水溶液の入った反応槽に6.0mol/lのアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が0.4mol/l、反応槽中の余剰の水酸基濃度が0.01mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が40となるように供給し続けた。反応槽中に生成したNi-Co-Mn-Mg水酸化物はオーバーフローされ、オーバーフロー管に連結された濃縮槽で濃縮し、反応槽へ循環を行った。反応槽と沈降槽中のNi-Co-Mn-Mg水酸化物濃度が4mol/lになるまで40時間反応を行った。
Ni-Co-Mn水酸化物粒子の組成をNi:Co:Mn=60:20:20になるように行った以外は、実施例7と同様に行ってNi-Co-Mn水酸化物粒子粉末を得た。得られたNi-Co-Mn水酸化物粒子粉末と平均粒子径が0.4μmの酸化ジルコニウムの粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Mn+Zr)=1.04になるように混合した。この混合物を酸素雰囲気下、890℃にて3.33時間焼成し、解砕し、Li-Ni複合酸化物粒子粉末を得た。この材料の組成はLi1.040Ni0.600Co0.200Mn0.198Zr0.002O2であった。平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
実施例1と同様に行ってNi-Co水酸化物粒子を得た。得られたNi-Co水酸化物粒子粉末と、一次粒子径が0.5μmで平均粒子径1.5μmの水酸化アルミニウムの粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Al)=0.98となるように混合した以外は、実施例1と同様に行い、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。このLi-Ni複合酸化物粒子のSEM写真を図2に示す。このようにxが1.00より小さい場合には、高い電池容量のLi-Ni複合酸化物を得ることができない。
実施例1と同様に行ってNi-Co水酸化物粒子を得た。得られたNi-Co水酸化物粒子粉末と、一次粒子径が0.5μmで平均粒子径1.5μmの水酸化アルミニウムの粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Al)=1.12となるように混合した以外は、実施例1と同様に行い、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルトをNi:Co=84:16になるように混合した水溶液の入った反応槽に6.0mol/lのアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が1.6mol/l、反応槽中の余剰の水酸基濃度が0.1mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が16となるように供給し続けた以外は、実施例3と同様に行って、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルトをNi:Co=84:16になるように混合した水溶液の入った反応槽に6.0mol/lのアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が0.4mol/l、反応槽中の余剰の水酸基濃度が0.08mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が5となるように供給し続けた以外は、実施例3と同様に行って、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
実施例7と同様に行ってNi-Co-Mn水酸化物粒子を得た。得られたNi-Co-Mn水酸化物粒子粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Mn)=0.98または1.12となるように混合した以外は、実施例7と同様に行い、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルト及び硫酸マンガンをNi:Co:Mn=80:10:10になるように混合した水溶液の入った反応槽に6.0mol/lのアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が1.6mol/l、反応槽中の余剰の水酸基濃度が0.1mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が16となるように供給し続けた以外は、実施例7と同様に行って、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルト及び硫酸マンガンをNi:Co:Mn=80:10:10になるように混合した水溶液の入った反応槽に6.0mol/lのアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が0.4mol/l、反応槽中の余剰の水酸基濃度が0.08mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が5となるように供給し続けた以外は、実施例7と同様に行って、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
実施例11と同様に行ってNi-Co-Mn水酸化物粒子を得た。得られたNi-Co-Mn水酸化物粒子粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Mn)=0.98または1.12となるように混合した以外は、実施例11と同様に行い、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
実施例13と同様に行ってNi-Co-Mn水酸化物粒子を得た。得られたNi-Co-Mn水酸化物粒子粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末をモル比でLi/(Ni+Co+Mn)=0.98または1.12となるように混合した以外は、実施例13と同様に行い、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルト及び硫酸マンガンをNi:Co:Mn=75:10:15になるように混合した水溶液の入った反応槽に6.0mol/lのアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が1.6mol/l、反応槽中の余剰の水酸基濃度が0.1mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が16となるように供給し続けた以外は、実施例13と同様に行って、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
2mol/lの硫酸ニッケルと硫酸コバルト及び硫酸マンガンをNi:Co:Mn=75:10:15になるように混合した水溶液の入った反応槽に6.0mol/lのアンモニア水溶液及び2mol/lの水酸化ナトリウム水溶液を供給した。反応槽は羽根型攪拌機で常に攪拌を行い、アンモニア水溶液と水酸化ナトリウム水溶液は常に、反応槽中のアンモニア濃度が0.4mol/l、反応槽中の余剰の水酸基濃度が0.08mol/lで、(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が5となるように供給し続けた以外は、実施例13と同様に行って、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
実施例19と同様に行ってNi-Co-Mn水酸化物粒子を得た。得られたNi-Co-Mn水酸化物粒子粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Mn)=1.12となるように混合した以外は、実施例19と同様に行い、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
実施例20と同様に行ってNi-Co-Mn水酸化物粒子を得た。得られたNi-Co-Mn水酸化物粒子粉末と、予め粉砕機によって粒度調整を行った炭酸リチウム含有量が0.3wt%、平均粒子径10μmの水酸化リチウム・1水塩の粉末とをモル比でLi/(Ni+Co+Mn)=1.12となるように混合した以外は、実施例20と同様に行い、化学組成の異なるLi-Ni複合酸化物粒子粉末を得た。これらの材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。
組成をNi:Co:Mn=50:20:30になるように行った以外は実施例7と同様にしてNi-Co-Mn水酸化物粒子粉末を得た。得られたNi-Co-Mn水酸化物粒子粉末と炭酸リチウムの粉末とをモル比でLi/(Ni+Co+Mn)=1.02になるように混合した。この混合物を空気雰囲気下、950℃にて3.67時間焼成し、解砕し、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。このようにaが0.25より大きい場合には、初期充放電容量が著しく低下する。
組成をNi:Co:Mn=33:33:33になるように行った以外は実施例7と同様に行ってNi-Co-Mn水酸化物粒子粉末を得た。得られたNi-Co-Mn水酸化物粒子粉末と炭酸リチウムの粉末とをモル比でLi/(Ni+Co+Mn)=1.02になるように混合した。この混合物を空気雰囲気下、930℃にて10時間焼成し、解砕し、Li-Ni複合酸化物粒子粉末を得た。この材料の組成、平均粒子径及びBET比表面積を表1に、リチウムサイトのメタル席占有率、結晶子サイズ、リチウムサイトのメタル席占有率と結晶子サイズの積、初期放電容量及び発熱速度を表2に示す。このようにyが0.25より大きい場合には、初期充放電容量が著しく低下する。
Claims (7)
- 組成がLixNi1-y-a-bCoyM1aM2bO2(1.00≦x≦1.10、0<y≦0.25、0<a≦0.25、0≦b≦0.10、M1はAl、Mnから選ばれる少なくとも一種の元素、M2はZr、Mgから選ばれる少なくとも一種の元素)であるLi-Ni複合酸化物であって、X線回折のリートベルト解析から得られるリチウムサイトのメタル席占有率(%)とリートベルト解析から得られる結晶子サイズ(nm)の積が700以上、1400以下であることを特徴とするLi-Ni複合酸化物粒子粉末。
- 前記Li-Ni複合酸化物のリートベルト解析から得られるリチウムサイトのメタル席占有率が2%以上、7%以下である請求項1に記載のLi-Ni複合酸化物粒子粉末。
- 前記Li-Ni複合酸化物のリートベルト解析から得られる結晶子サイズが500nm以下である請求項1又は2に記載のLi-Ni複合酸化物粒子粉末。
- 平均粒子径が1~20μmであり、BET比表面積が0.1~1.6m2/gである請求項1~3のいずれかに記載のLi-Ni複合酸化物粒子粉末。
- リチウム化合物の粉末とNi-Co水酸化物粒子粉末とを混合し、得られた混合物を焼成するLi-Ni複合酸化物粒子粉末の製造方法であって、前記Ni-Co水酸化物粒子粉末は、金属元素の硫酸塩水溶液と、アンモニア水溶液と、水酸化ナトリウム水溶液とを混合し、反応槽中のアンモニア濃度が1.4mol/l以下、かつ(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が6以上になるように制御してNi-Co水酸化物を得る、請求項1~4のいずれかに記載のLi-Ni複合酸化物粒子粉末の製造方法。
- リチウム化合物の粉末とNi-Co水酸化物粒子粉末とアルミニウムの化合物の粉末及び/又はジルコニウムの化合物の粉末を混合し、得られた混合物を焼成するLi-Ni複合酸化物粒子粉末の製造方法であって、Ni-Co水酸化物粒子粉末は、金属元素の硫酸塩水溶液と、アンモニア水溶液と、水酸化ナトリウム水溶液とを混合し、反応槽中のアンモニア濃度が1.4mol/l以下、かつ(反応槽中のアンモニア濃度)/(反応槽中の余剰の水酸基濃度)が6以上になるように制御してNi-Co水酸化物を得る、請求項1~4のいずれかに記載のLi-Ni複合酸化物粒子粉末の製造方法。
- 請求項1~4のいずれかに記載のLi-Ni複合酸化物粒子粉末からなる正極活物質を含有する正極を用いた非水電解質二次電池。
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Also Published As
Publication number | Publication date |
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EP2911224B1 (en) | 2019-07-03 |
KR102168980B1 (ko) | 2020-10-22 |
JPWO2014061653A1 (ja) | 2016-09-05 |
CN104704659B (zh) | 2017-11-14 |
CN104704659A (zh) | 2015-06-10 |
EP2911224A1 (en) | 2015-08-26 |
US20150249248A1 (en) | 2015-09-03 |
EP2911224A4 (en) | 2016-06-01 |
KR20150073969A (ko) | 2015-07-01 |
CA2888419A1 (en) | 2014-04-24 |
JP6107832B2 (ja) | 2017-04-05 |
US9698420B2 (en) | 2017-07-04 |
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