Sumitomo Metal Mining Company, Ltd.

Yasutaka Kamata

Katsuya Kase

Kazuomi Ryoshi

Hiroyuki Toya

Taira Aida

Kensaku Mori

Tetsufumi Komukai

Takahiro Toma

Tomomichi Nihei

Hideo Sasaoka

Yuji Kawakami

Takuya Yamauchi

The nickel-containing composite hydroxide disclosed herein contain secondary particles, which are formed from an aggregation of numerous primary particles, which have an average particle size of the primary particles is 0.01 μm to 0.40 μm. These secondary particles have a spherical or ellipsoidal shape, an average particle size of 20 μm to 50 μm, and a BET value of 12 m/g to 50 m/g after being roasted in air for 2 hours at 800° C.

Nickel-containing composite hydroxide and production process thereof

The production method is a method for producing a positive electrode active material for a lithium ion secondary battery which contains at least nickel and lithium, the method including: a firing process in which a mixture of a nickel compound powder and a lithium compound powder is fired; and a water washing process in which a lithium-nickel composite oxide powder obtained in the firing process is washed with water, wherein the firing process is performed under conditions such that a value obtained by dividing a ratio of an amount-of-substance of lithium to a total amount-of-substance of transition metals other than lithium in the lithium-nickel composite oxide powder after the washing with water by a ratio of an amount-of-substance of lithium to a total amount-of-substance of transition metals other than lithium in the lithium-nickel composite oxide powder before the washing with water exceeds 0.95.

Positive electrode active material for lithium ion secondary batteries and method for producing same

The presently disclosed subject matter is directed to a positive electrode active material for a non-aqueous electrolyte secondary battery including a lithium transition metal-containing composite oxide, comprising secondary particles formed by aggregates of primary particles. The secondary particles comprise: an outer-shell section formed by an aggregate of the primary particles; at least one aggregate section formed by an aggregate of primary particles and existing on an inside of the outer-shell section, and electrically and structurally connected to the outer-shell section; and at least one space section existing on the inside of the outer-shell section and in which there are no primary particles. The average particle size of the secondary particles being within the range 1 &#x3bc;m to 15 &#x3bc;m, an index [(d90-d10)/average particle size] that indicates a spread of a particle size distribution of the secondary particles being 0.7 or less, and the surface area per unit volume being 1.7 m/cmor greater.

Transition metal-containing composite hydroxide and manufacturing method thereof, positive electrode active material for a non-aqueous electrolyte secondary battery and manufacturing method thereof, and non-aqueous electrolyte secondary battery

Transition metal composite hydroxide particles as a precursor to a cathode active material for use in a non-aqueous electrolyte rechargeable battery, where the transition metal composite hydroxide has secondary particles formed by an aggregation of plate-shaped primary particles and fine primary particles, are described. The secondary particles have a center section formed by the plate-shaped primary particles, a layered structure with a low-density section formed by the fine primary particles, and a high-density section formed by the plate-shaped primary particles on the outside of the center section. The average value of the ratio of the center section outer diameter to the particle size of the secondary particles is 30% to 80%, and the average value of the ratio of the high-density section radial direction thickness to the particle size of the secondary particles is 5% to 25%.

Transition metal composite hydroxide particles and production method thereof, cathode active material for non-aqueous electrolyte rechargeable battery and production method thereof, and nonaqueous electrolyte rechargeable battery

Provided is a nickel-containing composite hydroxide that is a precursor of a positive-electrode active material with which a nonaqueous-electrolyte secondary battery having a low irreversible capacity and a high energy density can be configured. An aqueous alkaline aqueous solution and a complexing agent are added to an mixed aqueous solution including at least nickel and cobalt to regulate the pH (measured at a reference liquid temperature of 25&#xb0; C.) of this mixed aqueous solution to 11.0 to 13.0, the ammonium concentration to 4 to 15 g/L, and the reaction temperature to 20&#xb0; C. to 45&#xb0; C. Using stirring blades having an inclination angle of 20&#xb0; to 60&#xb0; with respect to a horizontal plane, the mixture is stirred to conduct a crystallization reaction under such conditions that when the nickel-containing composite hydroxide to be obtained is roasted in air at 800&#xb0; C. for 2 hours, the roasted composite hydroxide has a BET value of 12 to 50 m/g. Thus a nickel-containing composite hydroxide expressed by NiCoAlM(OH)(where, 0&#x3c;x&#x2264;0.20, 0&#x3c;y&#x2264;0.15, 0&#x2264;t&#x2264;0.10, 0&#x2264;&#x3b1; 0.50, and M is one or more kind of element selected from among Mg, Ca, Ba, Nb, Mo, V, Ti, Zr and Y), or the general formula: NiCoMnM(OH)(where 0&#x3c;x&#x2264;0.50, 0&#x3c;z&#x2264;0.50, x+z&#x2264;0.70, 0&#x2264;t&#x2264;0.10, 0&#x2264;&#x3b1;&#x2264;0.50, and M is one or more kind of element selected from among Mg, Ca, Ba, Nb, Mo, V, Ti, Zr and Y) is obtained.

Nickel-containing composite hydroxide and production process therefor, positive-electrode active material for a nonaqueous-electrolyte secondary battery and production process therefor, and nonaqueous-electrolyte secondary battery

The presently disclosed subject matter is directed to transition metal-containing composite hydroxides, their use, and manufacturing methods thereof. More particularly, the subject matter describes a positive electrode active material for a non-aqueous electrolyte secondary battery that uses a transition metal-containing composite hydroxide as a precursor and a manufacturing method thereof. In some embodiments, the non-aqueous electrolyte secondary battery uses a positive electrode active material for a non-aqueous electrolyte secondary battery as a positive electrode material.

Provided is a cathode active material that can simultaneously improve the capacity characteristics, output characteristics, and cycling characteristics of a rechargeable battery when used as cathode material for a non-aqueous electrolyte rechargeable battery. After performing nucleation by controlling an aqueous solution for nucleation that includes a metal compound that includes at least a transition metal and an ammonium ion donor so that the pH value becomes 12.0 to 14.0 (nucleation process), nuclei are caused to grow by controlling aqueous solution for particle growth that includes the nuclei so that the pH value is less than in the nucleation process and is 10.5 to 12.0 (particle growth process). When doing this, the reaction atmosphere in the nucleation process and at the beginning of the particle growth process is a non-oxidizing atmosphere, and in the particle growth process, atmosphere control by which the reaction atmosphere is switched from this non-oxidizing atmosphere to an oxidizing atmosphere, and is then switched again to a non-oxidizing atmosphere is performed at least one time. Cathode active material is obtained with the composite hydroxide particles that are obtained by this kind of crystallization reaction as a precursor.

To improve cycling characteristics of a non-aqueous electrolyte secondary battery by obtaining a nickel-cobalt composite hydroxide having a sharp particle size distribution as a precursor, a slurry including a nickel-cobalt composite hydroxide obtained by continuously supplying an aqueous solution that includes at least nickel and cobalt, an ammonium ion donor aqueous solution and a caustic alkali aqueous solution to a reaction vessel and reacting, is continuously extracted and separated into a large particle size portion and s small particle size portion by classification, and the small particle size portion is continuously returned to the reaction vessel. As a result, a nickel-cobalt composite hydroxide is obtained that is expressed by the general formula: NiCoM(OH)(where, 0.05&#x2264;x&#x2264;0.50, 0&#x2264;y&#x2264;0.10, 0.05&#x2264;x+y&#x2264;0.50, and M is at least one kind of metal element selected from among Al, Mg, Mn, Ti, Fe, Cu, Zn and Ga, and that satisfies the relationships (D50&#x2212;D10)/D50&#x2264;0.30, and (D90&#x2212;D50)/D50&#x2264;0.30 among D10, D50 and D90 of this composite hydroxide.

Nickel-cobalt composite hydroxide and method and device for producing same, cathode active material for non-aqueous electrolyte secondary battery and method for producing same, and non-aqueous electrolyte secondary battery

Achieved is a nickel-cobalt-manganese composite hydroxide which is excellent in reactivity with a lithium compound, and able to achieve a positive electrode active material which has excellent thermal stability and battery characteristics. The nickel-cobalt-manganese composite hydroxide is intended to serve as a precursor for a positive electrode active material of a non-aqueous electrolyte secondary battery, and represented by a general formula: NiCoMnM(OH)(0&#x3c;x&#x2264;&#x2153;, 0&#x3c;y&#x2264;&#x2153;, 0&#x2264;z&#x2264;0.1, M represents one or more elements selected from Mg, Al, Ca, Ti, V, Cr, Zr, Nb, Mo, and W), and the nickel-cobalt-manganese composite hydroxide has a specific surface area of 3.0 to 11.0 m/g as measured by a BET method through nitrogen adsorption, and an average valence of 2.4 or more for Co and Mn as obtained by redox titration.

Nickel-cobalt-manganese composite hydroxide, and production method therefor

Achieved is a nickel-cobalt-manganese composite hydroxide which is excellent in reactivity with a lithium compound, and excellent thermal stability and battery characteristics. The nickel-cobalt-manganese composite hydroxide is represented by a general formula: NiCoMnM(OH)(0&#x3c;x&#x2264;&#x2153;, 0&#x3c;y&#x2264;&#x2153;, 0&#x2264;z&#x2264;0.1, M represents one or more elements selected from Mg, Al, Ca, Ti, V, Cr, Zr, Nb, Mo, and W), to serve as a precursor for a positive electrode active material of a non-aqueous electrolyte secondary battery, and the nickel-cobalt-manganese composite hydroxide has a specific surface area of 3.0 to 11.0 m/g as measured by a nitrogen adsorption BET method, and a ratio I(101)/I(100) of peak intensity I(101) of plane (101) to peak intensity I(100) of plane (100) less than 0.300 through an X-ray diffraction measurement.

Nickel-cobalt-manganese composite hydroxide and method for producing same

Process for manufacturing nickel-cobalt composite represented by NiCoMnM(OH)(where, 0.05&#x2266;x&#x2266;0.95, 0&#x2266;y&#x2266;0.55, 0&#x2266;z&#x2266;0.1, x+y+z&#x3c;1, and M is at least one metal-element selected from Al, Mg, and the like), includes: forming seed particle, while reaction solution having mixed solution containing metal compounds and ammonia solution containing ammonium ion supply source at discharge head of an impeller from 50-100 m/s, the concentration of nickel ions is maintained within range 0.1-5 ppm by mass, whereby seed particles are formed; and growing seed particle wherein solution is obtained by supplying mixed and ammonium solutions to reaction solution is agitated with a concentration of nickel ions being maintained within range 5-300 ppm by mass and higher than the concentration of nickel ions in seed particle formation, whereby seed particles are grown up.

Nickel-cobalt composite hydroxide and process for manufacturing same

Process for manufacturing nickel-cobalt composite represented by NiCoMnM(OH)(where, 0.05&#x2266;x&#x2266;0.95, 0&#x2266;y&#x2266;0.55, 0&#x2266;z&#x2266;0.1, x+y+z&#x3c;1, and M is at least one metal element selected from Al, Mg, and the like), includes: forming seed particle, while reaction solution having mixed solution containing metal compounds and ammonia solution containing ammonium ion supply source at discharge head of an impeller from 50-100 m/s, the concentration of nickel ions is maintained within range 0.1-5 ppm by mass, whereby seed particles are formed; and growing seed particle wherein solution is obtained by supplying mixed and ammonium solutions to reaction solution is agitated with a concentration of nickel ions being maintained within range 5-300 ppm by mass and higher than the concentration of nickel ions in seed particle formation, whereby seed particles are grown up.

The present invention provides nickel-cobalt-manganese composite hydroxide and a method for manufacturing same, the nickel-cobalt-manganese composite hydroxide as a precursor allowing a positive electrode active material having excellent battery characteristics and a high-density to be manufactured. The nickel-cobalt-manganese composite hydroxide is represented by a general formula: NiCoMnM(OH)(wherein 0&#x3c;x&#x2266;1/3, 0&#x3c;y&#x2266;1/3, 0&#x2266;z&#x2266;0.1, and M is at least one element selected from Mg, Al, Ca, Ti, V, Cr, Zr, Nb, Mo, and W) and serves as a precursor of a positive electrode active material for nonaqueous electrolyte secondary batteries; wherein the specific surface area measured by a nitrogen adsorption BET method is 1.0 to 10.0 m/g, the carbon content measured by a high frequency combustion infrared absorption method is not more than 0.1% by mass, and the half-value width of a plane in X-ray diffraction is not more than 1.5&#xb0;.

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Ehime, Japan

Yasutaka Kamata