Sumitomo Metal Mining Company, Ltd.

Toyota Jidosha Kabushiki Kaisha

Denso Corporation

Katsuya Kase

Yasutaka Kamata

Yutaka Oyama

Ryuichi Kuzuo

Syuhei Oda

Kazuomi Ryoshi

Hideo Sasaoka

Kensaku Mori

Hiroyuki Toya

Manabu Yamada

Satoru Suzuki

Hirofumi Iisaka

Minoru Shiraoka

Tomoyoshi Ueki

Takuichi Arai

Tomomichi Nihei

Kazuhiro Ohkawa

Shigeki Kubo

Ko Nozaki

Takuya Yamauchi

Koichi Yokoyama

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

A non-aqueous electrolyte secondary battery is provided that has both good safety and durability characteristics while at the same time has high charge/discharge capacity. The cathode active material for a non-aqueous electrolyte secondary battery of the present invention is a lithium nickel composite oxide to which at least two or more kinds of metal elements including aluminum are added, and comprises secondary particles that are composed of fine secondary particles having an average particle size of 2 &#x3bc;m to 4 &#x3bc;m, and rough secondary particles having an average particle size of 6 &#x3bc;m to 15 &#x3bc;m, with an overall average particle size of 5 &#x3bc;m to 15 &#x3bc;m; where the aluminum content of fine secondary particles (metal mole ratio: SA) is greater than the aluminum content of rough secondary particles (metal mole ratio: LA), and preferably the aluminum concentration ratio (SA/LA) is within the range 1.2 to 2.6.

Cathode active material for non-aqueous electrolyte secondary battery, manufacturing method thereof, and non-aqueous electrolyte secondary 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

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

A method for producing coated nickel hydroxide powder for a positive electrode of an alkaline secondary battery wherein the pH of a suspension of a nickel hydroxide powder is kept at 8 to 11.5, and an aqueous cobalt salt solution and an aqueous alkali solution are supplied to the suspension to coat the surface of nickel hydroxide particles with cobalt hydroxide. Then, the pH of a slurry of the cobalt hydroxide-coated nickel hydroxide powder is adjusted to 12.5 to 13.0, and oxygen is supplied to the slurry so that the total amount of oxygen supplied per mole of cobalt in the coating is 30 l/mol or more to oxidize the cobalt hydroxide.

Coated nickel hydroxide powder for positive electrode active material for alkaline secondary battery, and production method therefor

Cathode active material for non-aqueous electrolyte secondary battery manufacturing method thereof, and non-aqueous electrolyte secondary battery

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

A coated nickel hydroxide powder that has a cobalt compound coating having improved uniformity and adhesion properties on the surface of particles thereof and is therefore suitable for a positive electrode active material of an alkaline secondary battery is obtained by coating the surface of nickel hydroxide particles with a cobalt compound, and has a transmittance ratio of 30% or higher as determined by (A&#x2212;B)/(B&#x2212;B). The transmittance A (coated nickel hydroxide powder), the transmittance B(nickel hydroxide powder), or the transmittance B(nickel hydroxide powder and cobalt compound containing cobalt in an amount corresponding to the amount of cobalt contained in the coating) can be determined by measuring the transmittance of a tubular transparent cell after shaking the tightly-closed transparent cell containing each powder for a certain time and then taking the contents out of the transparent cell.

Coated nickel hydroxide powder for positive electrode active material of alkaline secondary battery, and evaluation method for coating adhesion properties of coated nickel hydroxide powder

Provided is a cathode active material for a non-aqueous electrolyte secondary battery capable of obtaining high initial discharge capacity and good output characteristics at low temperature. In order to achieve this, a cathode active material that is a lithium nickel composite oxide composed of secondary particles that are an aggregate of primary particles is expressed by the general expression: Li(NiCoAl)MO(where 0.98&#x2266;w&#x2266;1.10, 0.05&#x2266;x&#x2266;0.3, 0.01&#x2266;y&#x2266;0.1, 0&#x2266;z&#x2266;0.05, and M is at least one metal element selected from a group consisting of Mg, Fe, Cu, Zn and Ga), and where the crystallite diameter at (003) plane of that lithium nickel composite oxide that is found by X-ray diffraction and the Scherrer equation is within the range of 1200 &#x212b; to 1600 &#x212b; is used as the cathode material.

Positive electrode active material for non-aqueous electrolyte secondary battery and production method for same, precursor for positive electrode active material, and non-aqueous electrolyte secondary battery using positive electrode active material

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;.

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

Disclosed is a nonaqueous secondary battery () comprising a positive electrode () having a positive current collector () made of a metal, and a positive electrode active material () composed of a lithium-metal complex oxide. The surface of the positive electrode active material () is coated with a lithium salt () having an average thickness of 20-50 nm.

Coated positive electrode active material, positive electrode for nonaqueous secondary battery, nonaqueous secondary battery, and their production methods

Provided is a cathode active material for a non-aqueous electrolyte secondary battery capable of obtaining high initial discharge capacity and good output characteristics at low temperature. In order to achieve this, a cathode active material that is a lithium nickel composite oxide composed of secondary particles that are an aggregate of primary particles is expressed by the general expression: Li(NiCoAl)MO(where 0.98&#x2266;w&#x2266;1.10, 0.05&#x2266;x&#x2266;0.3, 0.01&#x2266;y&#x2266;0.1, 0&#x2266;z&#x2266;0.05, and M is at least one metal element selected from a group consisting of Mg, Fe, Cu, Zn and Ga), and where the crystallite diameter at (003) plane of that lithium nickel composite oxide that is found by X-ray diffraction and the Scherrer equation is within the range of 1200 {acute over (&#x212b;)} to 1600 {acute over (&#x212b;)} is used as the cathode material.

An active material for positive electrode for a non-aqueous electrolyte secondary battery comprises a lithium-metal composite oxide that is expressed by the general formula of Li(NiCo)MO(where 0.98&#x2266;x&#x2266;1.10, 0.05&#x2266;y&#x2266;0.4, 0.01&#x2266;z&#x2266;0.2, and where M is at least one metal element selected from the group of Al, Mg, Mn, Ti, Fe, Cu, Zn and Ga), and where the SOion content is in the range from 0.4 weight % to 2.5 weight %, and the occupancy rate of lithium found from the X-ray diffraction chart and using Rietveld analysis is 98% or greater, and the carbon amount measured by way of the high frequency heating-infrared adsorption method is 0.12 weight % or less, and that the Karl Fischer water content due to heating at 180&#xb0; C. be 0.2 weight % or less.

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Ehime, Japan

Katsuya Kase