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Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueous-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery

A composite hydroxide and cathode active material technology, applied in the direction of non-aqueous electrolyte batteries, active material electrodes, secondary batteries, etc., can solve the problems of undeveloped particle size uniformity, particle degradation, and no particle size, etc., to achieve Suitable for large-scale production and high industrial value

Active Publication Date: 2016-10-26
SUMITOMO METAL MINING CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0023] However, for the positive electrode active material disclosed in Japanese Patent Application Laid-Open No. 2004-253174, since it is a hollow particle, it is expected to increase the specific surface area compared with the solid particle, but there is no description about the particle size.
Therefore, although the improvement of the reactivity with the electrolyte solution due to the increase in the specific surface area is expected, the effect of the micronization on the migration distance of the above-mentioned lithium ions is unclear, and sufficient output characteristics cannot be expected. improve
In addition, its particle size distribution is considered to be equivalent to that of conventional positive electrode active materials. Therefore, there is a high possibility that the selectivity of fine particles will deteriorate due to the unevenness of the applied voltage in the electrode, and the battery capacity will decrease.
[0024] As described above, a lithium composite oxide capable of sufficiently improving the performance of lithium-ion secondary batteries and a composite hydroxide as a raw material for the composite oxide have not been developed at the present stage.
In addition, although various studies have been made on the production method of composite hydroxide, a method capable of producing composite hydroxide as a raw material of composite oxide capable of sufficiently improving the performance of lithium-ion secondary batteries has not been developed on an industrial scale. method
That is, a positive electrode active material with high particle size uniformity and an appropriate particle size, especially a particle size of about 8 to 16 μm, has not been developed, and a positive electrode active material with a large reaction area, such as a hollow structure, has not been developed. , it is necessary to develop this positive electrode active material and its industrial manufacturing method

Method used

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  • Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueous-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery
  • Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueous-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery
  • Nickel composite hydroxide and manufacturing method thereof, cathode active material for nonaqueous-electrolyte secondary battery and manufacturing method thereof, and nonaqueous-electrolyte secondary battery

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0297] [Manufacture of nickel composite hydroxide]

[0298] (nucleation process)

[0299] Add 7.2 L of water to a baffled reaction tank with a capacity of 50 L capable of maintaining the environment in the tank, and flow nitrogen gas while stirring at 500 rpm with an inclined paddle-type stirring blade, thereby reducing the oxygen concentration in the environment in the reaction tank to less than 1% by volume, and adjusted the temperature in the tank to 40°C. Add an appropriate amount of 25% by mass sodium hydroxide aqueous solution and 25% by mass ammonia water to the reaction tank, adjust the pH value of the reaction solution in the tank under the liquid temperature standard of 25°C to be 12.6 and adjust the ammonia concentration to be 10g / L, thus forming a reaction pre-water solution.

[0300]Next, 35 mL of a mixed aqueous solution of 1.9 mol / L obtained by dissolving nickel sulfate and manganese sulfate (the molar ratio of metal elements being Ni:Mn=50:50) in water was ad...

Embodiment 2

[0326] In the composite hydroxide manufacturing process, in addition to nickel sulfate and manganese sulfate, sodium tungstate is also dissolved in water to form a mixed aqueous solution, except that it is operated in the same manner as in Example 1 to obtain a non-aqueous electrolyte secondary battery A positive electrode active material was used and evaluated. In addition, in this mixed aqueous solution, the molar ratio of each metal element was adjusted to Ni:Mn:W=49.75:49.75:0.5. The composition of the obtained composite hydroxide is Ni 0.4975 mn 0.4975 W 0.005 (OH) 2+a (0≤a≤0.5). In addition, the composition of the obtained positive electrode active material is Li 1.20 Ni 0.4975 mn 0.4975 W 0.005 o 2 , It was confirmed by powder X-ray diffraction that it is composed of a single phase of hexagonal layered crystal lithium-nickel-manganese composite oxide.

Embodiment 3

[0328] In the composite hydroxide production process, in addition to nickel sulfate and manganese sulfate, zirconium sulfate was also dissolved in water to form a mixed aqueous solution, except that it was performed in the same manner as in Example 1 to obtain a non-aqueous electrolyte secondary battery. A positive electrode active material was used and evaluated. In addition, in this mixed aqueous solution, the molar ratio of each metal element was adjusted to Ni:Mn:Zr=49.75:49.75:0.5. The composition of the obtained hydroxide is Ni 0.4975 mn 0.4975 Zr 0.005 (OH) 2+a (0≤a≤0.5). In addition, the composition of the obtained positive electrode active material is Li 1.20 Ni 0.4975 mn 0.4975 Zr 0.005 o 2, It was confirmed by powder X-ray diffraction that it is composed of a single phase of hexagonal layered crystal lithium-nickel-manganese composite oxide.

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Abstract

Provided are a cathode active material having a suitable particle size and high uniformity, and a nickel composite hydroxide as a precursor of the cathode active material. When obtaining nickel composite hydroxide by a crystallization reaction, nucleation is performed by controlling a nucleation aqueous solution that includes a metal compound, which includes nickel, and an ammonium ion donor so that the pH value at a standard solution temperature of 25 DEG C. becomes 12.0 to 14.0, after which, particles are grown by controlling a particle growth aqueous solution that includes the formed nuclei so that the pH value at a standard solution temperature of 25 DEG C. becomes 10.5 to 12.0, and so that the pH value is lower than the pH value during nucleation. The crystallization reaction is performed in a non-oxidizing atmosphere at least in a range after the processing time exceeds at least 40% of the total time of the particle growth process from the start of the particle growth process where the oxygen concentration is 1 volume % or less, and with controlling an agitation power requirement per unit volume into a range of 0.5 kW / m3 to 4 kW / m3 at least during the nucleation process.

Description

[0001] The application date is April 03, 2012, the application number is 201280038633.0, and the invention name is "nickel composite hydroxide and its manufacturing method, positive electrode active material for non-aqueous electrolyte secondary battery and its manufacturing method, and non-aqueous electrolyte A divisional application for the application of "Secondary Batteries". technical field [0002] The present invention relates to a nickel composite hydroxide as a precursor of a positive electrode active material for a non-aqueous electrolyte secondary battery and a method for producing the same, and a positive electrode active material for a secondary battery using the nickel composite hydroxide as a raw material and a method for producing the same , and a nonaqueous electrolyte secondary battery using the positive electrode active material for a nonaqueous electrolyte secondary battery as a positive electrode material. Background technique [0003] In recent years, a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01G53/04H01M4/525
CPCH01M4/525C01G53/04C01G53/006C01G53/50C01P2002/52C01P2004/03C01P2004/34C01P2004/51C01P2004/61C01P2006/11C01P2006/12Y02E60/10H01M4/139H01M4/48H01M4/485H01M4/505H01M10/052C01P2004/32C01P2004/62C01P2006/40H01M10/0525H01M2004/028
Inventor 福井笃井之上胜哉小田周平户屋广将
Owner SUMITOMO METAL MINING CO LTD
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