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A kind of fluorine-doped nickel-cobalt-manganese precursor and its preparation method and application

A precursor, nickel-cobalt-manganese technology, applied in the direction of structural parts, electrical components, battery electrodes, etc., can solve the problems of poor sphericity, small particle size, difficult to clean, etc., to improve the tap density and specific surface area, and improve the vibration Density, the effect of increasing the specific surface area

Active Publication Date: 2020-08-04
湖南金富力新能源股份有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] However, it is difficult to synthesize nickel-cobalt-manganese hydroxide precursors by the traditional co-precipitation method, mainly because the precipitation concentration product of manganese ions is several orders of magnitude different from the precipitation concentration product of nickel and cobalt elements. The precipitation speed with hydroxide is very fast, and it is easy to form flocculent precipitation, which makes it difficult to grow the precursor particle size, and the prepared precursor has low tap density, poor sphericity, small particle size, and is difficult to clean, etc.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] A method for preparing a fluorine-doped nickel-cobalt-manganese precursor provided in this embodiment includes the following steps:

[0028] (1) Nickel nitrate and cobalt nitrate are formulated into the first mixed solution containing nickel salt and cobalt salt, and the concentration of the first mixed solution is 1mol / L; Manganese nitrate and sodium fluoride are mixed into the second mixed solution; wherein, The molar ratio of nickel, cobalt, and manganese ions is 5:2:3; the molar ratio of fluoride ions to manganese ions is 2:1;

[0029] (2) Aqueous ammonia solution with a pH value of 10 is used as the bottom liquid, and the first mixed solution and the second mixed solution obtained in step (1) are oxidized with a concentration of 2 mol / L of hydrogen under the condition of feeding argon as a protective gas. The sodium solution and the ammonia solution with a concentration of 5mol / L were poured into the reaction kettle with an ultrasonic device in parallel, the temper...

Embodiment 2

[0037] A method for preparing a fluorine-doped nickel-cobalt-manganese precursor provided in this embodiment includes the following steps:

[0038] (1) Nickel chloride and cobalt chloride are formulated into the first mixed solution containing nickel salt and cobalt salt, and the concentration of the first mixed solution is 1.5mol / L; Manganese chloride and potassium fluoride are mixed into the second mixed solution Liquid; Wherein, the molar ratio of nickel, cobalt, manganese ion is 1:1:1; The molar ratio of fluoride ion and manganese ion is 1:1;

[0039] (2) With the ammonia solution with a pH value of 11 as the bottom liquid, under the condition of feeding nitrogen as the protective gas, the first mixed solution and the second mixed solution obtained in step (1) and the sodium hydroxide concentration of 6mol / L The solution and the ammonia solution with a concentration of 8mol / L were poured into the reaction kettle with an ultrasonic device in parallel, kept at a temperature ...

Embodiment 3

[0045] A method for preparing a fluorine-doped nickel-cobalt-manganese precursor provided in this embodiment includes the following steps:

[0046] (1) Nickel chloride and cobalt chloride are formulated into the first mixed solution containing nickel salt and cobalt salt, and the concentration of the first mixed solution is 1.5mol / L; Manganese chloride and potassium fluoride are mixed into the second mixed solution Liquid; Wherein, the mol ratio of nickel, cobalt, manganese ion is 5:2:3; The mol ratio of fluoride ion and manganese ion is 5:1;

[0047] (2) the aqueous ammonia solution with a pH value of 11 is used as the bottom liquid, and the first mixed solution and the second mixed solution obtained in step (1) and the sodium hydroxide with a concentration of 8mol / L are mixed under the condition of feeding nitrogen as a protective gas. The solution and the ammonia solution with a concentration of 10mol / L were poured into the reaction kettle with an ultrasonic device in paral...

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Abstract

The invention provides a fluorine-doped nickel-cobalt-manganese precursor and a preparation method and application thereof. The method comprises the steps of preparing first mixed liquid containing anickel salt and a cobalt salt from soluble salts of nickel and cobalt; preparing second mixed liquid from a soluble salt solution of manganese and a soluble fluoride complexing agent under the condition of introducing a protective gas; carrying out forward feeding of the first mixed liquid, the second mixed liquid, a sodium hydroxide solution and an aqueous ammonia solution into a reactor with anultrasonic device, keeping the temperature at 50-60 DEG C and mixing at a speed of 500-800r / min until reaction is ended, carrying out aging and solid-liquid separation and then obtaining sediments; and washing and drying the obtained sediments to obtain a fluoride ion-doped nickel-cobalt-manganese precursor. The obtained precursor material has a sphere-like structure, the specific surface area is5.6-6.3m<2> / g, the tap density is 2.2-2.7g / cm<3> and the obtained positive electrode material is good in electrochemical performance.

Description

technical field [0001] The invention relates to the technical field of battery material preparation, in particular to a fluorine-doped nickel-cobalt-manganese precursor and a preparation method and application thereof. Background technique [0002] Lithium-ion batteries have the advantages of high energy, long life, no memory effect and low pollution, and are widely used in mobile phones, computers, electric vehicles and other fields. At present, the positive electrode materials used in lithium-ion batteries mainly include lithium cobalt oxide, lithium iron phosphate, lithium manganese oxide, and nickel-cobalt lithium manganese oxide. Among them, the positive electrode material with the largest market share is lithium cobaltate, but cobalt is a strategic resource with few reserves and is expensive, and the safety performance of lithium cobaltate is poor, which limits the further development of this material. Lithium nickel cobalt manganese oxide has the advantages of high s...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/505H01M4/525H01M10/0525
CPCH01M4/505H01M4/525H01M10/0525Y02E60/10
Inventor 杨亿华钟毅王海涛宋杰
Owner 湖南金富力新能源股份有限公司
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