CN103259010B - Preparation method of amphoteric metal element doped lithium-ion cathode material precursor - Google Patents
Preparation method of amphoteric metal element doped lithium-ion cathode material precursor Download PDFInfo
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- CN103259010B CN103259010B CN201310142559.3A CN201310142559A CN103259010B CN 103259010 B CN103259010 B CN 103259010B CN 201310142559 A CN201310142559 A CN 201310142559A CN 103259010 B CN103259010 B CN 103259010B
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Abstract
The invention relates to a preparation method of amphoteric metal element doped lithium-ion cathode material precursor. The preparation method is characterized by comprising the following steps of: (1) preparing raw material liquid; (2) reacting: adding pure water into a reaction kettle, stirring, adding the ammonia-water solution obtained in the step (1), then adjusting the PH value of the water solution to be 11.5 by sodium hydroxide, controlling the temperature to be 40-60 DEG C, respectively adding three feed liquids by a metering pump, wherein the flow rate of metal salt solution in the step (1) is 20-40 ml/min, the flow rate of the mixed solution of sodium hydroxide and aluminum sulfate in the step (1) is 5-20ml/min, and the flow rate of the ammonia-water solution in the step (1) is 2-5ml/min, and carrying out reaction; and (3) washing and drying. According to the amphoteric metal element doped precursor, the doped element is evenly distributed in the precursor, so that the high density of the precursor can be realized, and the precursor has good degree of sphericity.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion anode material presoma of the tellurium that adulterates.
Background technology
Present lithium ion anode material is mainly cobalt acid lithium, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate and LiFePO4 etc. now.The lithium ion anode material its preparation method overwhelming majority produced on the market is now high temperature solid-phase sintering method.Be characterized in: equipment and process preparation condition is easy to control, be easy to realize industrialization.Preparation process is usually first by oxide, the hydroxide of lithium salts and Ni, Co, Mn or carbonic acid thing directly fully mixes and then carry out high temperature sintering to it thus obtain lithium ion anode material under different atmosphere.
Usually crystallization control method is adopted to prepare presoma in prior art, as cobalt hydroxide, cobalt carbonate, cobaltosic oxide can be used as the presoma producing cobalt acid lithium, nickel hydroxide, nickelous carbonate are the presomas of lithium nickelate, manganese dioxide is the main precursor of LiMn2O4, and the oxide of Ni Co Mn, hydroxide are the presomas of nickle cobalt lithium manganate.We are also referred to as ternary material.In industry, major part sintering producer oneself does not produce presoma.But buying presoma only sinters.
Preparing the advantage of presoma: as cell positive material, for reaching desirable chemical property, requiring that it has low impurity content to adulterate useful metallic element simultaneously; There is quite harsh requirement to its physical property: as higher tap density, suitable particle size range, specific area, degree of crystallinity etc. simultaneously.The realization of these performance index mainly controls in precursor power process.
The current state of the art and Problems existing are: the lithium ion anode material of the amphotere such as adulterated al, Zn obtains extensive approval and the expectation in market.In traditional doping process, aluminum soluble salt is formulated in host element salting liquid, but aluminium ion first generates precipitation in lower pH value scope in course of reaction, cause the effect that can not reach with host element co-precipitation, the generation of this phenomenon not only can not reach equally distributed effect, largely disturbs particle normal growth simultaneously.The product density prepared is low, sphericity is poor, and the problem that chemical property reduces greatly never obtains the solution of essence in the industry.
Summary of the invention
The object of this invention is to provide a kind of preparation method of lithium ion anode material presoma of the tellurium that adulterates, can prepare that doped chemical is evenly distributed, the presoma of high density, good sphericity.
Adulterate the preparation method of lithium ion anode material presoma of tellurium, and its special feature is, comprises the steps:
(1) preparation of material liquid:
Compound concentration is the soluble metal salt solution of the nickel of 0.5-2 mol/L, cobalt or manganese, compound concentration is the sodium hydroxide solution of 2-10 mol/L, and Solid aluminum sulfate is added in the sodium hydroxide solution prepared, the addition of aluminum sulfate controls in 0.01-0.1 mol/L, be stirred to aluminum sulfate to dissolve completely, compound concentration is that the ammonia spirit of 2-4 mol/L is stand-by;
(2) react:
Add pure water in a kettle., open and stir, then add the ammonia spirit of step (1), the amount adding ammonia spirit controls ammonia density in solution upon mixing in 0.2-0.5 mol/L, then regulate aqueous ph value to be 11.5 with NaOH, control temperature is at 40-60 DEG C;
Three kinds of feed liquids are added respectively with measuring pump, wherein the metal salt solution flow of step (1) is: 20-40ml/min, the NaOH of step (1) and the mixed solution flow of aluminum sulfate are: 5-20ml/min, and the ammonia spirit flow of step (1) is: 2-5ml/min, reacts;
In course of reaction, three kinds of feed liquids are continual is added in reactor, and the suspension containing slaine be obtained by reacting constantly is discharged from the overfall of reactor;
(3) washing and drying:
By the suspension pure water of discharging to solution pH value lower than less than 9.5, centrifugally to dry.
Material liquid PH value 11.5 ± 0.2 is controlled, feed temperature 45 ± 2 DEG C when reacting in step (2).
Be add 20L pure water in a kettle. in step (2), open after stirring and add 1L ammoniacal liquor again.
Soluble metal salt solution specifically nickelous sulfate, cobaltous sulfate, manganese sulfate, nickel chloride, cobalt chloride or the manganese chloride solution of nickel, cobalt or manganese in step (1).
Regulate the pH value of the aqueous solution with 0.5-2 mol/L NaOH in step (2).
Preparation method of the present invention is by changing the doping way of tellurium in precursor of lithium ionic cell positive material preparation process such as aluminium, make doped chemical reach the effect of co-precipitation with host element, thus prepare the presoma of high density, good sphericity.And the presoma containing tellurium doping prepared by the inventive method, doped chemical is evenly distributed in presoma, can realize the high density of presoma, all has good sphericity.
Accompanying drawing explanation
Accompanying drawing 1 is the nickel hydroxide presoma shape appearance figure that the method in background technology is prepared, and as can be seen from the figure product density is low, sphericity is poor;
Accompanying drawing 2 is the nickel hydroxide presoma shape appearance figure that the method for the embodiment of the present invention 1 is prepared, as can be seen from the figure high, the good sphericity of product density;
Accompanying drawing 3 is Zn distribution diagram of element in the middle nickel hydroxide presoma prepared of the method in background technology, as can be seen from the figure existing process sample Zn element (tellurium of Al element or other doping) skewness in spheroid;
Accompanying drawing 4 is Zn distribution diagram of element in the middle nickel hydroxide presoma prepared of the method for the embodiment of the present invention 1, and the tellurium as can be seen from the figure adulterated is uniformly distributed in spheroid.
Embodiment
Embodiment 1:
Adulterate the preparation method of lithium ion anode material presoma of tellurium, comprises the steps:
(1) preparation of material liquid:
Compound concentration is 2 mol/L nickel sulfate solutions, compound concentration is the sodium hydroxide solution of 4 mol/L, and Solid aluminum sulfate is added in the sodium hydroxide solution prepared to the concentration of aluminum sulfate in sodium hydroxide solution be 0.1 mole/L, be stirred to aluminum sulfate to dissolve completely, compound concentration is that the ammonia spirit of 2 mol/L is stand-by;
(2) react:
In 50L reactor, add 20L pure water, open and stir, speed of agitator controls at 200r/min, then adds the ammoniacal liquor of 1L step (1), and then regulate aqueous ph value to be 11.5 with 0.1mol/L sodium hydroxide solution, control temperature is at 50 DEG C;
Add three kinds of feed liquids with measuring pump respectively, wherein the nickel sulfate solution flow of step (1) is: 30ml/min, and the NaOH of step (1) and the mixed solution flow of aluminum sulfate are: 15ml/min, and the ammonia spirit flow of step (1) is: 3ml/min; Control material liquid PH value 11.5 ± 0.2 when reacting, feed temperature 45 ± 2 DEG C, reacts.
After sustained response 8-10 hour, the suspension containing nickel hydroxide is discharged from the overfall of reactor;
In course of reaction, three kinds of feed liquids are continual is added in reactor, and through continuous print reaction, the suspension containing nickel hydroxide is constantly discharged from the overfall of reactor.
(3) washing and drying:
By discharge suspension pure water to solution pH value lower than less than 9.5, dry moisture with centrifuge, can nickel hydroxide be obtained with baking oven 110 DEG C of oven dry.
Embodiment 2:
Adulterate the preparation method of lithium ion anode material presoma of tellurium, comprises the steps:
(1) preparation of material liquid:
Compound concentration is 2 mol/L nickel sulfate solutions, compound concentration is the sodium hydroxide solution of 4 mol/L, and Solid aluminum sulfate is added in the sodium hydroxide solution prepared to the concentration of aluminum sulfate in sodium hydroxide solution be 0.1 mole/L, be stirred to aluminum sulfate to dissolve completely, compound concentration is that the ammonia spirit of 2 mol/L is stand-by;
(2) react:
Add 20L pure water in a kettle., open and stir, speed of agitator controls at 200r/min, then adds the ammoniacal liquor of 1L step (1), and then regulate aqueous ph value to be 11.5 with 0.1mol/L sodium hydroxide solution, control temperature is at 50 DEG C;
Add three kinds of feed liquids with measuring pump respectively, wherein the nickel sulfate solution flow of step (1) is: 30ml/min, and the NaOH of step (1) and the mixed solution flow of aluminum sulfate are: 15ml/min, and the ammonia spirit flow of step (1) is: 3ml/min; Control material liquid PH value 11.5 ± 0.2 when reacting, feed temperature 45 ± 2 DEG C, reacts.
When sustained response to the suspension containing nickel hydroxide arrives overfall place, the suspension containing nickel hydroxide is discharged from the overfall of reactor;
In course of reaction, three kinds of feed liquids are continual is added in reactor, and through continuous print reaction, the suspension containing nickel hydroxide is constantly discharged from the overfall of reactor.
(3) washing and drying:
By discharge suspension pure water to solution pH value lower than less than 9.5, dry moisture with centrifuge, can nickel hydroxide be obtained with baking oven 110 DEG C of oven dry.
Claims (2)
1. adulterate the preparation method of lithium ion anode material presoma of tellurium, it is characterized in that, comprise the steps:
(1) preparation of material liquid:
Compound concentration is the soluble metal salt solution of the nickel of 0.5-2 mol/L, cobalt or manganese, compound concentration is the sodium hydroxide solution of 2-10 mol/L, and Solid aluminum sulfate is added in the sodium hydroxide solution prepared, the addition of aluminum sulfate controls in 0.01-0.1 mol/L, be stirred to aluminum sulfate to dissolve completely, compound concentration is that the ammonia spirit of 2-4 mol/L is stand-by;
(2) react:
Add pure water in a kettle., open and stir, then add the ammonia spirit of step (1), the amount adding ammonia spirit controls ammonia density in solution upon mixing in 0.2-0.5 mol/L, then regulate aqueous ph value to be 11.5 with NaOH, control temperature is at 40-60 DEG C;
Three kinds of feed liquids are added respectively with measuring pump, wherein the metal salt solution flow of step (1) is: 20-40ml/min, the NaOH of step (1) and the mixed solution flow of aluminum sulfate are: 5-20ml/min, and the ammonia spirit flow of step (1) is: 2-5ml/min, reacts;
In course of reaction, three kinds of feed liquids are continual is added in reactor, and the suspension containing slaine be obtained by reacting constantly is discharged from the overfall of reactor;
(3) washing and drying:
By the suspension pure water of discharging to solution pH value lower than less than 9.5, centrifugally to dry;
Material liquid PH value 11.5 ± 0.2 is controlled, feed temperature 45 ± 2 DEG C when reacting in step (2);
Soluble metal salt solution specifically nickelous sulfate, cobaltous sulfate, manganese sulfate, nickel chloride, cobalt chloride or the manganese chloride solution of nickel, cobalt or manganese in step (1);
Regulate the pH value of the aqueous solution with 0.5-2 mol/L NaOH in step (2).
2. the preparation method of the lithium ion anode material presoma of a kind of tellurium that adulterates as claimed in claim 1, is characterized in that: be add 20L pure water in a kettle. in step (2), opens after stirring and adds 1L ammoniacal liquor again.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104319394A (en) * | 2014-10-17 | 2015-01-28 | 金川集团股份有限公司 | Method for preparing pure-phase spherical nickel hydroxide |
| CN106299526B (en) * | 2016-09-19 | 2018-11-06 | 中国电子科技集团公司第十八研究所 | Recycling method of strong alkali solution in waste lithium battery recycling industry |
| CN108232185B (en) * | 2017-12-18 | 2020-11-10 | 佛山市德方纳米科技有限公司 | Synthetic method of liquid-phase doped ternary precursor |
| CN113809321A (en) * | 2021-09-15 | 2021-12-17 | 深圳石墨烯创新中心有限公司 | Preparation method and application of precursor of aluminum and zirconium doped lithium nickelate cathode material |
| CN115321610A (en) * | 2022-08-31 | 2022-11-11 | 荆门市格林美新材料有限公司 | Zirconium-aluminum double-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof |
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| CN1221707A (en) * | 1998-12-11 | 1999-07-07 | 清华大学 | Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process |
| JP2006127955A (en) * | 2004-10-29 | 2006-05-18 | Sumitomo Metal Mining Co Ltd | Positive electrode active substance for nonaqueous secondary cell and its manufacturing method |
| CN101577333A (en) * | 2009-06-10 | 2009-11-11 | 江门市长优实业有限公司 | High specific capacity discharge platform spherical nickel hydroxide |
| JP2009298679A (en) * | 2008-06-17 | 2009-12-24 | Sumitomo Metal Mining Co Ltd | Production method of aluminum-containing nickel hydroxide particle |
| CN101694876A (en) * | 2009-10-22 | 2010-04-14 | 江西江特锂电池材料有限公司 | Lithium-rich manganese-based anode material and preparation method thereof |
| CN102306765A (en) * | 2011-08-18 | 2012-01-04 | 合肥国轩高科动力能源有限公司 | Preparation method for nickel-manganese-cobalt anode material of lithium ion battery |
| CN102569781A (en) * | 2012-03-27 | 2012-07-11 | 天津理工大学 | High-voltage lithium ion battery cathode material and preparation method thereof |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1221707A (en) * | 1998-12-11 | 1999-07-07 | 清华大学 | Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process |
| JP2006127955A (en) * | 2004-10-29 | 2006-05-18 | Sumitomo Metal Mining Co Ltd | Positive electrode active substance for nonaqueous secondary cell and its manufacturing method |
| JP2009298679A (en) * | 2008-06-17 | 2009-12-24 | Sumitomo Metal Mining Co Ltd | Production method of aluminum-containing nickel hydroxide particle |
| CN101577333A (en) * | 2009-06-10 | 2009-11-11 | 江门市长优实业有限公司 | High specific capacity discharge platform spherical nickel hydroxide |
| CN101694876A (en) * | 2009-10-22 | 2010-04-14 | 江西江特锂电池材料有限公司 | Lithium-rich manganese-based anode material and preparation method thereof |
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| CN102569781A (en) * | 2012-03-27 | 2012-07-11 | 天津理工大学 | High-voltage lithium ion battery cathode material and preparation method thereof |
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