CN103259010A - 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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- CN103259010A CN103259010A CN2013101425593A CN201310142559A CN103259010A CN 103259010 A CN103259010 A CN 103259010A CN 2013101425593 A CN2013101425593 A CN 2013101425593A CN 201310142559 A CN201310142559 A CN 201310142559A CN 103259010 A CN103259010 A CN 103259010A
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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 mixes.
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 who produces on the market is the high temperature solid-phase sintering method now.Be characterized in: equipment and technology preparation condition are easy to control, are easy to realize industrialization.The common elder generation of preparation process is with the direct fully mixing of oxide, hydroxide or the carbonic acid thing of lithium salts and Ni, Co, Mn and then under different atmosphere thereby it is carried out high temperature sintering acquisition lithium ion anode material.
Usually adopt the crystallization control method to prepare presoma in the prior art, can be used as the presoma of producing cobalt acid lithium as cobalt hydroxide, cobalt carbonate, cobaltosic oxide, nickel hydroxide, nickelous carbonate are that presoma, the manganese dioxide of lithium nickelate is the main precursor of LiMn2O4, the presoma that the oxide of Ni Co Mn, hydroxide are nickle cobalt lithium manganate.We also are referred to as ternary material.In industry, most of sintering producer oneself does not produce presoma.But the buying presoma only carries out sintering.
The advantage of preparation presoma: as cell positive material, for reaching desirable chemical property, require it that low impurity content useful metallic element that mixes is simultaneously arranged; Simultaneously its physical property there is quite harsh requirement: as higher tap density, suitable particle size range, specific area, degree of crystallinity etc.The realization of these performance index is mainly controlled in the presoma preparation process.
The present state of the art and the problem of existence are: the lithium ion anode material of amphoteres such as adulterated al, Zn obtains extensive approval and the expectation in market.In traditional doping process, aluminum soluble salt is formulated in the host element salting liquid, yet aluminium ion has generated precipitation earlier in lower pH value scope in course of reaction, cause the effect that can not reach with the host element co-precipitation, the generation of this phenomenon not only can not reach equally distributed effect, largely disturbs the particle normal growth simultaneously.The product density of preparing 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 preparation method who the purpose of this invention is to provide a kind of lithium ion anode material presoma of the tellurium that mixes can prepare that doped chemical is evenly distributed, the presoma of high density, good sphericity.
A kind of preparation method of lithium ion anode material presoma of the tellurium that mixes, its special feature is, comprises the steps:
(1) preparation of material liquid:
Compound concentration is the soluble metal salting liquid of nickel, cobalt or the manganese of 0.5-2 mol, compound concentration is the sodium hydroxide solution of 2-10 mol, and solid sulphuric acid aluminium is added in the sodium hydroxide solution for preparing, the addition control of aluminum sulfate is in the 0.01-0.1 mol, be stirred to the aluminum sulfate dissolving fully, compound concentration is that the ammonia spirit of 2-4 mol is stand-by;
(2) reaction:
In reactor, add pure water, open to stir, add the ammonia spirit of step (1) again, the amount control that adds ammonia spirit after mixing the ammonia concentration in the solution in the 0.2-0.5 mol, regulating pH value of water solution with NaOH then is 11.5, and the control temperature is at 40-60 ℃;
Add three kinds of feed liquids with measuring pump respectively, 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, react;
Three kinds of continual being added in the reactor of feed liquid in the course of reaction, the suspension that contains slaine that reaction obtains is constantly discharged from the overfall of reactor;
(3) washing and drying:
The suspension of discharging washed to the pH value of solution value with pure water be lower than below 9.5, centrifugal oven dry gets final product.
Control material liquid pH value 11.5 ± 0.2 when reacting in the step (2), 45 ± 2 ℃ of feed temperatures.
Be to add the 20L pure water in reactor in the step (2), unlatching adds 1L ammoniacal liquor after stirring again.
The soluble metal salting liquid of nickel, cobalt or manganese specifically is nickelous sulfate, cobaltous sulfate, manganese sulfate, nickel chloride, cobalt chloride or manganese chloride solution in the step (1).
Regulate pH value of aqueous solution with 0.5-2 mol NaOH in the step (2).
Preparation method of the present invention is by the doping way of tellurium in the precursor of lithium ionic cell positive material preparation process such as change aluminium, make doped chemical reach the effect of co-precipitation with host element, thus the presoma of the high density of preparing, good sphericity.And the presoma that contains the tellurium doping of the inventive method preparation, doped chemical is evenly distributed in presoma, can realize the high density of presoma, and good sphericity is all arranged.
Description of drawings
The nickel hydroxide presoma shape appearance figure that accompanying drawing 1 is prepared for the method in the background technology, as can be seen from the figure product density is low, sphericity is poor;
The nickel hydroxide presoma shape appearance figure that accompanying drawing 2 is prepared for the method for the embodiment of the invention 1, as can be seen from the figure product density height, good sphericity;
Zn distribution diagram of element, as can be seen from the figure existing technology sample Zn element (tellurium of Al element or other doping) skewness in spheroid in the middle nickel hydroxide presoma that accompanying drawing 3 is prepared for the method in the background technology;
Zn distribution diagram of element in the middle nickel hydroxide presoma that accompanying drawing 4 is prepared for the method for the embodiment of the invention 1, as can be seen from the figure the tellurium of Can Zaing evenly distributes in spheroid.
Embodiment
Embodiment 1:
A kind of preparation method of lithium ion anode material presoma of the tellurium that mixes comprises the steps:
(1) preparation of material liquid:
Compound concentration is 2 mol nickel sulfate solutions, compound concentration is the sodium hydroxide solution of 4 mol, and solid sulphuric acid aluminium is added in the sodium hydroxide solution for preparing to the concentration of aluminum sulfate in sodium hydroxide solution be 0.1 mole/L, be stirred to the aluminum sulfate dissolving fully, compound concentration is that the ammonia spirit of 2 mol is stand-by;
(2) reaction:
Add the 20L pure water in the 50L reactor, open and stir, speed of agitator is controlled at 200r/min, adds the ammoniacal liquor of 1L step (1) again, and regulating pH value of water solution with the 0.1mol/L sodium hydroxide solution then is 11.5, and the control temperature is at 50 ℃;
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, the ammonia spirit flow of step (1) is: 3ml/min; Control material liquid pH value 11.5 ± 0.2 when reacting, 45 ± 2 ℃ of feed temperatures react.
After sustained response 8-10 hour, the suspension that will contain nickel hydroxide is discharged from the overfall of reactor;
Three kinds of continual being added in the reactor of feed liquid in the course of reaction, through continuous reaction, the suspension that contains nickel hydroxide is constantly discharged from the overfall of reactor.
(3) washing and drying:
The suspension of discharging washed to the pH value of solution value with pure water be lower than below 9.5, dry moisture with centrifuge, can obtain nickel hydroxide with baking oven 110 ℃ of oven dry.
Embodiment 2:
A kind of preparation method of lithium ion anode material presoma of the tellurium that mixes comprises the steps:
(1) preparation of material liquid:
Compound concentration is 2 mol nickel sulfate solutions, compound concentration is the sodium hydroxide solution of 4 mol, and solid sulphuric acid aluminium is added in the sodium hydroxide solution for preparing to the concentration of aluminum sulfate in sodium hydroxide solution be 0.1 mole/L, be stirred to the aluminum sulfate dissolving fully, compound concentration is that the ammonia spirit of 2 mol is stand-by;
(2) reaction:
Add the 20L pure water in reactor, open and stir, speed of agitator is controlled at 200r/min, adds the ammoniacal liquor of 1L step (1) again, and regulating pH value of water solution with the 0.1mol/L sodium hydroxide solution then is 11.5, and the control temperature is at 50 ℃;
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, the ammonia spirit flow of step (1) is: 3ml/min; Control material liquid pH value 11.5 ± 0.2 when reacting, 45 ± 2 ℃ of feed temperatures react.
When sustained response arrived the overfall place to the suspension that contains nickel hydroxide, the suspension that will contain nickel hydroxide was discharged from the overfall of reactor;
Three kinds of continual being added in the reactor of feed liquid in the course of reaction, through continuous reaction, the suspension that contains nickel hydroxide is constantly discharged from the overfall of reactor.
(3) washing and drying:
The suspension of discharging washed to the pH value of solution value with pure water be lower than below 9.5, dry moisture with centrifuge, can obtain nickel hydroxide with baking oven 110 ℃ of oven dry.
Claims (5)
1. the preparation method of the lithium ion anode material presoma of the tellurium that mixes is characterized in that, comprises the steps:
(1) preparation of material liquid:
Compound concentration is the soluble metal salting liquid of nickel, cobalt or the manganese of 0.5-2 mol, compound concentration is the sodium hydroxide solution of 2-10 mol, and solid sulphuric acid aluminium is added in the sodium hydroxide solution for preparing, the addition control of aluminum sulfate is in the 0.01-0.1 mol, be stirred to the aluminum sulfate dissolving fully, compound concentration is that the ammonia spirit of 2-4 mol is stand-by;
(2) reaction:
In reactor, add pure water, open to stir, add the ammonia spirit of step (1) again, the amount control that adds ammonia spirit after mixing the ammonia concentration in the solution in the 0.2-0.5 mol, regulating pH value of water solution with NaOH then is 11.5, and the control temperature is at 40-60 ℃;
Add three kinds of feed liquids with measuring pump respectively, 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, react;
Three kinds of continual being added in the reactor of feed liquid in the course of reaction, the suspension that contains slaine that reaction obtains is constantly discharged from the overfall of reactor;
(3) washing and drying:
The suspension of discharging washed to the pH value of solution value with pure water be lower than below 9.5, centrifugal oven dry gets final product.
2. the preparation method of the lithium ion anode material presoma of a kind of tellurium that mixes as claimed in claim 1 is characterized in that: control material liquid pH value 11.5 ± 0.2 when reacting in the step (2), 45 ± 2 ℃ of feed temperatures.
3. the preparation method of the lithium ion anode material presoma of a kind of tellurium that mixes as claimed in claim 1 is characterized in that: be to add the 20L pure water in reactor in the step (2), add 1L ammoniacal liquor again after the unlatching stirring.
4. the preparation method of the lithium ion anode material presoma of a kind of tellurium that mixes as claimed in claim 1 is characterized in that: the soluble metal salting liquid of nickel, cobalt or manganese specifically is nickelous sulfate, cobaltous sulfate, manganese sulfate, nickel chloride, cobalt chloride or manganese chloride solution in the step (1).
5. the preparation method of the lithium ion anode material presoma of a kind of tellurium that mixes as claimed in claim 1 is characterized in that: regulate pH value of aqueous solution with 0.5-2 mol NaOH in the step (2).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106299526A (en) * | 2016-09-19 | 2017-01-04 | 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 |
| CN108232185A (en) * | 2017-12-18 | 2018-06-29 | 佛山市德方纳米科技有限公司 | The synthetic method of liquid phase doping 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106299526A (en) * | 2016-09-19 | 2017-01-04 | 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 |
| 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 |
| CN108232185A (en) * | 2017-12-18 | 2018-06-29 | 佛山市德方纳米科技有限公司 | The synthetic method of liquid phase doping ternary precursor |
| 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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