CN103922426A - Preparation method of low-chloride high-purity cobalt carbonate - Google Patents
Preparation method of low-chloride high-purity cobalt carbonate Download PDFInfo
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- CN103922426A CN103922426A CN201410086956.8A CN201410086956A CN103922426A CN 103922426 A CN103922426 A CN 103922426A CN 201410086956 A CN201410086956 A CN 201410086956A CN 103922426 A CN103922426 A CN 103922426A
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Abstract
The invention relates to a preparation method of low-chloride high-purity cobalt carbonate. The preparation method is characterized by comprising the following steps: using ammonium bicarbonate as a precipitator, adding ammonium bicarbonate which accounts for 4-6 times of molar ratio of cobalt chloride into a cobalt chloride solution containing a foam inhibitor at one time under the conditions of normal temperature and continuous agitation, standing for at least 12 hours, washing a product obtained, filtering and drying to obtain a high-purity cobalt carbonate product. Content of chlorine in the prepared high-purity cobalt carbonate product is less than 500ppm, but the content of chlorine in the prior art is high than 1000ppm. Meanwhile, the preparation method has a simple technology; by the use of ammonium bicarbonate, there is no introduction of new impurity elements; and with the addition of the foam inhibitor, speed of carbon dioxide overflowing from the solution is reduced so as to achieve the effect of full reaction. Thus, purity of the product is raised; overswelling is avoided; and capacity is greatly increased.
Description
Technical field
The present invention relates to the preparation method of the high-purity cobaltous carbonate of a kind of low chlorine root.
Background technology
At Wimet, do in industry, cobalt powder is as the binding agent of producing Wimet.Cobalt powder as hardmetall binder requires extremely low foreign matter content.From cobalt salt solution electrolysis or the cobalt powder produced by the hydrogen reduction of technical grade cobalt oxide, be all difficult to meet these requirements.The cobalt powder that most CEMENTED CARBIDE PRODUCTION is used is that the high-purity cobaltous carbonate that adopts the cobalt salt precipitator method to produce is raw material, then with hydrogen reduction or pyrolysis, makes satisfactory cobalt powder.
Due to the fast development of lithium-ion secondary cell industry, as cobalt acid lithium, the nickle cobalt lithium manganate cobalt of battery industry positive electrode material, consume and surpass cemented carbide industry in recent years, become China's cobalt and consume the first rich and influential family.As the cobaltous carbonate of producing lithium cell raw material precursor, as producing high reactivity, there is higher lithium storage content and the better positive electrode material of cycle life, requiring it to have the features such as high purity, fine size, narrow diameter distribution, is the indispensable material of producing lithium ion battery with high energy density positive electrode material.
Summary of the invention
The preparation method who the object of this invention is to provide the high-purity cobaltous carbonate of a kind of low chlorine root, can prepare high purity, and especially chloride content is less than the cobaltous carbonate product that is suitable for Wimet and lithium electricity positive electrode material of 500ppm.
The preparation method of the high-purity cobaltous carbonate of a kind of low chlorine root, its special feature is, comprise the steps: to adopt bicarbonate of ammonia as precipitation agent, under normal temperature and lasting agitation condition, to the disposable cobalt chloride mol ratio 4-6 bicarbonate of ammonia doubly that adds in the cobalt chloride solution that contains foam inhibiting agent, standing at least 12 hours then by the product obtaining through washing, obtain high-purity cobaltous carbonate product after filtering, drying.
Wherein in cobalt chloride solution, the volumetric molar concentration of cobalt chloride is 1-2mol/L.
Wherein foam inhibiting agent adopts organo-siloxane, polyethers, silicon and ether grafting, contains amine, imines and amides foam inhibiting agent, and the consumption of foam inhibiting agent is the 1-2% of cobalt chloride solution weight or the 1-5% of cobalt chloride solution cumulative volume.
Wherein wash, filter, dry specifically product through 3-5 all over pure water rinsing, then enter whizzer or pressure filter dehydration, put into afterwards baking oven and dry 6-8 hour at 90-100 ℃, finally cross 200 mesh sieves.
After wherein adding bicarbonate of ammonia, also to continue to stir 15min-1 hour.
Chlorine root in high-purity cobaltous carbonate product prepared by the present invention is less than 500ppm, and in prior art chloride content higher than 1000ppm, preparation method's technique of this invention is simultaneously simple, use bicarbonate of ammonia and introduce without new impurity element, adding of foam inhibiting agent reduces the speed that carbonic acid gas overflows from solution, thereby reaches the effect of abundant reaction, not only improved the purity of product, avoid emitting groove phenomenon simultaneously, greatly increased production capacity.
Accompanying drawing explanation
Accompanying drawing 1 is the Electronic Speculum figure of the cobaltous carbonate of the embodiment of the present invention 1 preparation;
Accompanying drawing 2 is the XRD spectra of the cobaltous carbonate of the embodiment of the present invention 1 preparation.
Embodiment
The subject matter of current high-purity cobaltous carbonate product is that cl content is higher, conventionally can reach 1000-20000ppm.The content of chlorine is higher, has not only affected the microstructure and properties of Wimet, is unfavorable for the chemical property of positive electrode material simultaneously in lithium ion battery.Existing production technology mainly adopts liquid-phase precipitation method, and selecting sodium carbonate, sodium bicarbonate and bicarbonate of ammonia is that precipitation agent reacts with solubility cobalt salt, prepares cobaltous carbonate powder.Due to OH in reaction process
-the existence of (hydrolysis reaction causes) makes can not generate in reaction process the cobaltous carbonate of pure thing phase, but part generates cobaltous dihydroxycarbonate, residual a large amount of chlorine root in fact this cobaltous dihydroxycarbonate, and this material is to be difficult to remove in subsequent processes.Meanwhile, everybody is for reduce the OH in reaction system as far as possible
-, reaction process is selected the ph value of reaction reducing in controlling, but there is again a problem in this: under low PH, cobalt ion reaction not exclusively causes productive rate to reduce.Generally lower than 95%.
Advantage of the present invention is: the high-purity cobaltous carbonate product that can prepare super low loading chlorine root.Cl content < 500ppm wherein, meanwhile, productive rate reaches more than 99%.
1, the precipitation agent of conventionally selecting is sodium carbonate, sodium bicarbonate and bicarbonate of ammonia.In the present invention, selecting bicarbonate of ammonia is precipitation agent, is because the pH value of bicarbonate of ammonia after water-soluble is all low compared with the first two kind, shown in table specific as follows.
Meanwhile, bicarbonate of ammonia is not brought Na ion into, is convenient to follow-up washing.
2, select the disposable reason adding to be: the most of degree of its moment reaction process is carried out under low pH value.Simultaneously disposable adding, in reaction process, moment produces great amount of carbon dioxide and forms carbonic acid, effectively keeps low pH value environment.(reaction process is actually carbonic acid gas or perhaps carbonic acid as precipitation agent)
3, the consumption of 4-6 times of bicarbonate of ammonia guarantees the amount of carbonic acid gas and reacts completely.
4, foam inhibiting agent is a kind of organism, can not bring new impurity.It act as and reduces the speed that carbonic acid gas overflows from solution, thereby reaches the effect of abundant reaction.Preventing that a large amount of carbon dioxide from generating to cause emits groove.
5, time of repose guarantees that noncrystal cobaltous carbonate is to transformation of crystal.
Embodiment 1:
1, the preparation of stock liquid: the cobalt chloride solution of preparation 1 mol/L;
2, reaction:
The first step: add the cobalt chloride solution 25L configuring in 50L reactor, 1 mole/L of cobalt chloride solution, opens and be stirred to 100r/min.
Second step: add 20ml foam inhibiting agent, specifically adopt polydimethylsiloxane or polypropylene glycerol aether all can.
The 3rd step: continuing under stirring the disposable solid ammonium bicarbonate 100mol(8Kg that adds);
The 4th step: add after material, then continue to stir 1 hour then standing 24 hours.
3, washing, oven dry:
Material is washed to solution pH value 7.6 with pure water, and centrifugation post-drying, specifically dries 7 hours at 100 ℃, finally crosses 200 mesh sieves.
Following table is the analysis to the cobaltous carbonate product obtaining:
| Material performance | Loose density | Median size (D50) |
| Detected value | 0.55 | 0.816 |
More than the cobaltous carbonate sample data on bulk analysis of preparation: be mainly chlorine root index, industry standard is less than 0.05%, and prepared by the present invention is 0.01%, cobaltous carbonate product prepared by the method, owing to having used the cause of foam inhibiting agent, this technique output capacity is greater than 99%, than the output capacity that does not add foam inhibiting agent, exceeds 2%.
Be illustrated in figure 2 the cobaltous carbonate XRD spectra of preparation, as can be seen from the figure this product is high-purity cobaltous carbonate.
Claims (5)
1. the preparation method of the high-purity cobaltous carbonate of low chlorine root, it is characterized in that, comprise the steps: to adopt bicarbonate of ammonia as precipitation agent, under normal temperature and lasting agitation condition, to the disposable cobalt chloride mol ratio 4-6 bicarbonate of ammonia doubly that adds in the cobalt chloride solution that contains foam inhibiting agent, standing at least 12 hours then by the product obtaining through washing, obtain high-purity cobaltous carbonate product after filtering, drying.
2. the preparation method of the high-purity cobaltous carbonate of a kind of low chlorine root as claimed in claim 1, is characterized in that: wherein in cobalt chloride solution, the volumetric molar concentration of cobalt chloride is 1-2mol/L.
3. the preparation method of the high-purity cobaltous carbonate of a kind of low chlorine root as claimed in claim 1, it is characterized in that: wherein foam inhibiting agent adopts organo-siloxane, polyethers, silicon and ether grafting, contains amine, imines and amides foam inhibiting agent, and the consumption of foam inhibiting agent is the 1-2% of cobalt chloride solution weight or the 1-5% of cobalt chloride solution cumulative volume.
4. the preparation method of the high-purity cobaltous carbonate of a kind of low chlorine root as claimed in claim 1, it is characterized in that: wherein wash, filter, dry specifically by 3-5 time pure water rinsing of product process, then enter whizzer or pressure filter dehydration, put into afterwards baking oven and dry 6-8 hour at 90-100 ℃, finally cross 200 mesh sieves.
5. the preparation method of the high-purity cobaltous carbonate of a kind of low chlorine root as claimed in claim 1, is characterized in that: after wherein adding bicarbonate of ammonia, also will continue to stir 15min-1 hour.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944475A (en) * | 2015-07-16 | 2015-09-30 | 南京寒锐钴业股份有限公司 | Preparation method of cobalt carbonate with super coarse particles and high purity |
| CN106673073A (en) * | 2016-12-23 | 2017-05-17 | 荆门市格林美新材料有限公司 | Method for preparing small-particle size large-bulk cobalt carbonate |
| CN111807420A (en) * | 2019-04-12 | 2020-10-23 | 荆门市格林美新材料有限公司 | Preparation method of high-density low-chlorine cobalt carbonate |
| CN113044888A (en) * | 2019-12-26 | 2021-06-29 | 荆门市格林美新材料有限公司 | Preparation method of amorphous cobalt carbonate |
| CN113292109A (en) * | 2020-02-24 | 2021-08-24 | 荆门市格林美新材料有限公司 | Preparation method of low-sodium superfine cobalt carbonate |
| CN113800573A (en) * | 2020-06-16 | 2021-12-17 | 荆门市格林美新材料有限公司 | Low-chloride ion washing method for cobalt carbonate |
| CN114455641A (en) * | 2020-11-10 | 2022-05-10 | 荆门市格林美新材料有限公司 | Preparation method of cobalt carbonate with low chlorine content |
-
2014
- 2014-03-11 CN CN201410086956.8A patent/CN103922426A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944475A (en) * | 2015-07-16 | 2015-09-30 | 南京寒锐钴业股份有限公司 | Preparation method of cobalt carbonate with super coarse particles and high purity |
| CN106673073A (en) * | 2016-12-23 | 2017-05-17 | 荆门市格林美新材料有限公司 | Method for preparing small-particle size large-bulk cobalt carbonate |
| CN111807420A (en) * | 2019-04-12 | 2020-10-23 | 荆门市格林美新材料有限公司 | Preparation method of high-density low-chlorine cobalt carbonate |
| CN111807420B (en) * | 2019-04-12 | 2023-11-07 | 荆门市格林美新材料有限公司 | Preparation method of high-density low-chlorine cobalt carbonate |
| CN113044888A (en) * | 2019-12-26 | 2021-06-29 | 荆门市格林美新材料有限公司 | Preparation method of amorphous cobalt carbonate |
| CN113292109A (en) * | 2020-02-24 | 2021-08-24 | 荆门市格林美新材料有限公司 | Preparation method of low-sodium superfine cobalt carbonate |
| CN113292109B (en) * | 2020-02-24 | 2023-11-07 | 荆门市格林美新材料有限公司 | Preparation method of low-sodium superfine cobalt carbonate |
| CN113800573A (en) * | 2020-06-16 | 2021-12-17 | 荆门市格林美新材料有限公司 | Low-chloride ion washing method for cobalt carbonate |
| CN114455641A (en) * | 2020-11-10 | 2022-05-10 | 荆门市格林美新材料有限公司 | Preparation method of cobalt carbonate with low chlorine content |
| CN114455641B (en) * | 2020-11-10 | 2023-09-05 | 荆门市格林美新材料有限公司 | Preparation method of cobalt carbonate with low chlorine content |
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