CN1189402C - High-purity spherical cobalto-cobaltic oxide, and its preparing method and use - Google Patents
High-purity spherical cobalto-cobaltic oxide, and its preparing method and use Download PDFInfo
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- CN1189402C CN1189402C CNB031480926A CN03148092A CN1189402C CN 1189402 C CN1189402 C CN 1189402C CN B031480926 A CNB031480926 A CN B031480926A CN 03148092 A CN03148092 A CN 03148092A CN 1189402 C CN1189402 C CN 1189402C
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to high purity spherical tricobalt tetraoxide, a preparation method thereof and an application thereof. In the method, a cobalt salt water solution and sodium carbonate or sodium bicarbonate generate basic cobalt carbonate precipitates under the pH value of 6.5 to 9.0 +/-0.5 at the temperature of 30 to 90 DEG C, spherical basic cobalt carbonate is generated through filter, washing and drying, then the reaction with hydrogen peroxide is carried out, high purity spherical tricobalt tetraoxide is generated through filter, washing and drying, and the spherical tricobalt tetraoxide can also be generated through the calcination of the basic cobalt carbonate. The present invention has the advantages and effects of good flowability, narrow grain diameter range, increased tap density, high content of tricobalt tetraoxide and low impurities.
Description
Technical field
The present invention relates to a kind of preparation method of cobalt oxide, particularly the preparation method of high purity spherical cobaltic-cobaltous oxide belongs to Chemicals, is used for anode material for lithium-ion batteries.
Background technology
Lithium ion battery is a kind of emerging power supply, and therefore plurality of advantages such as it has, and voltage height, capacity are big, safety and environmental protection are being subjected to accepting extensively of people.The positive electrode material of present lithium ion battery is used the most general cobalt acid lithium, and during preparation cobalt acid lithium, used tricobalt tetroxide mainly adopts cobalt chloride or the preparation of cobalt oxalate method for calcinating, resulting tricobalt tetroxide shape is unformed, destroy spheroidal particle, can reduce tap density when synthesizing cobalt acid cobalt, increased volume of battery, and calcining reduce the electrochemical activity of tricobalt tetroxide, influence the electrochemical properties of final cobalt acid lithium, K in the while tricobalt tetroxide, impurity levels such as Na are also many, and it is mobile poor to cause, the grain graininess scope is wider and inhomogeneous, increased the internal resistance of battery, because impurity is many, three degree processing costs height.
Summary of the invention
Purpose of the present invention is the shortcoming and deficiency in order to overcome above-mentioned prior art just, and a kind of preparation method with high purity spherical cobaltic-cobaltous oxide of good fluidity is provided, thereby improves the lithium ion battery chemical property, has improved the quality of battery.
The objective of the invention is to realize by following technical proposal:
The high purity spherical cobaltic-cobaltous oxide is characterized in that this tricobalt tetroxide is a spheroidal crystal, 5～30 microns of median sizes, tap density 〉=1.2g/cm
3, tricobalt tetroxide content 〉=99.5%, other metallic cation total content is less than 0.2%.
The preparation method of high purity spherical cobaltic-cobaltous oxide is characterized in that it is undertaken by following step:
A) at first respectively the cobalt salt of technical grade is mixed with the cobalt saline solution of 0.5～2.0M with deionized water, the yellow soda ash of technical grade or sodium bicarbonate are mixed with the aqueous solution of 0.5～2.0M;
B) in reaction vessel, add a) deionized water more than 1/2nd of the cobalt saline solution volume of a preparation, and be stirred and heated to 30～90 ℃, add a) cobalt salt solution of item with 2～5ml/min flow velocity then, and the pH value of yellow soda ash of using a) or sodium bicarbonate aqueous solution conditioned reaction system is 6.5～9.0 ± 0.5, charging finishes back restir 0.5～1 hour, generates the cobaltous dihydroxycarbonate precipitation;
C) filter b then) precipitation, and with the deionized water wash of 1～20 times of volume of filter cake weight 1～3 time, up to the pH value less than 7.2, filtration then, filter cake dries by the fire more than 6 hours in 60～120 ℃ baking oven, obtains the spheric cobaltous dihydroxycarbonate;
D) in another container, add the technical grade superoxol of 1～10% concentration, be stirred and heated to 60～90 ℃, adding c) cobaltous dihydroxycarbonate, both consumptions are that the by weight/volume of cobaltous dihydroxycarbonate and hydrogen peroxide is 1: 0.5～5, stirred after 2 hours still aging 1 hour, cobaltous dihydroxycarbonate becomes black, filter then, and with the deionized water wash of 1～20 times of volume of filter cake weight 1～3 time, filter then, filter cake dries by the fire more than 6 hours in 60～120 ℃ baking oven, obtains the tricobalt tetroxide product of purity 〉=99.5% spheroidal crystal.
Described preparation method can obtain purity 〉=99.5% spheric tricobalt tetroxide with the cobaltous dihydroxycarbonate that makes 300～900 ℃ of temperature lower calcinations 1～6 hour, and described cobalt salt is cobalt chloride or Xiao Suangu or rose vitriol.
The purposes of spherical cobaltic-cobaltous oxide is used to prepare anode material for lithium-ion batteries.
Product of the present invention all adopts automatic control system in preparation process, to guarantee the strictness control in the reaction conditions.Products obtained therefrom is analyzed particle with scanning electronic microscope, utilizes X fluorescent spectroscopy particulate composition, and the quality of products obtained therefrom is reliable.
Owing to adopt technique scheme, make the technology of the present invention compared with the prior art have following advantage and effect:
A) the available spherical cobalt acid lithium of the production of high purity spherical cobaltic-cobaltous oxide that obtains of the present invention and Quilonum Retard building-up reactions, its granulometric range is narrower, therefore can improve tap density, reduce the size of battery, be convenient to be applied to electrical source of power, and good fluidity, reduced the internal resistance of lithium ion battery, improved the chemical property of lithium ion battery;
B) adopt strong oxidizer and spherical cobaltous dihydroxycarbonate, can obtain spherical cobaltic-cobaltous oxide, can not destroy spheroidal particle, also reduced the foreign matter content of tricobalt tetroxide simultaneously, reduced the three wastes processing costs in the production process, guaranteed that also environment is not contaminated;
C) adopt the heat method to obtain tricobalt tetroxide, guaranteed the simple of technology, reduced the use of pure water;
D) preparation method's process automation degree height, processing parameter control is strict, guarantees the quality of product.
Embodiment:
Raw materials usedly be commercially available technical grade product.
Embodiment 1:
The cobalt chloride of getting technical grade is mixed with the cobalt chloride salt brine solution 2000ml of 0.5M with deionized water, it is standby that yellow soda ash is made into the aqueous solution 2000ml of 0.5M, in 10 liters glass reaction container, add deionized water 1000ml earlier, be heated with stirring to 30 ℃, in the speed adding reactor of 2000ml cobalt chloride salt brine solution with above-mentioned 0.5M with 2ml/min, and regulate constant pH 6.5 ± 0.5 with the aqueous solution of the yellow soda ash of 0.5M, restir 0.5 hour, generation cobaltous dihydroxycarbonate precipitation, filtering-depositing then, get filter cake 200g, add deionized water 200ml, wash three times, less than 7.2, filter then up to the pH value, filter cake was dried 10 hours under 60 ℃ of temperature, obtain the spheric cobaltous dihydroxycarbonate, get 10 liters of glass reactors again, add the technical grade hydrogen peroxide 2500ml of 1% concentration, 60 ℃ of stirring heating, add and state cobaltous dihydroxycarbonate 500g stirring 2 hours, still aging 1 hour, after the cobaltous dihydroxycarbonate blackening, filter then, filter cake adds three after-filtration of deionized water 500ml washing, and filter cake was dried 10 hours under 60 ℃ of temperature, obtained the high purity spherical cobaltic-cobaltous oxide, 30 microns of mean particle sizes, tap density 1.45g/cm
3, tricobalt tetroxide content 99.5%, other metallic cation total content 0.20%.
Embodiment 2:
The rose vitriol of getting technical grade is mixed with the rose vitriol salt brine solution 2000ml of 1.2M with deionized water, it is standby that sodium bicarbonate is joined the 2000ml aqueous solution of 1.3M, in 10 liters glass reaction container, add deionized water 1100ml earlier, be heated with stirring to 55 ℃, in the speed adding reaction vessel of 2000ml rose vitriol salt brine solution with above-mentioned 1.2M with 5ml/min, and regulate constant pH 8.0 ± 0.5 with the aqueous solution of the yellow soda ash of 1.3M, restir 0.8 hour, generation cobaltous dihydroxycarbonate precipitation, filtering-depositing then, get filter cake 400g, add deionized water 4000ml, the washing secondary, up to the pH value less than 7.2, filter then, filter cake was dried 8 hours under 80 ℃ of temperature, obtain the spheric cobaltous dihydroxycarbonate, get 10 liters of glass reaction containers again, the hydrogen peroxide 1000ml that adds 5% concentration, 75 ℃ of stirring heating are added and are stated cobaltous dihydroxycarbonate 500g stirring 2 hours, left standstill heavyization 1 hour, after the cobaltous dihydroxycarbonate blackening, filter then, after filter cake adds deionized water 5000ml washing secondary, filter cake was dried 8 hours under 80 ℃ of temperature, obtained the high purity spherical cobaltic-cobaltous oxide.20 microns of mean particle sizes, tap density 1.41g/cm
3, tricobalt tetroxide content 99.7%, other metallic cation total content 0.18%.
Embodiment 3:
The Xiao Suangu of getting technical grade is mixed with the aqueous solution 2000ml of 2.0M with deionized water, it is standby that yellow soda ash is made into the aqueous solution 2000ml of 2.0M, in 10 liters Glass Containers, add deionized water 1300ml earlier, be heated with stirring to 90 ℃, in the speed adding reaction vessel of 2000ml Xiao Suangu salt brine solution with above-mentioned 2.0M with 3.5ml/min, and regulate constant pH 8.5 ± 0.5 with the aqueous solution of the yellow soda ash of 1.3M, restir 1.0 hours, generation cobaltous dihydroxycarbonate precipitation, filter then, get filter cake 200g, add deionized water 4000ml, washing once,, filter then less than 7.2 up to the pH value, filter cake was dried 6 hours under 120 ℃ of temperature, obtain spherical cobaltous dihydroxycarbonate, in getting 10 liters of Glass Containerss, add the hydrogen peroxide 250ml of 10% concentration, 90 ℃ of stirring heating, add and state cobaltous dihydroxycarbonate 500g stirring 2 hours, left standstill heavyization 1 hour, and after the cobaltous dihydroxycarbonate blackening, filtered then, filter cake adds deionized water 10000ml washing once dried 6 hours under 120 ℃ of temperature the back, obtain the high purity spherical cobaltic-cobaltous oxide, 6 microns of mean particle sizes, tap density 1.32g/cm
3, tricobalt tetroxide content 99.5%, other metallic cation total content 0.20%.
Embodiment 4:
The cobalt chloride of getting technical grade is mixed with the cobalt chloride salt brine solution 2000ml of 0.5M with deionized water, it is standby that yellow soda ash is made into the aqueous solution 2000ml of 0.5M, in 10 liters Glass Containers, add deionized water 1500ml earlier, be heated with stirring to 30 ℃, the 2000ml cobalt chloride solution of the above-mentioned 0.5M speed with 2ml/min is added in the container, and with the aqueous solution adjusting constant pH 7.5 ± 0.5 of the yellow soda ash of 0.5M, restir 0.5 hour, generation cobaltous dihydroxycarbonate precipitation is filtered then, gets filter cake 200g, add deionized water 200ml, wash three times, less than 7.2, filter then up to the pH value, filter cake was dried 8 hours under 80 ℃ of temperature, obtain spherical cobaltous dihydroxycarbonate, 300 degree calcinings are 6 hours in retort furnace, obtain the high purity spherical cobaltic-cobaltous oxide, 21 microns of mean particle sizes, tap density 1.40g/cm
3, tricobalt tetroxide content 99.5%, other metallic cation total content 0.20%.
Embodiment 5:
The Xiao Suangu of getting technical grade is mixed with the Xiao Suangu salt brine solution 2000ml of 2.0M with deionized water, it is standby that yellow soda ash is made into the aqueous solution 2000ml of 2.0M, in 10 liters Glass Containers, add deionized water 1200ml earlier, be heated with stirring to 90 ℃, the 2000ml cobalt nitrate aqueous solution of the above-mentioned 1.2M speed with 3.5ml/min is added in the reaction vessel, and with the aqueous solution adjusting constant pH 9.0 ± 0.5 of the yellow soda ash of 1.3M, restir 1.0 hours, generation cobaltous dihydroxycarbonate precipitation is filtered then, gets filter cake 200g, add deionized water 4000ml, washing once, is filtered less than 7.2 then up to the pH value, under 120 ℃ of temperature, dried 6 hours behind the filter cake, obtain spherical cobaltous dihydroxycarbonate, 900 degree calcinings are 1 hour in retort furnace, obtain the high purity spherical cobaltic-cobaltous oxide, 12 microns of mean particle sizes, tap density 1.22g/cm
3, tricobalt tetroxide content 99.5%, other metallic cation total content 0.20%.
Claims (1)
1, the preparation method of high purity spherical cobaltic-cobaltous oxide is characterized in that it is undertaken by following step:
A) at first respectively cobalt chloride, Xiao Suangu or the rose vitriol of technical grade is mixed with the cobalt saline solution of 0.5～2.0M with deionized water, the yellow soda ash of technical grade or sodium bicarbonate are mixed with the aqueous solution of 0.5～2.0M;
B) in reaction vessel, add a) deionized water more than 1/2nd of cobalt chloride, Xiao Suangu or the cobalt sulfate solution volume of a preparation, and be stirred and heated to 30～90 ℃, add a) cobalt salt solution of item with 2～5ml/min flow velocity then, and the pH value of yellow soda ash of using a) or sodium bicarbonate aqueous solution conditioned reaction system is 6.5～9.0 ± 0.5, charging finishes back restir 0.5～1 hour, generates the cobaltous dihydroxycarbonate precipitation;
C) filter b then) precipitation, and with the deionized water wash of 1～20 times of volume of filter cake weight 1～3 time, up to the pH value less than 7.2, filtration then, filter cake dries by the fire more than 6 hours in 60～120 ℃ baking oven, obtains the spheric cobaltous dihydroxycarbonate;
D) in another container, add the technical grade superoxol of 1～10% concentration, be stirred and heated to 60～90 ℃, adding c) cobaltous dihydroxycarbonate, both consumptions are that the by weight/volume of cobaltous dihydroxycarbonate and described superoxol is 1: 0.5～5, the unit of this ratio is a grams per milliliter, stirred after 2 hours still aging 1 hour, cobaltous dihydroxycarbonate becomes black, filter then, and with the deionized water wash of 1～20 times of volume of filter cake weight 1～3 time, filter then, filter cake dries by the fire more than 6 hours in 60～120 ℃ baking oven, obtains the tricobalt tetroxide product of purity 〉=99.5% spheroidal crystal.
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Cited By (1)
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| CN102910686A (en) * | 2011-08-04 | 2013-02-06 | 深圳市格林美高新技术股份有限公司 | Cobalt carbonate preparation method and superfine cobalt powder preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910686A (en) * | 2011-08-04 | 2013-02-06 | 深圳市格林美高新技术股份有限公司 | Cobalt carbonate preparation method and superfine cobalt powder preparation method |
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