CN107540024A - Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide - Google Patents
Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide Download PDFInfo
- Publication number
- CN107540024A CN107540024A CN201710828090.7A CN201710828090A CN107540024A CN 107540024 A CN107540024 A CN 107540024A CN 201710828090 A CN201710828090 A CN 201710828090A CN 107540024 A CN107540024 A CN 107540024A
- Authority
- CN
- China
- Prior art keywords
- kettle
- carbonate
- reaction
- cobalt
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of preparation method of spherical cobaltic-cobaltous oxide, process units and spherical cobaltic-cobaltous oxide, and material solution to cobalt carbonate granularity is continually fed into primary first-order equation kettle and reaches 8~10 microns.Transfer the material into again in secondary response kettle, be continually fed into material solution, reach 15~18 microns to cobalt carbonate granularity.Finally transfer the material into third-order reaction kettle, be continually fed into material solution and react to cobalt carbonate granularity and reach 22~25 microns.Cobalt ions solution and carbonate solution are continued through by Non-intermittent in each reactor so that reaction is lasting to be carried out, so as to improve the particle diameter uniformity of reaction efficiency and cobalt carbonate.Simultaneously according to the characteristics of reaction, constantly regulate response parameter, pH value, mixing speed, temperature is set also to be gradually reduced so that cobalt carbonate particle keeps spherical, while granularity is constantly increased.It is 15~25 μm thus finally to calcine obtained cobaltosic oxide particle size, and narrow particle size distribution, microscopic appearance are single spherical.
Description
Technical field
The present invention relates to lithium electricity positive electrode material precursor field, especially, is related to a kind of preparation of spherical cobaltic-cobaltous oxide
Method.Moreover, it relates to spherical cobaltic-cobaltous oxide made from a kind of preparation method including spherical cobaltic-cobaltous oxide with
And spherical cobaltic-cobaltous oxide process units.
Background technology
In recent ten years, due to being applied to secondary cell on a large scale with excellent chemical property, cobalt metal, especially
It is field of lithium ion battery anode.Ripe positive electrode mainly has cobalt acid lithium, LiMn2O4, nickel cobalt manganese in the market
Sour lithium, nickel cobalt lithium aluminate, LiFePO4 etc..Various material properties are different, slightly different using field.Cobalt acid lithium is due to its safety
The characteristics such as performance is good, energy density is high, capacitance is high, along with the rapid development of digital industry, it is made into various mobile phones, number
The battery of code-phase machine, is entered in daily life, and strong influence the life of people.Battery-grade cobaltosic oxide is made
For the primary raw material of cobalt acid lithium, its dosage explodes also with the demand of battery and significantly increased, and consumption is close to cobalt
70% or so of total burn-off.
The people of demand under the pressure of to(for) high capacity cell, the improvement of scientist and engineering staff for battery technology never stop
Only, the capacitance of cobalt acid lithium has become closer to theoretical level at present, but generally speaking, progress is limited, and off-capacity remains unchanged
It is the bottleneck of Mobile portable formula smart mobile phone, seriously reduces Consumer's Experience level.Therefore, people place hope on new battery material
Be announced to the world splendidly, what is more focused on is the sustained improvement of current material.Improve one by the granularity and pattern that improve cobaltosic oxide
It is directly the important method of improvement cobalt acid lithium electrical property recognized within the industry.The index that the preparation of cobaltosic oxide relates generally to is grain
Degree and pattern, downstream client are important to notice that high-tap density, big granularity, spherical morphology, the product of narrowly distributing.In order to simultaneously
Reach these targets, this turns into an industrial problem.
The content of the invention
The invention provides a kind of preparation method of spherical cobaltic-cobaltous oxide, process units and spherical cobaltic-cobaltous oxide, with
Solves the technical problem that existing cobaltosic oxide pattern is bad, size distribution is uneven.
The technical solution adopted by the present invention is as follows：
One aspect of the present invention provides a kind of preparation method of spherical cobaltic-cobaltous oxide, comprises the following steps：
Configure cobalt ions solution and carbonate solution.
Part thereof solution is added in primary first-order equation kettle, cobalt ions solution and carbon are continually fed into primary first-order equation kettle
Acid salt solution, and the reaction extremely generation under conditions of 40~60 DEG C, pH value are 7.0~7.6, mixing speed is 60~120rpm
Cobalt carbonate granularity reaches 8~10 microns.
Material in primary first-order equation kettle is transferred in secondary response kettle, it is molten to be continually fed into cobalt ions in secondary response kettle
Liquid and carbonate solution, and react under conditions of 40~60 DEG C, pH value are 7.0~7.6, mixing speed is 60~120rpm to
The cobalt carbonate granularity of generation reaches 15~18 microns.
Material in secondary response kettle is transferred in third-order reaction kettle, it is molten to be continually fed into cobalt ions in third-order reaction kettle
Liquid and carbonate solution, and react under conditions of 40~60 DEG C, pH value are 7.0~7.6, mixing speed is 60~120rpm to
The cobalt carbonate granularity of generation reaches 22~25 microns.
Cobalt carbonate in third-order reaction kettle is separated into calcining, obtains spherical cobaltic-cobaltous oxide.
Reaction temperature, pH value and mixing speed in wherein each reactor according to primary first-order equation kettle, secondary response kettle and
The order of third-order reaction kettle gradually reduces.
Further, in primary first-order equation kettle, reaction temperature is 50~55 DEG C, and pH value is 7.4~7.6, and mixing speed is
100~120rpm.
In secondary response kettle, reaction temperature be 45~50 DEG C, pH value be 7.2~7.4, mixing speed be 80~
100rpm。
In third-order reaction kettle, reaction temperature is 40~45 DEG C, and pH value is 7.0~7.2, and mixing speed is 60~80rpm.
Further, the reaction time in each reactor is according to primary first-order equation kettle, secondary response kettle and third-order reaction kettle
Order gradually rises.
Further, the reaction time in primary first-order equation kettle is 32~48 hours.
Reaction time in secondary response kettle is 64~76 hours.
Reaction time in third-order reaction kettle is 128~140 hours.
Further, the concentration of cobalt ions solution is 1.0~2.0M.The concentration of carbonate solution is 1.5~3.0M；It is each anti-
It is 1 to answer and the mol ratio of cobalt ions and carbonate is controlled when being reacted in kettle:2.0~2.5.
Further, the separation method of cobalt carbonate is centrifugal filtration.The calcining heat of cobalt carbonate is 600~800 DEG C, calcining
Time is 2~4 hours.
Further, the configuration temperature of cobalt ions solution and carbonate solution is 35~40 DEG C.
Further, one or more of the cobalt ions of cobalt ions solution in cobaltous sulfate or cobalt chloride.Carbonate is molten
One or more of the carbanion of liquid in sodium carbonate, ammonium hydrogen carbonate, sodium acid carbonate.
Another aspect of the present invention provides spherical cobaltic-cobaltous oxide made from the preparation method of above-mentioned spherical cobaltic-cobaltous oxide.
Present invention also offers a kind of process units of spherical cobaltic-cobaltous oxide, the process units of spherical cobaltic-cobaltous oxide is used
In the preparation method for implementing above-mentioned spherical cobaltic-cobaltous oxide, the process units of spherical cobaltic-cobaltous oxide include by conveying pipeline according to
Primary first-order equation kettle, secondary response kettle and the third-order reaction kettle of secondary connection.
The volume of primary first-order equation kettle, secondary response kettle and third-order reaction kettle gradually increases, and is equipped with subsider；Each reaction
Be continually fed into cobalt ions solution and carbonate solution in kettle, each reactor fill after material through subsider flow out cobalt ions solution and
Carbonate solution always flows into the material of volume, and to keep each reactor inner volume to balance, subsider sedimentation retention flows through material
Interior cobalt carbonate is simultaneously returned it in corresponding reactor.
The invention has the advantages that：The preparation method of above-mentioned spherical cobaltic-cobaltous oxide, on the one hand in each reactor
In cobalt ions solution and carbonate solution continued through by Non-intermittent so that reaction is lasting to be carried out, so as to improve reaction efficiency
With the particle diameter uniformity of cobalt carbonate.On the other hand material is shifted in each reactor, while according to the characteristics of reaction, constantly adjusted
Response parameter is saved, pH value is gradually reduced, stirs and constantly reduces, temperature is also gradually reduced so that cobalt carbonate particle keeps spherical,
Granularity is set constantly to increase simultaneously.It is 15~25 μm thus finally to calcine obtained cobaltosic oxide particle size, narrow particle size distribution, microcosmic
Pattern is single spherical.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
The accompanying drawing for forming the part of the application is used for providing a further understanding of the present invention, schematic reality of the invention
Apply example and its illustrate to be used to explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the XRD for the spherical cobaltic-cobaltous oxide that the preparation method of the spherical cobaltic-cobaltous oxide of the embodiment of the present invention 1 obtains
Figure；
Fig. 2 is the SEM for the spherical cobaltic-cobaltous oxide that the preparation method of the spherical cobaltic-cobaltous oxide of the embodiment of the present invention 1 obtains
Figure；
Fig. 3 is the particle size distribution figure for the cobalt carbonate that the preparation method of the spherical cobaltic-cobaltous oxide of the embodiment of the present invention 1 obtains；
Fig. 4 is the grain for the spherical cobaltic-cobaltous oxide that the preparation method of the spherical cobaltic-cobaltous oxide of the embodiment of the present invention 1 obtains
Spend distribution map；
Fig. 5 is the process units of the spherical cobaltic-cobaltous oxide of the present invention.
Description of reference numerals：100th, primary first-order equation kettle；200th, secondary response kettle；300th, third-order reaction kettle；400th, subsider；
410th, discharging tube；500th, feed tube.
Embodiment
Embodiments of the invention are described in detail below in conjunction with accompanying drawing, but the present invention can be defined by the claims
Implement with the multitude of different ways of covering.
Reference picture 5, the preferred embodiments of the present invention provide a kind of preparation method of spherical cobaltic-cobaltous oxide, including following
Step：
Configure cobalt ions solution and carbonate solution.
Part thereof solution is added in primary first-order equation kettle 100, it is molten to be continually fed into cobalt ions in primary first-order equation kettle 100
Liquid and carbonate solution, and react under conditions of 40~60 DEG C, pH value are 7.0~7.6, mixing speed is 60~120rpm to
The cobalt carbonate granularity of generation reaches 8~10 microns.
Material in primary first-order equation kettle 100 is transferred in secondary response kettle 200, persistently led in secondary response kettle 200
Enter cobalt ions solution and carbonate solution, and in the bar that 40~60 DEG C, pH value are 7.0~7.6, mixing speed is 60~120rpm
The cobalt carbonate granularity of reaction to generation reaches 15~18 microns under part.
Material in secondary response kettle 200 is transferred in third-order reaction kettle 300, persistently led in third-order reaction kettle 300
Enter cobalt ions solution and carbonate solution, and in the bar that 40~60 DEG C, pH value are 7.0~7.6, mixing speed is 60~120rpm
The cobalt carbonate granularity of reaction to generation reaches 22~25 microns under part.
Cobalt carbonate in third-order reaction kettle 300 is separated into calcining, obtains spherical cobaltic-cobaltous oxide.
Reaction temperature, pH value and mixing speed in wherein each reactor are according to the primary first-order equation kettle 100, secondary counter
Kettle 200 and the order of the third-order reaction kettle 300 is answered gradually to reduce.
The preparation method of existing cobaltosic oxide uses the reaction of the reactor or two discontinuous of a discontinuous more
Kettle is combined.Specifically in each reactor, cobalt ions solution and carbonate solution are passed through in reactor, when the liquid level in reactor
, it is necessary to stop feeding and stand the cobalt carbonate sedimentation layering so that being formed when reaching the top of reactor, supernatant is then extracted out,
Leave cobalt oxide precipitation and be used as crystal seed.Then the addition material solution into reactor is further continued for continue to react.During reaction, due to not
Energy continuous feed, therefore reaction efficiency is low, and the uniformity for reacting generation product is poor.When the reactor of two discontinuous is combined,
When the cobalt carbonate of generation is reacted in first reactor growing into certain particle diameter, it is transferred in second reactor, two anti-
To answer the reaction condition in kettle identical, do not do corresponding adjustment so that the pattern of cobalt carbonate is bad, and uniformity is poor, and finally
The particle diameter of obtained cobaltosic oxide is also smaller, it is difficult to reaches 15~25 μm.
In the present invention, cobalt carbonate is prepared using mode associated with three reactors.Fed in each reactor using lasting,
And not existing discontinuous charging.Continuing feeding manner can use the reactor with subsider 400 to realize, this kind of reactor
Connected with subsider 400, cobalt ions solution and carbonate solution are continually fed into reactor, when the certain liquid level for reaching reactor
During height, the partial material in reactor is flow in subsider 400, and wherein cobalt carbonate is back to after being settled in subsider 400
In reactor, and other solution are then discharged from subsider 400.Subsider 400 discharges the speed and cobalt ions solution, carbonic acid of solution
The two charging rate of salting liquid is identical so that the volume in reactor keeps balance.Due to being to continue charging in reactor, instead
It should be carried out continuously, hence it is evident that improve reaction efficiency；Meanwhile reacted relative to discontinuous needed opening and closing to stir every several hours
Mix, the phenomenon of the parameter such as regulation pH, persistently feed reactive mode during the course of the reaction without adjusting the parameters such as stirring and pH, reduce
The fluctuation of reaction condition, the risk and probability of maloperation are reduced, make the uniformity for the cobalt carbonate that reaction generates good, pattern
It is good.And the present invention uses different reaction conditions for the different stages of reaction, reaction is divided into three phases respectively once
Carried out in reactor 100, secondary response kettle 200 and third-order reaction kettle 300, the reaction condition of three stages of reaction is overall all 40
~60 DEG C, pH value be 7.0~7.6, in the range of mixing speed is 60~120rpm under conditions of suitable cobalt carbonate growth, simultaneously
Increase again with the particle diameter of cobalt carbonate, specific reaction condition is adjusted.Such as pH value is gradually reduced, on the one hand reduced
The consumption of ammonium bicarbonate solution, on the other hand reduces the remaining cobalt content in mother liquor；Stirring constantly reduces, and prevents from stirring shearing force
It is excessive, reduce short grained generation, avoid granularity from not growing up；Temperature is gradually reduced, and makes granular grows even closer, jolt ramming
Density is relatively higher, while granularity is constantly increased.And reacted in three reactors, the reaction bar in each reactor
Part is different, and the reaction condition in each reactor is constant, is easy to production to regulate and control.It is after the completion of each elementary reaction, this is anti-
All materials in kettle are answered to be transferred in next reactor.Can in addition, being previously added part thereof solution in primary first-order equation kettle 100
The pH helped to maintain in kettle is relatively stable, avoids pH during initial charge from larger fluctuation occur.
The invention has the advantages that：The preparation method of above-mentioned spherical cobaltic-cobaltous oxide, on the one hand in each reactor
In cobalt ions solution and carbonate solution continued through by Non-intermittent so that reaction is lasting to be carried out, so as to improve reaction efficiency
With the particle diameter uniformity of cobalt carbonate.On the other hand material is shifted in each reactor, while according to the characteristics of reaction, constantly adjusted
Response parameter is saved, pH value is gradually reduced, stirs and constantly reduces, temperature is also gradually reduced so that cobalt carbonate particle keeps spherical,
Granularity is set constantly to increase simultaneously.It is 15~25 μm thus finally to calcine obtained cobaltosic oxide particle size, narrow particle size distribution, microcosmic
Pattern is single spherical.
Alternatively, in primary first-order equation kettle 100, reaction temperature is 50~55 DEG C, and pH value is 7.4~7.6, and mixing speed is
100~120rpm.
In secondary response kettle 200, reaction temperature be 45~50 DEG C, pH value be 7.2~7.4, mixing speed be 80~
100rpm。
In third-order reaction kettle 300, reaction temperature be 40~45 DEG C, pH value be 7.0~7.2, mixing speed be 60~
80rpm。
Reaction condition in above-mentioned each reactor the reaction temperature of each reactor, pH value and stirs in addition to above-mentioned condition is met
The order that speed is mixed also according to the primary first-order equation kettle 100, secondary response kettle 200 and the third-order reaction kettle 300 gradually drops
It is low.Under reaction condition in above-mentioned each reactor, the reaction condition of each reactor is more suitable for the cobalt carbonate particle in the stage
Growth, makes its holding spherical, while granularity is constantly increased, and particle size distribution is narrow.
Alternatively, the reaction time in each reactor is according to primary first-order equation kettle 100, secondary response kettle 200 and third-order reaction
The order of kettle 300 gradually rises.
Bigger with the radius of cobalt carbonate particle, the growth rate of particle is slower, so being carried out continuously with reaction,
Reaction time needs more to grow.
Alternatively, the reaction time in primary first-order equation kettle 100 is 32~48 hours.During reaction in secondary response kettle 200
Between be 64~76 hours.Reaction time in third-order reaction kettle 300 is 128~140 hours.
Under this condition, the reaction time in each reactor is of convenient length, and fully meets cobalt carbonate particle in the reactor
Conditioned growth demand, while when the condition that cobalt carbonate particle is grown in the reactor limits its continued growth timely
Next reactor is transferred to, the uniformity of cobalt carbonate particle is good and pattern so as to improving, and avoids cobalt carbonate particle from existing
It can not be grown in reactor and cause raw material, the energy and waste of time.
Alternatively, the concentration of cobalt ions solution is 1.0~2.0M.The concentration of carbonate solution is 1.5~3.0M.
If the two concentration is too low, production efficiency is too low, and concentration is too high, solution in the winter time when easily crystallize, convey solution when
Easily block pipeline.It is 1 that the mol ratio of cobalt ions and carbonate is controlled when being reacted in each reactor:2.0~2.5, in the condition
The lower remaining cobalt content that can be reduced to greatest extent in mother liquor.
Alternatively, the separation method of cobalt carbonate is centrifugal filtration.The calcining heat of cobalt carbonate is 600~800 DEG C, during calcining
Between be 2~4 hours.
Centrifuge can be used to carry out washing and filtering to the solution that reaction is completed, obtain cobalt carbonate.Cobalt carbonate is 600~800
Calcined under conditions of DEG C 2~4 hours and obtained that granularity is 15~25 μm, tap density is 2.0~2.7g/cm3, size distribution
Narrow, microscopic appearance is single spherical big particle diameter high-density spherical cobaltic-cobaltous oxide.
Alternatively, the configuration temperature of cobalt ions solution and carbonate solution is 35~40 DEG C.
Alternatively, one or more of the cobalt ions of cobalt ions solution in cobaltous sulfate or cobalt chloride.Carbonate solution
One or more of the carbanion in sodium carbonate, ammonium hydrogen carbonate, sodium acid carbonate.
Another aspect of the present invention provides spherical cobaltic-cobaltous oxide made from the preparation method of above-mentioned spherical cobaltic-cobaltous oxide.
Present invention also offers a kind of process units of spherical cobaltic-cobaltous oxide, the process units of spherical cobaltic-cobaltous oxide is used
In the preparation method for implementing above-mentioned spherical cobaltic-cobaltous oxide, reference picture 5, the process units of spherical cobaltic-cobaltous oxide includes passing through
Primary first-order equation kettle 100, secondary response kettle 200 and the third-order reaction kettle 300 that conveying pipeline is sequentially connected.It is primary first-order equation kettle 100, secondary
The volume of reactor 200 and third-order reaction kettle 300 gradually increases, and is equipped with subsider 400；Cobalt is continually fed into each reactor
Solion and carbonate solution, each reactor is filled flows out cobalt ions solution and carbonate solution after material through subsider 400
Total material for flowing into volume, to keep each reactor inner volume to balance, the sedimentation retention of subsider 400 flows through the carbonic acid in material
Cobalt is simultaneously returned it in corresponding reactor.
Material between primary first-order equation kettle 100, secondary response kettle 200 and third-order reaction kettle 300 can be shifted by conveying pipeline,
Conveying pipeline is provided with dehvery pump.Cobalt ions solution and carbonate solution pass through corresponding feed tube respectively.The top of subsider 400
Connected with respective reaction kettle, top is provided with discharging tube 410.The material of discharge enters in subsider 400 in reactor, and cobalt carbonate sinks
Lower and be back in reactor, other materials are discharged through discharging tube 410.
The volume of primary first-order equation kettle 100, secondary response kettle 200 and third-order reaction kettle 300 gradually increases so that latter reaction
After receiving the material in previous reactor in kettle, capacity is molten less than that can continue to be passed through more volume cobalt ions solution and carbonate
Liquid, keep the volumetric balance in reactor by subsider 400 again after it reaches respective volume, continue to react.And with carbon
The volume increase of sour cobalt, it is also desirable to which larger reaction vessel provides larger reaction compartment, so that its continued growth.If three
Individual reactor volume is consistent do not increase successively if, secondary and third-order reaction will be by due to finite volume, in reactor
Cobalt carbonate precipitation is full of and can not continue to feed, and particle will not reach more than 22 microns.Volume such as primary first-order equation kettle 100 can be with
Volume for 1 cubic metre, secondary response kettle 200 can be 3 cubic metres, and the volume of third-order reaction kettle 300 can be 10 cubic metres.
Subsequent reactions kettle is usually 2~3 times of front volume.
Embodiment 1
1st, cobalt liquid configures：Configure 1.0mol/L cobalt chloride solution.
2nd, sodium carbonate configures：Configure 1.5mol/L sodium carbonate liquor.
3rd, by after the completion of 50L primary first-order equation kettle cleaning, 2.0L sodium carbonate liquors are added as bottom liquid.
4th, primary first-order equation：By temperature control at 55 DEG C, stir as 120 revolutions per minute, pH value 7.6, at the same be pumped into cobalt liquid and
Sodium carbonate liquor.After reaction 32 hours, detection granularity is 9.5 microns.
5th, the material of primary first-order equation is all transferred in 150L secondary response kettle 200.
6th, secondary response：In secondary response kettle 200, by temperature control at 50 DEG C, stir and be for 100 revolutions per minute, pH value
7.4, while it is pumped into cobalt liquid and sodium carbonate liquor.After reaction 64 hours, detection granularity is 16.2 microns, stops charging.Will reaction
Material be all transferred in 450L third-order reaction kettle 300.
7th, third-order reaction：In third-order reaction kettle 300, by temperature control at 45 DEG C, stir and be for 80 revolutions per minute, pH value
7.2, while it is pumped into cobalt liquid and ammoniacal liquor.After reaction 128 hours, detection granularity is 22.6 microns, stops charging.
8th, centrifuge：Obtained slurry will be reacted and carry out centrifugal dehydration, then with 80 DEG C of hot wash 30 minutes, obtained
Cobalt carbonate.The granularity of cobalt carbonate is tested, test result is as shown in Figure 3.It can be seen that the size distribution of cobalt carbonate is concentrated, it is homogeneous
Property is good.
9th, cobalt carbonate is calcined 3 hours in 750 DEG C of rotary kiln, obtained cobaltosic oxide XRD as shown in figure 1,
Shown in SEM and Fig. 2, image is simple cobaltosic oxide, and pattern is uniform spherical.The granularity of cobaltosic oxide is surveyed
Examination, test result are as shown in Figure 3.It can be seen that the size distribution of cobaltosic oxide is concentrated, homogeneity is good.
Embodiment 2
1st, cobalt liquid configures：Configure 1.5mol/L cobalt sulfate solution.
2nd, ammonium hydrogen carbonate configures：Configure 2.0mol/L ammonium bicarbonate soln.
3rd, by after the completion of 50L primary first-order equation kettle cleaning, 3.0L ammonium hydrogen carbonate is added as bottom liquid.
4th, primary first-order equation：By temperature control at 50 DEG C, stir as 100 revolutions per minute, pH value 7.4, at the same be pumped into cobalt liquid and
Ammonium bicarbonate soln.After reaction 40 hours, detection granularity is 8.2 microns.
5th, the material of primary first-order equation is all transferred in 150L secondary response kettle 200.
6th, secondary response：In secondary response kettle 200, by temperature control at 45 DEG C, stir and be for 80 revolutions per minute, pH value
7.2, while it is pumped into cobalt liquid and ammonium bicarbonate soln.After reaction 70 hours, detection granularity is 16.6 microns, stops charging.Will be anti-
The material answered all is transferred in 450L third-order reaction kettle 300.
7th, third-order reaction：In third-order reaction kettle 300, by temperature control at 40 DEG C, stir and be for 60 revolutions per minute, pH value
7.0, while it is pumped into cobalt liquid and ammonium bicarbonate soln.After reaction 134 hours, detection granularity is 24.1 microns, stops charging.
8th, centrifuge：Obtained slurry will be reacted and carry out centrifugal dehydration, then with 80 DEG C of hot wash 30 minutes, obtained
Cobalt carbonate.
9th, cobalt carbonate is calcined 2 hours in 800 DEG C of rotary kiln, obtained cobaltosic oxide.
Embodiment 3
1st, cobalt liquid configures：Configure 2.0mol/L carbonic acid cobalt liquor.
2nd, sodium acid carbonate configures：Configure 3.0mol/L sodium bicarbonate solution.
3rd, by after the completion of 50L primary first-order equation kettle cleaning, 2.5L sodium bicarbonate solutions are added as bottom liquid.
4th, primary first-order equation：By temperature control at 53 DEG C, stir as 110 revolutions per minute, pH value 7.5, at the same be pumped into cobalt liquid and
Sodium bicarbonate solution.After reaction 48 hours, detection granularity is 9.8 microns.
5th, the material of primary first-order equation is all transferred in 150L secondary response kettle 200.
6th, secondary response：In secondary response kettle 200, by temperature control at 48 DEG C, stir and be for 90 revolutions per minute, pH value
7.3 while it is pumped into cobalt liquid and sodium bicarbonate solution.After reaction 64 hours, detection granularity is 17.5 microns, stops charging.Will be anti-
The material answered all is transferred in 450L third-order reaction kettle 300.
7th, third-order reaction：In third-order reaction kettle 300, by temperature control at 42 DEG C, stir and be for 70 revolutions per minute, pH value
7.1, while it is pumped into cobalt liquid and sodium bicarbonate solution.After reaction 140 hours, detection granularity is 24.6 microns, stops charging.
8th, centrifuge：Obtained slurry will be reacted and carry out centrifugal dehydration, then with 80 DEG C of hot wash 30 minutes, obtained
Cobalt carbonate.
9th, cobalt carbonate is calcined 4 hours in 600 DEG C of rotary kiln, obtained cobaltosic oxide.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of spherical cobaltic-cobaltous oxide, it is characterised in that comprise the following steps：
Configure cobalt ions solution and carbonate solution；
Part thereof solution is added in primary first-order equation kettle (100), is continually fed into the primary first-order equation kettle (100) described
Cobalt ions solution and the carbonate solution, and 40~60 DEG C, pH value be 7.0~7.6, mixing speed be 60~120rpm's
Under the conditions of reaction to generation cobalt carbonate granularity reach 8~10 microns；
Material in the primary first-order equation kettle (100) is transferred in secondary response kettle (200), in the secondary response kettle
(200) the cobalt ions solution and the carbonate solution are continually fed into, and is 7.0~7.6, stirs in 40~60 DEG C, pH value
The cobalt carbonate granularity that speed is mixed as reaction to generation under conditions of 60~120rpm reaches 15~18 microns；
Material in the secondary response kettle (200) is transferred in third-order reaction kettle (300), in the third-order reaction kettle
(300) the cobalt ions solution and the carbonate solution are continually fed into, and is 7.0~7.6, stirs in 40~60 DEG C, pH value
The cobalt carbonate granularity that speed is mixed as reaction to generation under conditions of 60~120rpm reaches 22~25 microns；
Cobalt carbonate in the third-order reaction kettle (300) is separated into calcining, obtains spherical cobaltic-cobaltous oxide；
Reaction temperature, pH value and mixing speed in wherein each reactor are according to the primary first-order equation kettle (100), described secondary
The order of reactor (200) and the third-order reaction kettle (300) gradually reduces.
2. the preparation method of spherical cobaltic-cobaltous oxide according to claim 1, it is characterised in that
In the primary first-order equation kettle (100), reaction temperature is 50~55 DEG C, and pH value is 7.4~7.6, mixing speed is 100~
120rpm；
In the secondary response kettle (200), reaction temperature is 45~50 DEG C, and pH value is 7.2~7.4, mixing speed is 80~
100rpm；
In the third-order reaction kettle (300), reaction temperature is 40~45 DEG C, and pH value is 7.0~7.2, mixing speed is 60~
80rpm。
3. the preparation method of spherical cobaltic-cobaltous oxide according to claim 1, it is characterised in that the reaction in each reactor
Time according to the primary first-order equation kettle (100), the secondary response kettle (200) and the third-order reaction kettle (300) order by
Edge up height.
4. the preparation method of spherical cobaltic-cobaltous oxide according to claim 3, it is characterised in that
Reaction time in the primary first-order equation kettle (100) is 32~48 hours；
Reaction time in the secondary response kettle (200) is 64~76 hours；
Reaction time in the third-order reaction kettle (300) is 128~140 hours.
5. the preparation method of spherical cobaltic-cobaltous oxide according to claim 1, it is characterised in that the cobalt ions solution
Concentration is 1.0~2.0M；The concentration of the carbonate solution is 1.5~3.0M.
6. the preparation method of spherical cobaltic-cobaltous oxide according to claim 1, it is characterised in that when being reacted in each reactor
It is 1 to control the mol ratio of the cobalt ions and the carbonate:2.0~2.5.
7. the preparation method of spherical cobaltic-cobaltous oxide according to claim 1, it is characterised in that the separation of the cobalt carbonate
Method is centrifugal filtration；The calcining heat of the cobalt carbonate is 600~800 DEG C, and calcination time is 2~4 hours；The cobalt ions
The configuration temperature of solution and the carbonate solution is 35~40 DEG C.
8. according to the preparation method of spherical cobaltic-cobaltous oxide according to any one of claims 1 to 8, it is characterised in that described
One or more of the cobalt ions of cobalt ions solution in cobaltous sulfate or cobalt chloride；The carbanion of the carbonate solution
One or more in sodium carbonate, ammonium hydrogen carbonate, sodium acid carbonate.
A kind of 9. spherical four oxidation made from preparation method of spherical cobaltic-cobaltous oxide according to any one of claims 1 to 8
Three cobalts.
10. a kind of process units of spherical cobaltic-cobaltous oxide, it is characterised in that the process units of the spherical cobaltic-cobaltous oxide is used
In implement claim 1~8 any one of spherical cobaltic-cobaltous oxide preparation method, the spherical cobaltic-cobaltous oxide
Process units includes primary first-order equation kettle (100), secondary response kettle (200) and the third-order reaction kettle being sequentially connected by conveying pipeline
(300)；
The volume of the primary first-order equation kettle (100), the secondary response kettle (200) and the third-order reaction kettle (300) gradually increases
Greatly, and it is equipped with subsider (400)；Cobalt ions solution and carbonate solution are continually fed into each reactor, each reactor is filled
The cobalt ions solution is flowed out through subsider (400) after material and the carbonate solution always flows into the material of volume, to protect
Each reactor inner volume balance is held, subsider (400) the sedimentation retention flows through the cobalt carbonate in material and returns it to phase
In the reactor answered.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710828090.7A CN107540024A (en) | 2017-09-14 | 2017-09-14 | Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710828090.7A CN107540024A (en) | 2017-09-14 | 2017-09-14 | Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107540024A true CN107540024A (en) | 2018-01-05 |
Family
ID=60964297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710828090.7A Pending CN107540024A (en) | 2017-09-14 | 2017-09-14 | Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107540024A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109319846A (en) * | 2018-12-06 | 2019-02-12 | 怀化学院 | The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide |
| CN110217832A (en) * | 2019-04-23 | 2019-09-10 | 金川集团股份有限公司 | A kind of bulky grain narrow ditribution mixes the preparation method of aluminium cobaltosic oxide |
| CN110217831A (en) * | 2019-04-23 | 2019-09-10 | 金川集团股份有限公司 | A kind of preparation method of high voltage cobalt acid lithium large granular spherical narrow ditribution cobaltosic oxide |
| CN110342587A (en) * | 2019-04-23 | 2019-10-18 | 金川集团股份有限公司 | A kind of big granularity cobaltosic oxide preparation method of narrow ditribution |
| CN113277568A (en) * | 2021-05-14 | 2021-08-20 | 浙江中金格派锂电产业股份有限公司 | Preparation method of high-conductivity lithium cobalt oxide positive electrode material |
| CN113716619A (en) * | 2021-09-30 | 2021-11-30 | 衢州华友钴新材料有限公司 | Preparation method of large-particle spherical doped cobalt carbonate with uniformly distributed particle size |
| WO2023024591A1 (en) * | 2021-08-27 | 2023-03-02 | 广东邦普循环科技有限公司 | Crystal-transformed precursor and preparation method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583584A (en) * | 2012-03-27 | 2012-07-18 | 湖南雅城新材料发展有限公司 | Preparation method of spherical cobaltosic oxide |
| CN103803663A (en) * | 2012-11-06 | 2014-05-21 | 宁波科博特钴镍有限公司 | Production method of spherical tricobalt tetroxide |
| CN106784800A (en) * | 2017-01-12 | 2017-05-31 | 江苏凯力克钴业股份有限公司 | A kind of power lithium-ion battery activity spherical cobaltosic oxide and preparation method thereof |
-
2017
- 2017-09-14 CN CN201710828090.7A patent/CN107540024A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583584A (en) * | 2012-03-27 | 2012-07-18 | 湖南雅城新材料发展有限公司 | Preparation method of spherical cobaltosic oxide |
| CN103803663A (en) * | 2012-11-06 | 2014-05-21 | 宁波科博特钴镍有限公司 | Production method of spherical tricobalt tetroxide |
| CN106784800A (en) * | 2017-01-12 | 2017-05-31 | 江苏凯力克钴业股份有限公司 | A kind of power lithium-ion battery activity spherical cobaltosic oxide and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109319846A (en) * | 2018-12-06 | 2019-02-12 | 怀化学院 | The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide |
| CN110217832A (en) * | 2019-04-23 | 2019-09-10 | 金川集团股份有限公司 | A kind of bulky grain narrow ditribution mixes the preparation method of aluminium cobaltosic oxide |
| CN110217831A (en) * | 2019-04-23 | 2019-09-10 | 金川集团股份有限公司 | A kind of preparation method of high voltage cobalt acid lithium large granular spherical narrow ditribution cobaltosic oxide |
| CN110342587A (en) * | 2019-04-23 | 2019-10-18 | 金川集团股份有限公司 | A kind of big granularity cobaltosic oxide preparation method of narrow ditribution |
| CN110342587B (en) * | 2019-04-23 | 2021-06-29 | 金川集团股份有限公司 | Preparation method of narrow-distribution large-particle-size cobaltosic oxide |
| CN110217832B (en) * | 2019-04-23 | 2021-08-27 | 金川集团股份有限公司 | Preparation method of large-particle narrow-distribution aluminum-doped cobaltosic oxide |
| CN110217831B (en) * | 2019-04-23 | 2021-08-27 | 金川集团股份有限公司 | Preparation method of large-particle spherical narrow-distribution cobaltosic oxide for high-voltage lithium cobaltate |
| CN113277568A (en) * | 2021-05-14 | 2021-08-20 | 浙江中金格派锂电产业股份有限公司 | Preparation method of high-conductivity lithium cobalt oxide positive electrode material |
| WO2023024591A1 (en) * | 2021-08-27 | 2023-03-02 | 广东邦普循环科技有限公司 | Crystal-transformed precursor and preparation method therefor |
| GB2617938A (en) * | 2021-08-27 | 2023-10-25 | Guangdong Brunp Recycling Technology Co Ltd | Crystal-transformed precursor and preparation method therefor |
| CN113716619A (en) * | 2021-09-30 | 2021-11-30 | 衢州华友钴新材料有限公司 | Preparation method of large-particle spherical doped cobalt carbonate with uniformly distributed particle size |
| CN113716619B (en) * | 2021-09-30 | 2023-08-04 | 衢州华友钴新材料有限公司 | Preparation method of large-particle spherical doped cobalt carbonate with uniform particle size distribution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107540024A (en) | Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide | |
| JP5626382B2 (en) | Nickel-cobalt composite hydroxide and method for producing the same | |
| CN104201367B (en) | High density small particle nickel cobalt manganese hydroxide and preparation method thereof | |
| CN107324405B (en) | A kind of lithium nickel cobalt manganese oxide precursor and preparation method thereof and lithium ion battery by the precursor preparation | |
| CN108264097A (en) | A kind of preparation method of anode material for lithium-ion batteries bulky grain presoma | |
| JP6201895B2 (en) | Method for producing nickel cobalt manganese composite hydroxide | |
| CN110217832A (en) | A kind of bulky grain narrow ditribution mixes the preparation method of aluminium cobaltosic oxide | |
| CN108807968A (en) | Nickel-cobalt-manganese ternary persursor material and its synthetic method | |
| CN108807976A (en) | Nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution and preparation method thereof | |
| CN108365214A (en) | A kind of high-performance small particle ternary anode material precursor and preparation method thereof | |
| CN113373517B (en) | High-nickel single crystal small-particle ternary precursor and continuous preparation method thereof | |
| CN104201368B (en) | Lithium battery ternary material precursor nickel cobalt manganese hydroxide and preparation method thereof | |
| CN107293744A (en) | A kind of high voltage class monocrystalline tertiary cathode material and preparation method thereof | |
| CN109422297B (en) | Method for regulating and controlling nucleation in crystallization process of nickel-cobalt-manganese precursor | |
| CN106745335A (en) | A kind of preparation method from growth crystal seed regulation and control nickle cobalt lithium manganate growth | |
| CN105271441A (en) | Preparation method of battery-grade large-grained cobaltosic oxide | |
| CN104649336B (en) | A kind of preparation method of spherical nickel-cobalt aluminium hydroxide presoma | |
| CN103165878A (en) | Preparation method of spherical nickel-manganese binary material | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| CN111732131B (en) | Preparation method of core-shell structure ternary cathode material | |
| CN104418388A (en) | Process and device for continuous production of superfine cobalt carbonate powder | |
| CN108767248A (en) | Prepare the device of the nickel-cobalt-manganese ternary material precursor material of narrow particle diameter distribution | |
| CN108706638A (en) | A kind of preparation method of the fine nucleus of ternary precursor | |
| CN109354077A (en) | A kind of ternary precursor and preparation method thereof of polycrystalline form | |
| CN103803663A (en) | Production method of spherical tricobalt tetroxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180105 |