CN109179516A - Mix aluminium little particle spherical cobaltic-cobaltous oxide with and preparation method thereof - Google Patents
Mix aluminium little particle spherical cobaltic-cobaltous oxide with and preparation method thereof Download PDFInfo
- Publication number
- CN109179516A CN109179516A CN201811275016.8A CN201811275016A CN109179516A CN 109179516 A CN109179516 A CN 109179516A CN 201811275016 A CN201811275016 A CN 201811275016A CN 109179516 A CN109179516 A CN 109179516A
- Authority
- CN
- China
- Prior art keywords
- aluminium
- little particle
- particle spherical
- cobaltous oxide
- cobalt
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
Abstract
The present invention relates to battery material field, in particular to one kind mix aluminium little particle spherical cobaltic-cobaltous oxide with and preparation method thereof.The intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide, the following steps are included: carrying out multiple crystallization reaction under the conditions of 30-60 DEG C after the ratio of the metallic solution containing aluminium and cobalt and precipitant solution with volume ratio for 1:0.8-1.5 is mixed, the crystal grain of required granularity is obtained；Then carry out isolated supernatant liquor and final slurry；Then the final slurry progress is sintered described in obtaining stage by stage and mixes aluminium little particle spherical cobaltic-cobaltous oxide.The synthesis technology is simple, reacts easily controllable, reaction process is pollution-free, easy to industrialized production.And the cobaltosic oxide aluminium element being prepared is evenly distributed, surface topography rule, good sphericity, tap density are high.
Description
Technical field
The present invention relates to battery material field, in particular to one kind mix aluminium little particle spherical cobaltic-cobaltous oxide and
Preparation method.
Background technique
In anode material for lithium-ion batteries, LiCoO2The principal status of public economy is occupy always, this is because LiCoO2It is very suitable to lithium
The embedding of ion takes off, and has many advantages, such as that voltage is high, discharge steady, specific energy height, good cycle, preparation process are simple, Neng Goushi
Answer high current charge-discharge.Little particle cobaltosic oxide is mainly used to prepare high magnification cobalt acid lithium.Common small currently on the market
Grain cobaltosic oxide have tap density is low, sphericity is poor, doped chemical defect unevenly distributed, this will result in lithium from
Sub- cycle performance of battery difference and stability are weak etc..
Summary of the invention
The present invention provides a kind of intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide, synthesis technology letters
It is single, react easily controllable, reaction process is pollution-free, easy to industrialized production.
The present invention also provides one kind to mix aluminium little particle spherical cobaltic-cobaltous oxide, which is evenly distributed, surface shape
Looks rule, good sphericity, tap density are high.
The present invention is implemented as follows:
A kind of intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide, comprising the following steps:
After the ratio of metallic solution containing aluminium and cobalt and precipitant solution with volume ratio for 1:0.8-1.5 is mixed
Multiple crystallization reaction is carried out under the conditions of 30-60 DEG C, obtains the crystal grain of required granularity；
Then carry out isolated supernatant liquor and final slurry；
Then the final slurry progress is sintered described in obtaining stage by stage and mixes aluminium little particle spherical cobaltic-cobaltous oxide.
One kind mixing aluminium little particle spherical cobaltic-cobaltous oxide, aoxidizes three by above-mentioned intermittent aluminium little particle spherical shape four of mixing
The preparation method of cobalt is prepared.
The beneficial effects of the present invention are: the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide of the present invention passes through
Reaction temperature, the ratio of reaction raw materials and calcining manners are controlled, so that the cobaltosic oxide being prepared, with aluminium element point
The advantages that cloth is uniform, surface topography is regular, good sphericity, high tap density.Meanwhile the process flow is simple, reaction is easy to control
System, reaction process is pollution-free, easy to industrialized production.And the resistance to mistake of cobalt acid lithium of the little particle spherical cobaltic-cobaltous oxide preparation of synthesis
It fills, has many advantages, such as high circulation volume conservation rate, better stability and chemical property.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described.
Fig. 1 is the grain size distribution for the cobaltosic oxide that embodiment 2 provides；
Fig. 2 is the cobaltosic oxide EDS figure that embodiment 1 provides；
Fig. 3 is the cobaltosic oxide EDS figure that embodiment 2 provides；
Fig. 4 is the cobaltosic oxide EDS figure that embodiment 3 provides；
Fig. 5 is the cobaltosic oxide EDS figure that comparative example 1 provides；
Fig. 6 is the cobaltosic oxide EDS figure that comparative example 2 provides；
Fig. 7 is the cobaltosic oxide EDS figure that comparative example 3 provides；
Fig. 8 is the cobaltosic oxide EDS figure that comparative example 4 provides；
Fig. 9 is the cobaltosic oxide EDS figure that comparative example 5 provides；
Figure 10 is the cobaltosic oxide EDS figure that comparative example 6 provides.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to the embodiment of the present invention mix aluminium little particle spherical cobaltic-cobaltous oxide with and preparation method thereof carry out specifically
It is bright.
A kind of intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide, comprising the following steps:
S1, metallic solution and precipitating reagent solvent are prepared respectively:
Respectively using water dissolution cobalt source and silicon source, then again cobalt source solution and silicon source solution be mixed to get containing aluminium
With the metallic solution of cobalt.Cobalt source and silicon source are first dissolved to obtain solution respectively, are more advantageous to being uniformly mixed for cobalt source and silicon source,
Then guarantee that the cobaltosic oxide Elemental redistribution being prepared is uniform, good sphericity promotes its performance.
Further, the mass ratio of cobalt and aluminium is 100:0.01-2.5 in metallic solution.The matter of cobalt and aluminium in metallic solution
Amount is than that can guarantee that cobalt and aluminium content are suitable in the cobaltosic oxide being prepared, and then guarantee four oxidations three using aforementioned proportion
Cobalt is with good performance.
Further, cobalt source is cobalt salt, the cobalt salt in cobaltous sulfate, cobalt chloride and cobalt nitrate any one or extremely
It is two kinds few.
Silicon source is aluminium salt, the aluminium salt in aluminum nitrate, aluminum sulfate and aluminium chloride any one or at least two.
Precipitant solution is the solution obtained after mixing precipitating reagent with water, it is preferable that the precipitating reagent is carbonate, more excellent
Choosing, the carbonate be ammonium hydrogen carbonate, ammonium carbonate, sodium carbonate, in sodium bicarbonate any one or at least two.
The concentration of precipitant solution be 200-300g/L, using above-mentioned concentration can guarantee precipitating reagent well with cobalt, aluminium
Precipitating is formed, guarantees yield.
S2, crystallization reaction；
Metallic solution is mixed with precipitant solution cocurrent, then mixing speed is 200-600rpm, and temperature is 30-60 DEG C
Under the conditions of carry out crystallization reaction to obtain grain graininess being 2.0-3.0 microns of reaction.Specifically adding 500- in reaction kettle
1000L precipitant solution promotes sedimentation effect, then will heat up to after 30-60 DEG C, metallic solution is molten with precipitating reagent as bottom liquid
Liquid is mixed in manner of cocurrent flow, and liquid is stirred in mixed process, until reaction kettle is full, then stops charging, and continue
Stirring and heat preservation, obtain the particle with certain partial size.
Metallic solution is mixed by the way of cocurrent with precipitant solution, can be further ensured that in precipitant solution
Carbanion can be fully uniformly mixed with cobalt, the aluminium in metallic solution, then guarantee be prepared four oxidation three
Aluminium element is evenly distributed in cobalt.
Meanwhile nucleus can not only be made to carry out good package to aluminium, cobalt using above-mentioned mixing speed, promote package
Uniformity, while reducing the damage of nucleus, guarantee growing up for nucleus, guarantee the spherical shape of the subsequent cobaltosic oxide being prepared
The integrality of structure.And it can guarantee that crystallization reaction has good rate, can then guarantee to prepare within this temperature range
The integrality of the structure of obtained nucleus.
Further, the volume ratio of metallic solution and precipitant solution is 1:0.8-1.5, controls metallic solution and precipitating reagent
The ratio of solution promotes sedimentation effect, more conducively promotion yield.
Further, the flow of metallic solution is 400-900L/h, and the precipitant solution flow is 500-900L/h.Control
The flow of metallic solution processed and precipitant solution can effectively control the speed that nucleus is formed and grown up, then guarantee nucleus energy
It is spherical well to guarantee that the subsequent cobaltosic oxide being prepared has for enough stable and lasting growths, and surface topography rule.
Then when the granularity for the nucleus that crystallization reaction obtains for the first time is 2.0-3.0 microns, it is clear to carry out isolated upper layer
Liquid and the first slurry, the particle in the first slurry are only the lesser particle of granularity, and particle surface relative coarseness, irregularly.Cause
This, needs to carry out the first slurry again multiple circulation crystallization reaction, promotes growing up for the first slurry endoparticle, specifically, by the
It is anti-that one slurry mixes the progress i.e. first time circulation crystallization of second of crystallization reaction with the metallic solution and the precipitant solution
It answers, the flow and ratio of second of crystallization reaction metallic solution and precipitant solution and the flow of crystallization reaction and ratio one for the first time
It causes, nucleus is grown, is obtained when the granularity for the nucleus that first time circulation crystallization obtains relative to crystallization reaction for the first time
After nucleus increases 0.1-0.3 microns, separation obtains the second slurry, and carries out second of circulation crystallization to the second slurry, so
Reciprocation cycle, crystallization, until the granularity of the nucleus in finally obtained slurry is the granularity of required nucleus.
The nucleus granularity that crystallization reaction obtains for the first time is relatively large, after being the formation for the ease of observation nucleus and being convenient for
The growth of continuous nucleus then carries out the nucleus that raw material is wrapped up in circulation crystallization reaction repeatedly with the rate of 0.1-0.3 micron/time, promotees
Into the growth of nucleus, and guarantee the structural integrity for the nucleus being prepared, finally obtains the crystal grain containing required granularity, each grain
The amount of increase of degree is consistent.
Isolated final slurry is then carried out, final slurry is then washed and is centrifuged, and solid matter in slurry is removed
Ion or solvent remained on surface, and remove aqueous solution extra in slurry.
S3, it is sintered stage by stage；
Then the final slurry after centrifugation is sintered stage by stage, specifically, by the final slurry at 300-550 DEG C
At a temperature of be sintered 2-4 hours after, then 700-1000 DEG C at a temperature of be sintered 4-7 hours.Sintering can make water stage by stage
Point and oxygen discharge stage by stage, avoid being heated to high temperature suddenly and make vapor and carbon dioxide quick release simultaneously, and a large amount of
Vapor and oxygen the nucleus of structural integrity is impacted, be easy to cause nucleating surface to rupture, four then destroyed
The structure of Co 3 O.Therefore, using being sintered stage by stage, gas can be reduced stage by stage and slow release vapor and oxygen
Structural damage to cobaltosic oxide then guarantees cobaltosic oxide surface topography rule, the good sphericity, vibration being prepared
Real density is high.
Specifically, 300-550 DEG C at a temperature of be sintered, enable to the moisture in nucleus to become vapor, then delay
It is slow to overflow nucleus, then remove moisture removal, and decompose reaction in 700-1000 DEG C of at a temperature of sintering nucleus, production titanium dioxide
Carbon and cobaltosic oxide.
The embodiment of the present invention also provides one kind and mixes aluminium little particle spherical cobaltic-cobaltous oxide, and intermittent to mix aluminium small by above-mentioned
The preparation method of particle spherical cobaltic-cobaltous oxide is prepared.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of intermittent preparation methods for mixing aluminium little particle spherical cobaltic-cobaltous oxide, including following step
It is rapid:
S1, metallic solution and precipitating reagent solvent are prepared respectively:
It is utilized respectively deionized water dissolving aluminum sulfate and cobalt chloride, then mixes aluminum sulfate solution and cobalt chloride solution,
The metallic solution containing aluminium and cobalt is obtained, cobalt ions and aluminium ion are respectively 100g/L and 0.68g/L in metallic solution.By carbonic acid
Hydrogen ammonium dissolves in deionized water, so that the concentration of precipitant solution is 230g/L.
S2, crystallization reaction；
In 10m3500L ammonium bicarbonate soln is added in reaction kettle, by metallic solution and precipitating reagent after being then warming up to 46 DEG C
Solution is mixed in manner of cocurrent flow, and the flow of metallic solution is 400L/h, and precipitant solution flow is 560L/h, stirring speed
Degree is that 450rpm stops feeding until reaction kettle is full, and continues to stir and keep the temperature, and the granularity of crystallization reaction is 2.0- for the first time
2.5um；It carries out that the first slurry is obtained by filtration after granularity meets the requirements, then again by the first slurry and metallic solution and precipitating reagent
Solution mixing, the flow of metallic solution are 400L/h, and precipitant solution flow is 560L/h, mixing speed 450rpm, are carried out
The second slurry, the second slurry abundant first time is obtained by filtration after partial size increases 0.1-0.2 microns in the reaction of first time circulation crystallization
Circulation crystallization reaction, until partial size is isolated final slurry after targeted particle size, and to the washing of final slurry, centrifugation.
S3, it is sintered stage by stage；
By final slurry 350-450 DEG C at a temperature of sintering 3.5 hours after, then 700-800 DEG C at a temperature of be sintered 4
Hour, finally obtain cobaltosic oxide.
The present embodiment also provides a kind of cobaltosic oxide, intermittent mixes aluminium little particle spherical cobaltic-cobaltous oxide by above-mentioned
Preparation method be prepared, the cobaltosic oxide particle diameter distribution is referring to Fig. 1, specific nature are as follows: D50=3.52um, vibration density
Spend 2.02g/cm3。
Embodiment 2-6
The intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide and embodiment 1 that embodiment 2-6 is provided provide
The intermittent preparation method basic operation for mixing aluminium little particle spherical cobaltic-cobaltous oxide it is consistent, difference is, concrete operations condition
It changes.
Embodiment 2
Cobalt source is cobalt chloride, and silicon source is aluminum sulfate, in metallic solution cobalt ions and aluminium ion be respectively 100g/L with
0.68g/L, precipitating reagent are sodium carbonate, and precipitant solution concentration is 230g/L.
The amount of the precipitant solution of bottom liquid is 800L, and temperature is 46 DEG C, and the flow of metallic solution is 500L/h, and precipitating reagent is molten
Flow quantity is 700L/h, mixing speed 400rpm, and the granularity control of crystallization reaction is in 2.5-2.8um for the first time, and repeatedly circulation is tied
The amount of increase that crystalline substance reacts each granularity is 0.2-0.3 micron/time.
Sintering stage by stage is: first sintering temperature is 350~550 DEG C, is sintered 3.5 hours, second of sintering temperature exists
700~900 DEG C, sintering time 7 hours.
The property of obtained cobaltosic oxide: D50=4.31um, tap density 2.11g/cm3, and detect its partial size point
Cloth.
Embodiment 3
Cobalt source is cobalt chloride, and silicon source is aluminum sulfate, in metallic solution cobalt ions and aluminium ion be respectively 100g/L with
0.68g/L, precipitating reagent are sodium carbonate, and precipitant solution concentration is 230g/L.
The amount of the precipitant solution of bottom liquid is 900L, and temperature is 46 DEG C, and the flow of metallic solution is 600L/h, and precipitating reagent is molten
Flow quantity is 840L/h, mixing speed 350rpm, and the granularity control of crystallization reaction is in 3.0-3.5um for the first time, and repeatedly circulation is tied
The amount of increase that crystalline substance reacts each granularity is 0.1-0.3 micron/time.
Sintering stage by stage is: first sintering temperature is 350~550 DEG C, is sintered 3.5 hours, second of sintering temperature exists
700~900 DEG C, sintering time 6 hours.
The property of obtained cobaltosic oxide: D50=5.03um, tap density 2.22g/cm3。
Embodiment 4
Cobalt source is cobalt nitrate, and silicon source is aluminium chloride, and cobalt ions and aluminium ion are respectively 100g/L and 2.5g/ in metallic solution
L, precipitating reagent are sodium carbonate, and precipitant solution concentration is 200g/L.
The amount of the precipitant solution of bottom liquid is 600L, and temperature is 60 DEG C, and the flow of metallic solution is 450L/h, and precipitating reagent is molten
Flow quantity is 675L/h, mixing speed 600rpm, and the granularity control of crystallization reaction is in 2.0-3.0um for the first time, and repeatedly circulation is tied
The amount of increase that crystalline substance reacts each granularity is 0.2-0.25 micron/time.
Sintering stage by stage is: first sintering temperature is 300~550 DEG C, is sintered 2 hours, second of sintering temperature is 700
~1000 DEG C, sintering time 5 hours.
The property of obtained cobaltosic oxide: D50=5.8um, tap density 2.3g/cm3。
Embodiment 5
Cobalt source is cobaltous sulfate, and silicon source is aluminum nitrate, in metallic solution cobalt ions and aluminium ion be respectively 100g/L with
0.01g/L, precipitating reagent are sodium carbonate, and precipitant solution concentration is 300g/L.
The amount of the precipitant solution of bottom liquid is 1000L, and temperature is 30 DEG C, and the flow of metallic solution is 700L/h, precipitating reagent
Liquid inventory is 560L/h, mixing speed 200rpm, and the granularity control of crystallization reaction is repeatedly recycled in 2.2-2.7um for the first time
The amount of increase of each granularity of crystallization reaction is 0.15-0.2 micron/time.
Sintering stage by stage is: first sintering temperature is 400-450 DEG C, is sintered 4 hours, second of sintering temperature is in 850-
950 DEG C, sintering time 6.5 hours.
The property of obtained cobaltosic oxide: D50=3.14um, tap density 2.0g/cm3。
Embodiment 6
Cobalt source is cobalt chloride, and silicon source is aluminium chloride, and cobalt ions and aluminium ion are respectively 100g/L and 1.5g/ in metallic solution
L, precipitating reagent are sodium carbonate, and precipitant solution concentration is 265g/L.
The amount of the precipitant solution of bottom liquid is 750L, and temperature is 50 DEG C, and the flow of metallic solution is 900L/h, and precipitating reagent is molten
Flow quantity is 900L/h, mixing speed 550rpm, and the granularity control of crystallization reaction is in 2.3-2.6um for the first time, and repeatedly circulation is tied
The amount of increase that crystalline substance reacts each granularity is 0.16-0.25 micron/time.
Sintering stage by stage is: first sintering temperature is 370~550 DEG C, is sintered 2.5 hours, second of sintering temperature exists
800-950 DEG C, sintering time 5.5 hours.
The property of obtained cobaltosic oxide: D50=5.1um, tap density 2.25g/cm3。
Comparative example 1: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is the temperature at 350-450 DEG C
Lower sintering 7.5 hours.
Comparative example 2: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is the temperature at 700-800 DEG C
Lower sintering 7.5 hours.
Comparative example 3: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is the temperature of multiple crystallization reaction
Degree is 100 DEG C.
Comparative example 4: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is the temperature of multiple crystallization reaction
Degree is 10 DEG C.
Comparative example 5: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is stirring for multiple crystallization reaction
Mixing speed is 1000rpm.
Comparative example 6: preparing cobaltosic oxide in such a way that embodiment 1 provides, and difference is stirring for multiple crystallization reaction
Mixing speed is 50rpm.
The average grain diameter and tap density for the cobaltosic oxide that measurement comparative example 1-6 is prepared, specific testing result ginseng
It is shown in Table 1.
1 testing result of table
| Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| D50 | 3.52 | 4.8 | 4.12 | 6.8 | 3.89 | 3.72 | 8.7 |
| Tap density | 2.02 | 1.89 | 1.91 | 1.84 | 1.76 | 1.98 | 1.65 |
According to table 1, it does not use its granularity of sublevel section calcining to control with tap density unstable, changes the present invention and implement
The mixing speed of example causes granularity fluctuation too big, and the reaction temperature granularity for changing the embodiment of the present invention is bigger than normal or less than normal, vibration density
It spends all less than normal.
EDS detection is carried out to the cobaltosic oxide that embodiment 1-3 and comparative example 1-6 are prepared, testing result is referring to table
2- table 10 and Fig. 2-Figure 10.
The cobaltosic oxide EDS data of 2 embodiment 1 of table
The cobaltosic oxide EDS data of 3 embodiment 2 of table
The cobaltosic oxide EDS data of 4 embodiment 3 of table
The cobaltosic oxide EDS data of 5 comparative example 1 of table
By being sintered 7.5 hours at a temperature of 350-450 DEG C known to contrast table 2 and the data of table 5, the cobalt in cobalt oxide contains
Measure lower, cobalt carbonate decomposes incomplete.
The cobaltosic oxide EDS data of 6 comparative example 2 of table
7.5 hours are kept the temperature by 700-800 DEG C known to contrast table 2 and the data of table 6, the distribution uniform of aluminium element.
The cobaltosic oxide EDS data of 7 comparative example 3 of table
It is excessively high by reaction temperature known to contrast table 2 and the data of table 7, cause aluminium element segregation serious.
The cobaltosic oxide EDS data of 8 comparative example 4 of table
By reaction temperature known to contrast table 2 and the data of table 8 be it is too low cause aluminium element segregation serious, content difference compared with
Greatly.
The cobaltosic oxide EDS data of 9 comparative example 5 of table
Uniformity by aluminium known to contrast table 2 and the data of table 9 is preferable.
The cobaltosic oxide EDS data of 10 comparative example 6 of table
When lower by mixing speed known to contrast table 2 and the data of table 10, aluminium degree of segregation is larger.
It is utilized respectively the cobaltosic oxide preparation cobalt acid lithium of embodiment 1-3 and comparative example 1-6, preparation cobalt acid lithium is using existing
Prepared by technology, then can be carried out detection to the electrochemistry of cobalt acid lithium, when detection voltage is 4.5V, charge/discharge capacity
Testing result is referring to table 11.
11 chemical property of table
As can be seen from Table 11, invention charging capacity with higher and discharge capacity as can be seen from the table.
In conclusion the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide of the present invention passes through control reaction temperature
Degree, the ratio of reaction raw materials and calcining manners, so that the cobaltosic oxide being prepared, there is aluminium element to be evenly distributed, table
The advantages that face morphological rules, good sphericity, high tap density.Meanwhile the process flow is simple, reacts easily controllable, reacted
Journey is pollution-free, easy to industrialized production.And the cobalt acid lithium overcharging resisting of the little particle spherical cobaltic-cobaltous oxide preparation of synthesis, have and follows
The advantages that ring capacity retention ratio height, better stability and chemical property.
The foregoing is merely the preferred embodiment of the present invention, are not intended to restrict the invention, for this field
For technical staff, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any
Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide, which comprises the following steps:
In 30-60 after the ratio of metallic solution containing aluminium and cobalt and precipitant solution with volume ratio for 1:0.8-1.5 is mixed
Multiple crystallization reaction is carried out under the conditions of DEG C, obtains the crystal grain of required granularity；
Then carry out isolated supernatant liquor and final slurry；
Then the final slurry progress is sintered described in obtaining stage by stage and mixes aluminium little particle spherical cobaltic-cobaltous oxide.
2. the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide according to claim 1, which is characterized in that
Multiple crystallization reaction is to mix and carry out crystallization reaction for the first time for the metallic solution and the precipitant solution, is then obtained
First slurry, then first slurry mixes with the metallic solution and the precipitant solution to carry out multiple circulation crystallization anti-
It answers.
3. the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide according to claim 2, which is characterized in that
The granularity of nucleus is 2.0-3.0 microns in first slurry, and the nucleus for the slurry that circulation crystallization reaction is every time
Granularity increase with 0.1-0.3 micron/time until the long crystal grain to required granularity of the granularity of the nucleus of slurry.
4. the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide according to claim 2, which is characterized in that
For the first time crystallization reaction be after the metallic solution and the precipitant solution being used the mode of cocurrent mix low whipping speed for
200-600rpm, reaction obtains the reaction that grain graininess is 2.0-3.0 microns under the conditions of temperature is 30-60 DEG C.
5. the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide according to claim 1, which is characterized in that
The flow of the metallic solution is 400-900L/h, and the precipitant solution flow is 500-900L/h.
6. the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide according to claim 1, which is characterized in that
The precipitant solution is the solution obtained after mixing precipitating reagent with water,
It is preferred that the precipitating reagent is carbonate, it is further preferred that the carbonate is ammonium hydrogen carbonate, ammonium carbonate, sodium carbonate, bicarbonate
Any one in sodium or at least two.
7. the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide according to claim 1, which is characterized in that
The metallic solution is the solution obtained after mixing cobalt source, silicon source and water,
It is preferred that the mass ratio of cobalt and aluminium is 100:0.01-2.5 in the metallic solution；
It is preferred that the cobalt source be cobalt salt, the cobalt salt in cobaltous sulfate, cobalt chloride and cobalt nitrate any one or at least two
Kind；
It is preferred that source of aluminium is aluminium salt, the aluminium salt in aluminum nitrate, aluminum sulfate and aluminium chloride any one or at least two
Kind.
8. the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide according to claim 1, which is characterized in that
Stage by stage sintering be by the final slurry 300-550 DEG C at a temperature of sintering 2-4 hours after, then in 700-1000 DEG C of temperature
Degree lower sintering 4-7 hours.
9. the intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide according to claim 8, which is characterized in that
The final slurry is washed and is centrifuged before sintering.
10. one kind mixes aluminium little particle spherical cobaltic-cobaltous oxide, which is characterized in that it passes through described in claim 1-9 any one
The intermittent preparation method for mixing aluminium little particle spherical cobaltic-cobaltous oxide be prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811275016.8A CN109179516B (en) | 2018-10-30 | 2018-10-30 | Aluminum-doped small-particle spherical cobaltosic oxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811275016.8A CN109179516B (en) | 2018-10-30 | 2018-10-30 | Aluminum-doped small-particle spherical cobaltosic oxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109179516A true CN109179516A (en) | 2019-01-11 |
| CN109179516B CN109179516B (en) | 2020-12-25 |
Family
ID=64940554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811275016.8A Active CN109179516B (en) | 2018-10-30 | 2018-10-30 | Aluminum-doped small-particle spherical cobaltosic oxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109179516B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142120A (en) * | 2020-09-29 | 2020-12-29 | 格林美股份有限公司 | Method for producing cobaltosic oxide by calcining aluminum and manganese doped small-particle-size cobalt carbonate |
| CN113292106A (en) * | 2020-02-24 | 2021-08-24 | 荆门市格林美新材料有限公司 | Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide |
| CN113651366A (en) * | 2020-05-12 | 2021-11-16 | 荆门市格林美新材料有限公司 | Secondary calcination preparation method of small-particle-size aluminum-doped cobaltosic oxide |
| CN113697865A (en) * | 2021-08-27 | 2021-11-26 | 湖南中伟新能源科技有限公司 | Cobaltosic oxide, preparation method thereof and lithium ion battery |
| CN114632338A (en) * | 2022-03-28 | 2022-06-17 | 河北惠尔信新材料有限公司 | Titanium dioxide washing mother liquor concentration treatment system |
| WO2023020040A1 (en) * | 2021-08-18 | 2023-02-23 | 广东邦普循环科技有限公司 | Method for preparing aluminum-doped cobalt carbonate having flake morphology and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982422A (en) * | 2010-10-21 | 2011-03-02 | 江苏东新能源科技有限公司 | Method for preparing cobaltosic oxide with large grain size and high safety |
| CN105399148A (en) * | 2015-12-07 | 2016-03-16 | 衢州华友钴新材料有限公司 | Preparation method of large-particle-size and high-density spherical cobalt oxide |
| CN207238446U (en) * | 2017-08-23 | 2018-04-17 | 江苏东新能源科技有限公司 | A kind of ultra-fine powder screening plant of cobaltosic oxide |
| CN108649219A (en) * | 2018-05-14 | 2018-10-12 | 荆门市格林美新材料有限公司 | A kind of big grain size mixes the preparation method of aluminium cobaltosic oxide |
-
2018
- 2018-10-30 CN CN201811275016.8A patent/CN109179516B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982422A (en) * | 2010-10-21 | 2011-03-02 | 江苏东新能源科技有限公司 | Method for preparing cobaltosic oxide with large grain size and high safety |
| CN105399148A (en) * | 2015-12-07 | 2016-03-16 | 衢州华友钴新材料有限公司 | Preparation method of large-particle-size and high-density spherical cobalt oxide |
| CN207238446U (en) * | 2017-08-23 | 2018-04-17 | 江苏东新能源科技有限公司 | A kind of ultra-fine powder screening plant of cobaltosic oxide |
| CN108649219A (en) * | 2018-05-14 | 2018-10-12 | 荆门市格林美新材料有限公司 | A kind of big grain size mixes the preparation method of aluminium cobaltosic oxide |
Non-Patent Citations (2)
| Title |
|---|
| 刘人生等: "提高掺铝四氧化三钴均匀性研究", 《世界有色金属》 * |
| 朱贤徐: "湿法制备电池级四氧化三钴的研究", 《精细化工中间体》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292106A (en) * | 2020-02-24 | 2021-08-24 | 荆门市格林美新材料有限公司 | Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide |
| CN113292106B (en) * | 2020-02-24 | 2023-07-25 | 荆门市格林美新材料有限公司 | Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide |
| CN113651366A (en) * | 2020-05-12 | 2021-11-16 | 荆门市格林美新材料有限公司 | Secondary calcination preparation method of small-particle-size aluminum-doped cobaltosic oxide |
| CN112142120A (en) * | 2020-09-29 | 2020-12-29 | 格林美股份有限公司 | Method for producing cobaltosic oxide by calcining aluminum and manganese doped small-particle-size cobalt carbonate |
| WO2023020040A1 (en) * | 2021-08-18 | 2023-02-23 | 广东邦普循环科技有限公司 | Method for preparing aluminum-doped cobalt carbonate having flake morphology and use thereof |
| GB2617937A (en) * | 2021-08-18 | 2023-10-25 | Guangdong Brunp Recycling Technology Co Ltd | Method for preparing aluminum-doped cobalt carbonate having flake morphology and use thereof |
| CN113697865A (en) * | 2021-08-27 | 2021-11-26 | 湖南中伟新能源科技有限公司 | Cobaltosic oxide, preparation method thereof and lithium ion battery |
| CN114632338A (en) * | 2022-03-28 | 2022-06-17 | 河北惠尔信新材料有限公司 | Titanium dioxide washing mother liquor concentration treatment system |
| CN114632338B (en) * | 2022-03-28 | 2024-01-19 | 河北惠尔信新材料股份有限公司 | Titanium white water washing mother liquor concentration processing system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109179516B (en) | 2020-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109179516A (en) | Mix aluminium little particle spherical cobaltic-cobaltous oxide with and preparation method thereof | |
| CN104556248B (en) | The method of continuous production large granular spherical cobalt carbonate | |
| JP5409599B2 (en) | PCC manufacturing method | |
| CN104201367B (en) | High density small particle nickel cobalt manganese hydroxide and preparation method thereof | |
| CN110217832A (en) | A kind of bulky grain narrow ditribution mixes the preparation method of aluminium cobaltosic oxide | |
| CN107180950A (en) | A kind of ternary cathode material of lithium ion battery NCM, NCA spray drying process preparation method | |
| CN108609666A (en) | A kind of preparation method of the cobaltosic oxide of metallic element grade doping | |
| CN107834064A (en) | A kind of nickelic small particle nickel cobalt manganese hydroxide and preparation method thereof | |
| CN107640792A (en) | A kind of high compact small particle nickel cobalt manganese hydroxide and preparation method thereof | |
| CN105322154B (en) | Electrode active substance precursor nickel manganese oxide with special morphology | |
| CN104779388B (en) | Nickel cobalt binary positive material forerunner's preparation and this legal system obtain nickel cobalt binary positive material presoma | |
| JP2002201028A (en) | High density nickel hydroxide coprecipitated with cobalt and manganese, and method for producing the same | |
| CN110217831A (en) | A kind of preparation method of high voltage cobalt acid lithium large granular spherical narrow ditribution cobaltosic oxide | |
| CN110611098B (en) | High-radiation and high-tap-density nickel-cobalt lithium aluminate precursor and preparation method thereof | |
| CN112939095A (en) | Spherical high-nickel cobalt-free single crystal precursor and preparation method thereof | |
| CN101973592A (en) | Preparation method of high-gravity spherical cobalt carbonate | |
| JPH10265225A (en) | Manufacturing device of metallic hydroxide for battery component | |
| EP2883838A1 (en) | Method for preparing lithium metal phosphor oxide | |
| CN107540024A (en) | Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide | |
| CN113636604A (en) | Preparation method of high-aluminum-doped small-particle-size cobalt carbonate particles | |
| CN109179519A (en) | A kind of NiMnO3Porous nano ball material and its preparation method and application | |
| CN105810894A (en) | Multilayer coated structure lithium ion battery positive electrode material preparation method | |
| CN109354077A (en) | A kind of ternary precursor and preparation method thereof of polycrystalline form | |
| CN109686967A (en) | A kind of lithium-rich manganese-based anode material and preparation method thereof | |
| CN115321606A (en) | Aluminum-doped cobalt carbonate particles and preparation method and application thereof |
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 | ||
| CB02 | Change of applicant information |
Address after: 554300 intersection of trunk road No. 2 and No. 1 road, DLONG Economic Development Zone, Tongren, Guizhou Applicant after: Zhongwei new materials Co.,Ltd. Applicant after: HUNAN ZHONGWEI NEW ENERGY TECHNOLOGY CO.,LTD. Address before: 554300 intersection of trunk road No. 2 and No. 1 road, DLONG Economic Development Zone, Tongren, Guizhou Applicant before: CNGR Co.,Ltd. Applicant before: HUNAN ZHONGWEI NEW ENERGY TECHNOLOGY CO.,LTD. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 410600 No. 1, Tanjin Road, Changxing village, Ningxiang Economic and Technological Development Zone, Ningxiang City, Changsha City, Hunan Province Patentee after: HUNAN ZHONGWEI NEW ENERGY TECHNOLOGY CO.,LTD. Patentee after: Zhongwei new materials Co.,Ltd. Address before: 554300 Intersection of Main Road 2 and 1 of Dalong Economic Development Zone, Tongren City, Guizhou Province Patentee before: Zhongwei new materials Co.,Ltd. Patentee before: Hunan Zhongwei New Energy Technology Co., Ltd |
|
| CP03 | Change of name, title or address |