CN105552363B - A kind of nickel cobalt aluminum oxide presoma, nickel cobalt aluminum oxide and preparation method thereof - Google Patents
A kind of nickel cobalt aluminum oxide presoma, nickel cobalt aluminum oxide and preparation method thereof Download PDFInfo
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- CN105552363B CN105552363B CN201511023197.1A CN201511023197A CN105552363B CN 105552363 B CN105552363 B CN 105552363B CN 201511023197 A CN201511023197 A CN 201511023197A CN 105552363 B CN105552363 B CN 105552363B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention provides a kind of preparation methods of nickel cobalt aluminum oxide presoma, it first passes through coprecipitation and the preferably dry nickel cobalt hydroxide of large specific surface area, sphericity is made, organic silicon source under molten condition is mixed with again, make under the action of negative pressure of vacuum aluminium element fully, in the cavernous structure of uniform adsorption to nickel cobalt hydroxide, realization makes aluminium element be evenly distributed in nickel cobalt hydroxide, and drying obtains the high nickel cobalt aluminum oxide presoma of good sphericity, tap density.The preparation method is simple for process, degree of controllability is high, and nickel, cobalt caused by solving the problems, such as in the preparation of nickel cobalt aluminum oxide persursor material in the prior art when aluminium ion cannot precipitate completely, three kinds of Elemental redistributions of aluminium are uneven and nickel cobalt aluminum material sphericity is bad.The present invention also provides the nickel cobalt aluminum oxide presomas as made from above-mentioned preparation method and a kind of nickel cobalt aluminum oxide and preparation method thereof.
Description
Technical field
The invention belongs to battery material preparing technical field more particularly to a kind of nickel cobalt aluminum oxide presoma, nickel cobalt aluminium
Oxide and preparation method thereof.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, and important function is increasingly shown in every field.And lithium is electric
The positive electrode in pond decides the performance, price and development of lithium battery.Ternary battery material (such as nickel cobalt aluminium) is because having at present
Excellent comprehensive performance and as research hotspot, because with relatively inexpensive nickel instead of in cobalt acid lithium 2/3 (or more) cobalt,
It has a clear superiority in terms of cost, meanwhile, the incorporation of aluminium can inhibit the crystal structure of cell positive material in charge and discharge process
Variation improves thermal stability, improves cycle performance, therefore, electrochemical capacity height, good cycle, cost are relatively low, stable structure
The preparation of nickel cobalt aluminium anode material nickel cobalt aluminium is the key that development high-energy density, the lithium ion battery of high circulation performance.
At present, nickel cobalt aluminum cell material precursor is mainly prepared by coprecipitation.Due to Al3+Property is special, Zhi Nengsheng
Into aluminum hydroxide precipitation, and Al3+Hydroxide precipitation property and Ni2+、Co2+Difference, three kinds of nickel, cobalt, aluminium ions are difficult to
It is equably co-precipitated, in addition Al3+Introducing, easily form colloid or reunited by superfine nano wadding grain into flocculent deposit, this is tight
The crystallinity of material is affected again, so as to reduce the physical and chemical performance of material.Patent CN201110140341 and
Using step-by-step precipitation method in CN103178262A, nickel cobalt hydroxide precipitation is first made, then aluminium salt and precipitation is added dropwise on its surface
Agent makes aluminium element gradually be deposited to nickel cobalt hydroxide surfaces, but the reaction step is relatively complicated, and time-consuming, and aluminium is in nickel cobalt
The degree of controllability of the deposition uniformity of hydroxide surfaces is low, and the sphericity of the nickel cobalt aluminium formed is not high.
Therefore, it is necessary to provide, a kind of Elemental redistribution is uniform, the preferable nickel cobalt aluminum material of sphericity and preparation method thereof.
The content of the invention
In consideration of it, the present invention provides a kind of lithium ion battery anode material nickel cobalt aluminum oxide presoma, nickel cobalt aluminas
Compound and preparation method thereof, the present invention first pass through coprecipitation and the preferably dry nickel cobalt hydrogen-oxygen of large specific surface area, sphericity are made
Compound；Then using organic silicon source under molten condition, can be convenient for being uniformly mixed with dry nickel cobalt hydroxide precursor,
The effect of negative pressure of vacuum makes aluminium element fully be adsorbed onto in the cavernous structure of nickel cobalt hydroxide, and realization is uniformly distributed aluminium element
In nickel cobalt hydroxide, drying or further calcining respectively obtain nickel cobalt aluminum oxide presoma and nickel cobalt aluminum oxide.
The simple for process of the preparation method, degree of controllability are high, solve the preparation of nickel cobalt aluminum oxide persursor material in the prior art
Middle nickel caused by when aluminium ion precipitation cannot precipitate completely, three kinds of cobalt, aluminium Elemental redistributions are uneven and nickel cobalt aluminum material is spherical
Spend the problem of bad.
In a first aspect, the present invention provides a kind of preparation methods of nickel cobalt aluminum oxide presoma, comprise the following steps：
(1) nickel salt, the mixing salt solution of cobalt salt are prepared, the molar ratio of nickel and cobalt ions is (1.5 in the mixing salt solution
~12):1, complexing agent, precipitating reagent are taken, the complexing agent, precipitating reagent and the mixing salt solution are added under conditions of stirring
Into reactor, carry out coprecipitation reaction, scope of the controlling reaction temperature at 45~70 DEG C in reaction process, pH value 9.5~
11.5 scope after abundant reaction, carries out the material after reaction separation of solid and liquid and obtains solid product, and the solid is produced
Object obtains nickel cobalt hydroxide after washing, drying；
(2) organic silicon source is taken to carry out heating melting, organic silicon source after melting and above-mentioned nickel cobalt hydroxide are mixed
It closes, and is stirred evenly in the environment of vacuumizing, the mixture drying after stirring evenly afterwards, before obtaining nickel cobalt aluminum oxide
Drive body.
In the present invention, first organic silicon source under molten condition is uniformly mixed with dry nickel cobalt hydroxide precursor,
Can make under the conditions of negative pressure of vacuum nickel cobalt presoma with melting silicon source adsorption reaction fully occurs, it is agitated afterwards uniformly,
Drying obtains nickel cobalt aluminum oxide presoma.Water is not introduced in organic silicon source and the mixed process of nickel cobalt hydroxide, is avoided
Aluminium is caused to can not achieve the problem of being uniformly distributed with two kinds of nickel, cobalt elements due to the hydrolysis of organic silicon source is uncontrollable.
Preferably, in step (1), the drying is segmentation drying, and the drying temperature of the first drying stage is 90~120
DEG C, drying time is 3~10h；The temperature of second drying stage is 200~300 DEG C, and drying time is 5~10h.
In the present invention, isolated nickel cobalt hydroxide solids product carries out segmentation drying after coprecipitation reaction,
First drying stage can fully remove the moisture contained in solid product, but the surface of spherical solid product relatively light at this time
Sliding, specific surface area is little, is unfavorable for the abundant absorption of aluminium element in follow-up organic silicon source；The temperature control of second drying stage is proper
When, the decomposition of nickel cobalt hydroxide will not be made to become nickel cobalt oxide, can make the surface of spherical solid product that certain atrophy occur,
Vesicular texture is generated, the specific surface area of nickel cobalt hydroxide is made about to increase 50%, is effectively increased to follow-up organic silicon source
The abundant absorption of middle aluminium element.The average grain diameter of nickel cobalt hydroxide after segmentation is dried is 4~15 μm.
Preferably, in step (1), the speed of the stirring is 90~150r/min.
Preferably, in step (1), the stirring is by motor agitating paddle to be driven to be stirred, the agitating paddle bag
Include propeller hub, blade and the agitating shaft being connected with motor, the propeller hub by the shaft hole sleeve of the propeller hub on agitating shaft, the paddle
Hub circumference has multiple blades, and the blade is tilting installation with wheel hub junction.
Preferably, the blade tilts the angle of installation as 30~60 ° with wheel hub junction, i.e., plane where described blade
Angle with the axis of agitating shaft is 30~60 °.
Preferably, the blade is in the circumference of hub equidistant placement.
Preferably, the blade is structure as a whole with wheel hub or is installed by welding manner.
In one embodiment of the invention, the number of the blade is 2~6.
In one embodiment of the invention, the blade is straight blades.
In the prior art, carry out liquid phase reactor (coprecipitation reaction) agitating paddle, typically select blade where plane with
The agitating paddle (i.e. blade plane is vertically-mounted, as shown in Figure 3) that the angle of the axis of agitating shaft is 0 °, it is impossible to be carried out to material
It is sufficiently stirred；There is the agitating paddle of certain angle to be stirred in the present invention using the axis of blade plane and agitating shaft, tilt
Blade can to material generate bigger shearing force, and then generate vortex, so as to accelerate the dissolving of chemical agent and mixing.Energy
It is enough more efficiently to make mixing or react the uniformity to improve, increase reactive material and have the identical contact several within the extremely short time
Rate, so as to produce the nickel cobalt hydroxide of performance more preferable (especially sphericity).
Preferably, in step (1), the nickel salt includes the one or more in nickel chloride, nickel sulfate, nickel nitrate.
Preferably, in step (1), the cobalt salt includes the one or more in cobalt chloride, cobaltous sulfate, cobalt nitrate.
As described in the present invention, in step (1), in the mixing salt solution mol ratio of nickel and cobalt ions for (1.5~
12):1.Preferably, in step (1), nickel ion, the total concentration of cobalt ions are 80-150g/L in the mixing salt solution.
Preferably, in step (1), the complexing agent is the ammonium hydroxide that concentration is 4~8g/L.
Preferably, in step (1), the precipitating reagent includes the NaOH or KOH solution that mass fraction is 15%~32%.
Preferably, in step (1), the addition speed of the mixing salt solution is 50-240L/h.
Preferably, in step (1), the addition speed of the precipitating reagent is 15-65L/h.
Preferably, in step (1), the addition speed of the complexing agent is 5-35L/h.
Preferably, in step (1), it is described by complexing agent, precipitating reagent and the mixing salt solution under conditions of stirring
It being added to before reactor, first adds in reaction bottom liquid in the reactor, the reaction bottom liquid is the ammonium hydroxide that concentration is 4~8g/L,
Wherein, the pH value of the reaction bottom liquid is 9.5~11.5, temperature is 45~70 DEG C.The pH value for reacting bottom liquid is sunk using highly basic
Shallow lake agent is adjusted.
Preferably, in step (1), when the washing is that the cleaning solution pH after solid product washing is less than 9, stop
Washing.
Preferably, in step (1), when the nickel salt, cobalt salt select nickel sulfate, cobaltous sulfate it is a kind of when, the washing is
When the sulfur content that the pH of cleaning solution after washing is less than 9, cleaning solution is less than 2000ppm, stop washing.
Preferably, in step (2), organic silicon source includes the one or more in aluminium ethylate and aluminium isopropoxide.
Preferably, in organic silicon source aluminium element molal quantity for nickel, cobalt, three kinds of elements of aluminium mole the sum of
0.015-0.2。
Preferably, in step (2), the temperature of the heating melting is 120~160 DEG C.
It is further preferred that in step (2), the temperature of the heating melting is 128~132 DEG C.
It is further preferred that in step (2), the temperature of the heating melting is 154~160 DEG C.
Preferably, in step (2), the time fully reacted is 12-24h.
In the present invention, in step (1), the structural formula of the nickel cobalt hydroxide is [Ni (OH)2]x·[Co(OH)2]y,
In, 1.5≤x/y≤12.
Second aspect, the present invention provides a kind of nickel cobalt aluminum oxide presoma, the nickel cobalt aluminum oxide presoma
Molecular formula is NixCoyAl1-x-y(OH)3-x-y, wherein 0 ＜ x ＜, 1,0 ＜ y ＜ 1 and 0 ＜ x+y ＜ 1,1.5≤x/y≤12.
It is highly preferred that 0 ＜ y ＜, 0.4,0 ＜ x ＜ 0.923.
Preferably, the nickel cobalt aluminum oxide presoma is regular spherical, and grain size is at 4~15 μm, tap density 1.8
~2.4g/cm3。
The nickel cobalt aluminum oxide presoma is prepared as the method described in first aspect present invention.
The shape of nickel cobalt aluminum oxide presoma provided by the invention is regular spherical, and sphericity is preferable, epigranular,
When carrying out the production of subsequent battery material, convenient for mixing, calcining to be made high charge-discharge capacity, high circulation performance with lithium salts etc.
Anode material of lithium battery.
The third aspect, the present invention provides a kind of preparation methods of nickel cobalt aluminum oxide, comprise the following steps：
(1) nickel salt, the mixing salt solution of cobalt salt are prepared, the molar ratio of nickel and cobalt ions is (1.5 in the mixing salt solution
~12):1, complexing agent, precipitating reagent are taken, the complexing agent, precipitating reagent and the mixing salt solution are added under conditions of stirring
Into reactor, carry out coprecipitation reaction, scope of the controlling reaction temperature at 45~70 DEG C in reaction process, pH value 9.5~
11.5 scope after abundant reaction, carries out the material after reaction separation of solid and liquid and obtains solid product, and the solid is produced
Object obtains nickel cobalt hydroxide after washing, drying；
(2) organic silicon source is taken to carry out heating melting, organic silicon source after melting and above-mentioned nickel cobalt hydroxide are mixed
It closes, and is stirred evenly in the environment of vacuumizing, the mixture drying after stirring evenly afterwards, before obtaining nickel cobalt aluminum oxide
Drive body；
(3) above-mentioned nickel cobalt aluminum oxide presoma is calcined, obtains nickel cobalt aluminum oxide.
Preferably, in step (3), the calcining is calcined for two-part, first segment：300-400 DEG C of calcining 3-5h, second segment
It calcines as 600-1200 DEG C, calcination time 6-15h.
Fourth aspect, the present invention provides a kind of nickel cobalt aluminum oxide, the nickel cobalt aluminum oxide is by the present invention the 3rd
Method described in aspect is prepared.
Preferably, the molecular formula of the nickel cobalt aluminum oxide is NixCoyAl1-x-yO1.5-0.5x-0.5y, wherein 0 ＜ x ＜, 1,0 ＜
Y ＜ 1 and 0 ＜ x+y ＜ 1,1.5≤x/y≤12.
It is highly preferred that 0 ＜ y ＜, 0.4,0 ＜ x ＜ 0.923.
Preferably, the nickel cobalt aluminum oxide is regular spherical, and tap density is 1.9~2.5g/cm3, apparent density
For 1.5~1.9g/cm3, average grain diameter is at 3.5~14.5 μm.
The shape of nickel cobalt aluminum oxide provided by the invention is regular spherical, and sphericity is preferable, epigranular, after progress
When continuous battery material produces, the uniformity of products obtained therefrom is preferable；When the nickel cobalt aluminum oxide is applied to lithium battery anode material
During the preparation field of material, in press molding and sintering process, the volume contraction very little of anode material of lithium battery is conducive to obtain
The anode material of lithium battery of high charge-discharge capacity, high circulation performance.
Nickel cobalt aluminum oxide presoma provided by the invention, nickel cobalt aluminum oxide and preparation method thereof have following beneficial
Effect：
(1) in the preparation method of nickel cobalt aluminum oxide presoma provided by the invention, the preparation method of nickel cobalt aluminum oxide,
It first passes through coprecipitation and is made the preferably dry nickel cobalt hydroxide of large specific surface area, sphericity, then by having under molten condition
Machine silicon source is mixed with, and makes uniform, sufficient adsorption reaction occurs between nickel cobalt presoma and the silicon source of melting, drying or into
One-step calcination respectively obtains nickel cobalt aluminum oxide presoma, nickel cobalt aluminum oxide.Solves nickel cobalt aluminum oxide in the prior art
Nickel caused by when aluminium ion precipitation cannot precipitate completely in prepared by persursor material, three kinds of cobalt, aluminium Elemental redistributions it is uneven and
The problem of nickel cobalt aluminum material sphericity is bad；
(2) preparation method of the nickel cobalt aluminum oxide presoma, the preparation method of nickel cobalt aluminum oxide, simple for process,
Degree of controllability is high, and high yield rate, purity is big, saves production cost；
(3) nickel cobalt aluminum oxide presoma provided by the invention, nickel cobalt aluminum oxide are regular spherical, sphericity compared with
Good, epigranular, apparent density and tap density are higher, are suitable as the presoma of industrialized production anode material of lithium battery.
Description of the drawings
Fig. 1 is the preparation method flow chart of nickel cobalt aluminum oxide presoma in the embodiment of the present invention；
Fig. 2 is the structure diagram of agitating paddle used in the embodiment of the present invention 2；
Fig. 3 is the structure diagram of agitating paddle commonly used in the prior art；
Fig. 4 is the scanning electron microscope of the nickel cobalt hydroxide after being dried for the first time in the embodiment of the present invention 1, after second of drying
(SEM) figure；
Fig. 5 is the SEM figures for the nickel cobalt hydroxide prepared in the prior art using agitating paddle shown in Fig. 3；
Fig. 6 is the SEM figures of nickel cobalt aluminum oxide made from the embodiment of the present invention 1；
Fig. 7 is the SEM figures of nickel cobalt aluminum oxide presoma prepared by the embodiment of the present invention 2；
Fig. 8 is the SEM figures of nickel cobalt aluminum oxide presoma prepared by the embodiment of the present invention 3；
Fig. 9 is the SEM figures of nickel cobalt aluminum oxide presoma prepared by the embodiment of the present invention 4；
Figure 10 is the SEM figures of nickel cobalt aluminum oxide presoma prepared by the embodiment of the present invention 5.
Specific embodiment
As described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
It please refers to Fig.1, Fig. 1 is the preparation method flow chart of nickel cobalt aluminum oxide presoma in the present invention, including following step
Suddenly：
S01, nickel salt, the mixing salt solution of cobalt salt are prepared, the molar ratio of nickel and cobalt ions is (1.5 in the mixing salt solution
~12):1, complexing agent, precipitating reagent are taken, the complexing agent, precipitating reagent and the mixing salt solution are added under conditions of stirring
Into reactor, carry out coprecipitation reaction, scope of the controlling reaction temperature at 45~70 DEG C in reaction process, pH value 9.5~
11.5 scope after abundant reaction, carries out the material after reaction separation of solid and liquid and obtains solid product, and the solid is produced
Object obtains nickel cobalt hydroxide after washing, drying；
S02, organic silicon source is taken to carry out heating melting, organic silicon source after melting and above-mentioned nickel cobalt hydroxide is mixed
It closes, and is stirred evenly in the environment of vacuumizing, the mixture drying after stirring evenly afterwards, before obtaining nickel cobalt aluminum oxide
Drive body.
Embodiment 1
A kind of preparation method of nickel cobalt aluminum oxide, comprises the following steps：
(1) nickel nitrate, the mixing salt solution of cobalt nitrate are prepared, the molar ratio of nickel and cobalt ions is in the mixing salt solution
9:0.085；In coprecipitation reaction kettle add in reaction bottom liquid, reaction bottom liquid for water, complexing agent --- ammonium hydroxide, sodium hydroxide mix
The concentration of ammonium hydroxide in the liquid of bottom is reacted for 4g/L by zoarium system when reacting initial, the pH value that reaction bottom liquid is adjusted with NaOH is 9.5, temperature
It spends for 45 DEG C, rotating speed 150r/min, is by ammonium hydroxide that prepared nickel cobalt mixing salt solution is 5~6g/L with concentration, concentration
32% NaOH solution cocurrent is added in reaction kettle, carries out coprecipitation reaction, wherein, the addition speed of nickel cobalt salt-mixture is
The addition speed of 100L/h, NaOH are 28L/h, and the addition speed of ammonium hydroxide is 12L/h, and controlling reaction temperature is 45 in reaction process
DEG C, pH value is 9.5 ± 0.05；
When reaching 36h between when reacted, separation of solid and liquid is carried out to the material after reaction and obtains solid product, and to separation after
Solid product washed, when the cleaning solution after washing pH be less than 9 when stop washing, by after washing solid product first exist
Drying 3h for the first time is carried out in 100 DEG C of baking oven, the drying 5h of second stage is carried out in 200 DEG C of Muffle furnace afterwards, obtains
Nickel cobalt hydroxide Ni0.9Co0.085(OH)1.97；
(2) aluminium ethylate 25g is weighed, and melting is heated at 160 DEG C, by the nickel after the aluminium ethylate after melting and above-mentioned drying
Cobalt hydroxide 1kg is uniformly mixed under agitation, and then mixed material is stirred evenly in the case where vacuumizing, treats spherical shape
Material after stirring evenly all after wetting, is put into 150 DEG C of drying in baking oven, obtains nickel cobalt aluminium by the surface of nickel cobalt hydroxide
Oxide precursor；
(3) above-mentioned nickel cobalt aluminum oxide presoma is first roasted into 5h, then 1200 DEG C of roasting 6h at 300 DEG C, after roasting
Sample is by crushing and screening to obtain nickel cobalt aluminum oxide.
In the present embodiment, when reacted between when reaching 36h, the nickel cobalt hydrogen-oxygen that obtains particle mean size as 4 μm and be evenly distributed
Compound, the SEM photograph of the solid product after the first time drying, the SEM photograph of the solid product after second of drying is (respectively
As shown in Figure 4), as can be seen from Figure 4, the surface of spherical nickel-cobalt hydroxide is more smooth after drying for the first time, and specific surface area is about
10 (a in Fig. 4), certain atrophy occurs for the surface of the sphere of nickel cobalt hydroxide after second of drying, generates vesicular texture,
Specific surface area is about 15 (b in Fig. 4).
The agitating paddle used when being stirred in the present embodiment 1 (agitating paddle used in embodiment 1 similar with such as Fig. 2 structures
It does not provide, is a difference in that in Fig. 2 it is the blade for having 4 straight blades, blade is tilting installation, blade institute with wheel hub junction
It is 45 ° in the angle of plane and the axis of agitating shaft), the agitating paddle includes propeller hub, blade and the agitating shaft being connected with motor
(here not drawing agitating shaft), by the shaft hole sleeve of the propeller hub on agitating shaft, the blade is the propeller hub with wheel hub
Integral structure has the blade of 6 straight blades in propeller hub circumference equidistant placement, but blade is being to tilt peace with wheel hub junction
Dress, the angle of the axis of plane and agitating shaft where blade is 60 °；And Fig. 3 is agitating paddle commonly used in the prior art, Fig. 3
In, blade is being vertically-mounted with wheel hub junction, and the angle of the axis of plane and agitating shaft where blade is 0 °.According to
Agitating paddle shown in Fig. 3 carries out the preparation of nickel cobalt hydroxide, and the nickel cobalt hydroxide prepared is rough, and cannot
Form homogeneous sphere, bad dispersibility, as shown in Figure 5.From the comparison of Fig. 5 and Fig. 4, using agitating paddle as shown in Figure 2,
It can contribute to obtain that surface is smooth, nickel cobalt hydroxide of size uniformity.
In the present embodiment, in step (2), the composition of gained nickel cobalt aluminum oxide presoma is Ni0.9Co0.085Al0.015
(OH)2.015, shape is regular spherical, and sphericity is preferable, size uniformity, and average grain diameter is at 4 μm, tap density 1.8g/
cm3；
In step (3), the shape of gained nickel cobalt aluminum oxide is regular spherical, and sphericity is higher, and grain size is more uniform, through meter
It calculates, average grain diameter is 4 μm (as shown in Figure 6)；By the nickel cobalt aluminum oxide sample using ICP and the method for titration, it is known that its
It forms as Ni0.9Co0.085Al0.015O1.0075；And the apparent density for measuring the nickel cobalt aluminum oxide is 1.9g/cm3, tap density
For 2.5g/cm3。
Embodiment 2
A kind of preparation method of nickel cobalt aluminum oxide, comprises the following steps：
(1) nickel sulfate, the mixing salt solution of cobaltous sulfate are prepared, the molar ratio of nickel and cobalt ions is in the mixing salt solution
8:1；Reaction bottom liquid is added in coprecipitation reaction kettle, reaction bottom liquid is water, complexing agent --- the mixing of ammonium hydroxide, sodium hydroxide
System reacts the concentration of ammonium hydroxide in the liquid of bottom for 5g/L when reacting initial, the pH value that reaction bottom liquid is adjusted with NaOH is 9.7, temperature
For 50 DEG C, rotating speed 130r/min is stirred using agitating paddle as shown in Figure 2；By prepared nickel cobalt mixing salt solution
The NaOH solution cocurrent that the ammonium hydroxide for being 5g/L with concentration, concentration are 30% is added in reaction kettle, carries out coprecipitation reaction, wherein,
The addition speed of nickel cobalt salt-mixture is 140L/h, and the addition speed of lye is 30L/h, and the addition speed of ammonium hydroxide is 10L/h, is reacted
Controlling reaction temperature is 50 DEG C in the process, and pH value is 9.7 ± 0.05；
When reaching 48h between when reacted, separation of solid and liquid is carried out to the material after reaction and obtains solid product, and to separation after
Solid product washed, stop when the pH of the cleaning solution after washing is less than when the 9, sulfur content of cleaning solution is less than 2000ppm
Solid product after washing is first carried out drying 10h for the first time, obtained spherical nickel-cobalt hydroxide by washing in 90 DEG C of baking oven
Object Ni0.8Co0.1(OH)1.8Surface it is more smooth, specific surface area is about 8, carries out second stage in 220 DEG C of Muffle furnace afterwards
Drying 7h, nickel cobalt hydroxide Ni0.8Co0.1(OH)1.8Spherome surface certain atrophy occurs, generate vesicular texture, than
Surface area is about 14；
(2) aluminium ethylate 25g is weighed, and melting is heated at 155 DEG C, by the nickel after the aluminium ethylate after melting and above-mentioned drying
Cobalt hydroxide 1kg is uniformly mixed under agitation, and then mixed material is placed in vacuum pump and is stirred evenly, dribbling
Material after stirring evenly all after wetting, is put into 150 DEG C of drying in baking oven, obtains nickel cobalt by the surface of shape nickel cobalt hydroxide
Aluminum oxide presoma；
(3) above-mentioned nickel cobalt aluminum oxide presoma is first roasted into 5h, then 800 DEG C of roasting 10h at 300 DEG C, after roasting
Sample is by crushing and screening to obtain nickel cobalt aluminum oxide.
In the present embodiment 2, the schematic diagram of agitating paddle used as shown in Fig. 2, the agitating paddle include propeller hub, blade and with electricity
Machine connection agitating shaft (here not drawing agitating shaft), the propeller hub by the shaft hole sleeve of the propeller hub on agitating shaft, institute
It is welded structure to state blade and wheel hub, and the propeller hub circumference equidistant placement has a blade of 4 straight blades, blade with wheel hub
Junction tilts installation, and the angle of the axis of plane and agitating shaft where blade is 45 °, and the stirring of agitating paddle is driven by motor
Axis stirs to realize.
In the step of embodiment of the present invention 2 (2), the composition of gained nickel cobalt aluminum oxide presoma is Ni0.8Co0.1Al0.1
(OH)2.1, SEM characterizations are carried out to the nickel cobalt aluminum oxide presoma, the results are shown in Figure 7, from figure 7 it can be seen that its shape is
Regular spherical, sphericity is higher, and grain size is more uniform, is computed, and average grain diameter is 6 μm, tap density 1.9g/cm3；It should
Nickel cobalt aluminum oxide presoma calcined obtained by nickel cobalt aluminum oxide sample carry out constituent analysis, it is known that consisting of
Ni0.8Co0.1Al0.1O1.05, which is regular spherical, and sphericity is preferable, epigranular, after tested, tap density
For 2.2g/cm3。
Embodiment 3
A kind of preparation method of nickel cobalt aluminum oxide, comprises the following steps：
(1) nickel sulfate, the mixing salt solution of cobaltous sulfate are prepared, the molar ratio of nickel and cobalt ions is in the mixing salt solution
5:1；Reaction bottom liquid is added in coprecipitation reaction kettle, reaction bottom liquid is water, complexing agent --- ammonium hydroxide, the mixture of sodium hydroxide
The concentration of ammonium hydroxide in the liquid of bottom is reacted for 8g/L by system when reacting initial, the pH value that reaction bottom liquid is adjusted with NaOH is 9.9, and temperature is
55 DEG C, rotating speed 100r/min is stirred using agitating paddle as shown in Figure 2；By prepared nickel cobalt mixing salt solution with
The NaOH solution cocurrent that ammonium hydroxide that concentration is 6g/L, concentration are 30% is added in reaction kettle, carries out coprecipitation reaction, wherein, nickel
The addition speed of cobalt salt-mixture is 150L/h, and the addition speed of lye is 35L/h, and the addition speed of ammonium hydroxide is 15L/h, is reacted
Controlling reaction temperature is 55 DEG C in journey, and pH value is 9.9 ± 0.05；
When reaching 72h between when reacted, separation of solid and liquid is carried out to the material after reaction and obtains solid product, and to separation after
Solid product washed, stop when the pH of the cleaning solution after washing is less than when the 9, sulfur content of cleaning solution is less than 2000ppm
Solid product after washing is first carried out drying 3h for the first time, obtained spherical nickel-cobalt hydroxide by washing in 120 DEG C of baking oven
The surface of object is more smooth, and specific surface area is about 7.5, carries out the drying 7h of second stage, nickel cobalt in 250 DEG C of Muffle furnace afterwards
Hydroxide Ni0.5Co0.1(OH)1.2Spherome surface certain atrophy occurs, generate vesicular texture, specific surface area is about 12；
(2) aluminium ethylate 25g is weighed, and melting is heated at 160 DEG C, by the nickel after the aluminium ethylate after melting and above-mentioned drying
Cobalt hydroxide 1kg is uniformly mixed under agitation, and then mixed material has been placed in vacuum pump and has been stirred evenly, band
Material after stirring evenly all after wetting, is put into 150 DEG C of drying in baking oven, obtains nickel by the surface of spherical nickel-cobalt hydroxide
Cobalt aluminum oxide presoma；
(3) above-mentioned nickel cobalt aluminum oxide presoma is calcined, obtains nickel cobalt aluminum oxide.
In the step of embodiment of the present invention 3 (2), the composition of gained nickel cobalt aluminum oxide presoma is Ni0.5Co0.1Al0.4
(OH)2.4, SEM characterizations are carried out to the nickel cobalt aluminum oxide presoma, the results are shown in Figure 8, from figure 8, it is seen that its shape
For regular spherical, sphericity is higher, and grain size is more uniform, is computed, and average grain diameter is 10 μm, tap density 2.0g/cm3；It will
The nickel cobalt aluminum oxide presoma calcined obtained by nickel cobalt aluminum oxide sample carry out constituent analysis, it is known that consisting of
Ni0.5Co0.1Al0.4O1.2, which is regular spherical, and sphericity is preferable, epigranular, tap density 2.3g/
cm3。
Embodiment 4
A kind of preparation method of nickel cobalt aluminum oxide, comprises the following steps：
(1) nickel nitrate, the mixing salt solution of cobalt nitrate are prepared, the molar ratio of nickel and cobalt ions is in the mixing salt solution
5:3；Reaction bottom liquid is added in coprecipitation reaction kettle, reaction bottom liquid is water, complexing agent --- ammonium hydroxide, the mixture of sodium hydroxide
The concentration of ammonium hydroxide in the liquid of bottom is reacted for 8g/L by system when reacting initial, the pH value that reaction bottom liquid is adjusted with NaOH is 10.5, and temperature is
65 DEG C, rotating speed 90r/min is stirred using agitating paddle as shown in Figure 2；By prepared nickel cobalt mixing salt solution with it is dense
It spends the ammonium hydroxide for 8g/L, in the NaOH solution cocurrent addition reaction kettle that concentration is 20%, carries out coprecipitation reaction, wherein, nickel cobalt
The addition speed of salt-mixture is 150L/min, and the addition speed of lye is 35L/h, and the addition speed of ammonium hydroxide is 15L/h, is reacted
Controlling reaction temperature is 65 DEG C in journey, and pH value is 10.5 ± 0.05；
When reaching 72h between when reacted, separation of solid and liquid is carried out to the material after reaction and obtains solid product, and to separation after
Solid product washed, when the cleaning solution after washing pH be less than 9 when stop washing, by after washing solid product first exist
Drying 7h for the first time is carried out in 120 DEG C of baking oven, the surface of obtained spherical nickel-cobalt hydroxide is more smooth, and specific surface area is about
7, the drying 5h, nickel cobalt hydroxide Ni of second stage are carried out in 300 DEG C of Muffle furnace afterwards0.5Co0.3(OH)1.6Sphere
Certain atrophy occurs for surface, generates vesicular texture, specific surface area is about 11；
(2) aluminium ethylate 30g is weighed, and melting is heated at 160 DEG C, by the nickel after the aluminium ethylate after melting and above-mentioned drying
Cobalt hydroxide 1kg is uniformly mixed under agitation, and then mixed material is placed in vacuum pump and is stirred evenly, dribbling
Material after stirring evenly all after wetting, is put into 150 DEG C of drying in baking oven, obtains nickel cobalt by the surface of shape nickel cobalt hydroxide
Aluminum oxide presoma；
(3) above-mentioned nickel cobalt aluminum oxide presoma is put into 500 DEG C of Muffle furnaces and calcines 10h, obtain nickel cobalt aluminum oxide.
In the step of embodiment of the present invention 4 (2), the composition of gained nickel cobalt aluminum oxide presoma is Ni0.5Co0.3Al0.2
(OH)2.2, SEM characterizations are carried out to the nickel cobalt aluminum oxide presoma, the results are shown in Figure 9, from fig. 9, it can be seen that its shape is
Regular spherical, sphericity is higher, and grain size is more uniform, is computed, and average grain diameter is 12 μm, tap density 2.1g/cm3；It should
Nickel cobalt aluminum oxide presoma calcined obtained by nickel cobalt aluminum oxide sample carry out constituent analysis, it is known that consisting of
Ni0.5Co0.3Al0.2O1.1, which is regular spherical, and sphericity is preferable, epigranular, after tested, tap density
For 2.2g/cm3, tap density 2.5g/cm3。
Embodiment 5
A kind of preparation method of nickel/cobalt composite oxide, comprises the following steps：
(1) nickel nitrate, the mixing salt solution of cobalt nitrate are prepared, the molar ratio of nickel and cobalt ions is in the mixing salt solution
8:1；Reaction bottom liquid is added in coprecipitation reaction kettle, reaction bottom liquid is water, complexing agent --- ammonium hydroxide, the mixture of sodium hydroxide
The concentration of ammonium hydroxide in the liquid of bottom is reacted for 8g/L by system when reacting initial, the pH value that reaction bottom liquid is adjusted with NaOH is 11.5, and temperature is
70 DEG C, rotating speed 90r/min is stirred using agitating paddle as shown in Figure 2；By prepared nickel cobalt mixing salt solution with it is dense
It spends the ammonium hydroxide for 7g/L, in the NaOH solution cocurrent addition reaction kettle that concentration is 15%, carries out coprecipitation reaction, wherein, nickel cobalt
The addition speed of salt-mixture is 110L/h, and the addition speed of NaOH is 24L/h, and the addition speed of ammonium hydroxide is 10L/h, reaction process
Middle controlling reaction temperature is 70 DEG C, and pH value is 11.5 ± 0.05；
When reaching 72h between when reacted, separation of solid and liquid is carried out to the material after reaction and obtains solid product, and to separation after
Solid product washed, when the cleaning solution after washing pH be less than 9 when stop washing, by after washing solid product first exist
Drying 9h for the first time is carried out in 100 DEG C of baking oven, the surface of obtained spherical nickel-cobalt hydroxide is more smooth, and specific surface area is about
7, the drying 10h, nickel cobalt hydroxide Ni of second stage are carried out in 200 DEG C of Muffle furnace afterwards0.8Co0.1(OH)1.8Sphere
Certain atrophy occurs for surface, generates vesicular texture, specific surface area is about 11；
(2) aluminium isopropoxide 31.5g is weighed, and melting is heated at 130 DEG C, after the aluminium ethylate after melting and above-mentioned drying
Nickel cobalt hydroxide 1kg be uniformly mixed under agitation, then mixed material is placed in the equipment vacuumized
It stirs evenly, after the surface whole wetting of spherical nickel cobalt hydroxide, the material after stirring evenly is put into 150 in baking oven
DEG C drying, obtain nickel cobalt aluminum oxide presoma；
(3) above-mentioned nickel cobalt aluminum oxide presoma is put into 500 DEG C of Muffle furnaces and calcines 10h, obtain nickel cobalt aluminum oxide.
In the step of embodiment of the present invention 5 (2), the composition of gained nickel cobalt aluminum oxide presoma is Ni0.8Co0.1Al0.1
(OH)2.1, SEM characterizations are carried out to the nickel cobalt aluminum oxide presoma, the results are shown in Figure 10, from fig. 10 it can be seen that its shape
For regular spherical, sphericity is higher, and grain size is more uniform, is computed, and average grain diameter is 10 μm, tap density 1.9g/cm3；It will
The nickel cobalt aluminum oxide presoma calcined obtained by nickel cobalt aluminum oxide sample carry out constituent analysis, it is known that consisting of
Ni0.8Co0.1Al0.1O1.05, which is regular spherical, and sphericity is preferable, epigranular, and average grain diameter is 12 μm；
After tested, tap density 2.2g/cm3。
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (9)
1. a kind of preparation method of nickel cobalt aluminum oxide presoma, which is characterized in that comprise the following steps：
(1) nickel salt, the mixing salt solution of cobalt salt are prepared, in the mixing salt solution molar ratio of nickel and cobalt ions for (1.5~
12):1, complexing agent, precipitating reagent are taken, the complexing agent, precipitating reagent and the mixing salt solution are added under conditions of stirring
In reactor, carry out coprecipitation reaction, scope of the controlling reaction temperature at 45~70 DEG C in reaction process, pH value 9.5~
11.5 scope after abundant reaction, carries out the material after reaction separation of solid and liquid and obtains solid product, and the solid is produced
Object obtains nickel cobalt hydroxide after washing, drying；
(2) organic silicon source is taken to carry out heating melting, the temperature of the heating melting is 120~160 DEG C；By the organo-aluminium after melting
Source is mixed with above-mentioned nickel cobalt hydroxide, and is stirred evenly in the environment of vacuumizing, mixed after stirring evenly afterwards
Object drying is closed, obtains nickel cobalt aluminum oxide presoma.
2. preparation method as described in claim 1, which is characterized in that in step (1), the drying is that segmentation is dried, first
The drying temperature of drying stage is 90~120 DEG C, drying time 3-10h；The temperature of second drying stage is 200~300 DEG C,
Drying time is 5-10h.
3. preparation method as described in claim 1, which is characterized in that organic silicon source is included in aluminium ethylate and aluminium isopropoxide
One or more.
4. preparation method as described in claim 1, which is characterized in that in step (1), the stirring is stirred by motor drive
Paddle is mixed to be stirred, the agitating paddle includes propeller hub, blade and the agitating shaft being connected with motor, and the propeller hub passes through the paddle
For the shaft hole sleeve of hub on agitating shaft, the propeller hub circumference has multiple blades, and the blade is tilting peace with wheel hub junction
Dress.
5. preparation method as claimed in claim 4, which is characterized in that the blade tilts the angle of installation with wheel hub junction
For 30~60 °.
6. preparation method as described in claim 1, which is characterized in that in step (1), the complexing agent is that concentration is 4~8g/
The ammonium hydroxide of L, the precipitant concentration are the NaOH or KOH solution that mass content is 15%~32%.
7. a kind of nickel cobalt aluminum oxide presoma, which is characterized in that using such as claim 1-6 any one of them preparation methods
It is made, the molecular formula of the nickel cobalt aluminum oxide presoma is NixCoyAl1-x-y(OH)3-x-y, wherein 0 ＜ x ＜, 1,0 ＜ y ＜ 1 and
0 ＜ x+y ＜ 1,1.5≤x/y≤12；The nickel cobalt aluminum oxide presoma be regular spherical, the nickel cobalt aluminum oxide forerunner
The tap density of body is 1.8-2.4g/cm3。
8. a kind of preparation method of nickel cobalt aluminum oxide, which is characterized in that comprise the following steps：
(1) nickel salt, the mixing salt solution of cobalt salt are prepared, in the mixing salt solution molar ratio of nickel and cobalt ions for (1.5~
12):1, complexing agent, precipitating reagent are taken, the complexing agent, precipitating reagent and the mixing salt solution are added under conditions of stirring
In reactor, carry out coprecipitation reaction, scope of the controlling reaction temperature at 45~70 DEG C in reaction process, pH value 9.5~
11.5 scope after abundant reaction, carries out the material after reaction separation of solid and liquid and obtains solid product, and the solid is produced
Object obtains nickel cobalt hydroxide after washing, drying；
(2) organic silicon source is taken to carry out heating melting, the temperature of the heating melting is 120~160 DEG C；By the organo-aluminium after melting
Source is mixed with above-mentioned nickel cobalt hydroxide, and is stirred evenly in the environment of vacuumizing, mixed after stirring evenly afterwards
Object drying is closed, obtains nickel cobalt aluminum oxide presoma；
(3) above-mentioned nickel cobalt aluminum oxide presoma is calcined, obtains nickel cobalt aluminum oxide.
9. a kind of nickel cobalt aluminum oxide, which is characterized in that be made using preparation method as claimed in claim 8, the nickel cobalt
The molecular formula of aluminum oxide is NixCoyAl1-x-yO1.5-0.5x-0.5y, wherein 0 ＜ x ＜, 1,0 ＜ y ＜ 1 and 0 ＜ x+y ＜ 1,1.5≤x/
y≤12；The nickel cobalt aluminum oxide is regular spherical, and the tap density of the nickel cobalt aluminum oxide is 1.9-2.5g/cm3, institute
The apparent density for stating nickel cobalt aluminum oxide is 1.5-1.9g/cm3。
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| CN107359322A (en) * | 2017-06-11 | 2017-11-17 | 成都吱吖科技有限公司 | A kind of preparation method of ball-shape nickel hydroxide cobalt aluminium presoma |
| CN110233257B (en) * | 2019-08-07 | 2020-01-10 | 湖南省正源储能材料与器件研究所 | Preparation method of solid spherical multiple annular lithium-rich manganese-based solid solution cathode material oxide precursor |
| CN113258061B (en) * | 2021-06-23 | 2021-10-15 | 湖南长远锂科股份有限公司 | Nickel-cobalt-manganese ternary cathode material and preparation method thereof |
| CN113277572B (en) * | 2021-07-22 | 2021-11-26 | 金驰能源材料有限公司 | Low-sodium-sulfur-nickel-cobalt composite hydroxide precursor and preparation method thereof |
| CN115064673A (en) * | 2022-06-28 | 2022-09-16 | 广东邦普循环科技有限公司 | Preparation method and application of tightly-coated cobalt oxide |
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