CN110028112A - A kind of method of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor - Google Patents
A kind of method of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor Download PDFInfo
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Abstract
The invention discloses a kind of methods of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor, coprecipitation wide size distribution ball-shape nickel hydroxide cobalt aluminium powder body in the reactor, synthesis process separates kettle construction granular gradient, particle size stable maintains two stages, process parameter control is carried out with different pH value process conditions, overflowing liquid passes through synthesis again and eliminates micro mist, obtain wide size distribution nickel cobalt aluminum hydroxide powder, residue in powder is removed after separation of solid and liquid by the way of strengthening washing and guarantees its dispersibility, it is adjustable at 10 ~ 15 μm that average grain diameter D50 sufficiently is made after drying, tap density is 2.0g/cm3Above nickel cobalt aluminium positive electrode material precursor.The preparation method process flow is simple, suitable for industrial large-scale production nickel cobalt aluminium positive electrode material precursor.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries preparation methods of hydroxide precursor material, especially relate to
And in a kind of lithium-ion-power cell nickel cobalt aluminium positive electrode wide size distribution hydroxide precursor material preparation method.
Background technique
Lithium ion battery due to energy density height, good cycle, it is environmentally protective the advantages that, be widely used in various movements
Formula electronic product, and electric car field will be increasingly being applied to.Positive electrode accounts in lithium ion battery product form
According to most important status, the quality of positive electrode directly determines the final performance of battery, and positive electrode battery at
Proportion is up to 40% or so in this.
In the case where new-energy automobile course continuation mileage requires the situation constantly promoted, there is decisive shadow to power battery energy density
Loud positive electrode develops toward nickelic direction, and has been technology most viable at present by the NCA material of success sizable application
Scheme, it could even be possible to occupying Future New Energy Source passenger car power battery leading market status.
High Ni system positive electrode is that it is difficult synthesis and has stoichiometry to broader applications, reason is not obtained at present
The material of ratio, the doping of aluminium can stablize the structure of nickel cobalt material, hence it is evident that inhibit the exothermic reaction in charge and discharge process, make material
Cycle performance and overcharge resistance performance can improve, therefore the emphasis of NCA positive electrode is mainly in the conjunction of nickel cobalt aluminium hydroxide precursor
Cheng Shang.
The preparation method of nickel cobalt aluminium positive electrode material precursor mainly has mixing oxides method, coprecipitation, sol-gel at present
Method etc..Different preparation methods have opposite impacts on the structure and chemical property of material.Preparation method is different, the material produced
Material has apparent difference.Aluminium-hydroxide powder is mixed into hydroxide nickel cobalt generally by way of mechanical mixture by mixing oxides method
In powder, simple process is at low cost, but aluminium cannot reach uniform mixing in nickel cobalt, causes product chemical property poor；It is coprecipitated
Shallow lake method process flow is relatively easy, but due to Al3+、Ni2+And Co2+The Ksp of three kinds of ions is respectively 1.9 × 10-33、2×10-15
With 1.6 × 10-15Differ too big, Al3+It is difficult and Ni2+、Co2+Realize homogeneous coprecipitation, presoma lattice order is deteriorated.But no
Same preparation method has respective advantage, for example reaction temperature is low, raw material is uniformly mixed, the reproducibility and consistency of material preparation
Preferably, extent of chemical reaction is easy to control, and can synthesize the good positive electrode of layer structure, but they also have accordingly
The drawbacks of, therefore, existing preparation method requires to continue Improvement.
Summary of the invention
The present invention existing method there are aiming at the problem that, a kind of better nickel cobalt aluminium positive electrode material precursor of effect is provided
Ground preparation method.
The technical scheme is that this method carries out as steps described below:
Step 1 synthesizes ball-shape nickel hydroxide cobalt aluminium of the average grain diameter D50 at 8 ~ 13 μm: by Ni2+、Co2+Mixing salt solution and aluminium salt
Solution, enveloping agent solution, precipitant solution cocurrent are added in the reactor equipped with bottom liquid, exist in 50 DEG C -75 DEG C, speed of agitator
Under the conditions of 300-600rpm, complexing agent concentration 0.15-0.3mol/L, by being carried out within the scope of 10-13 not to synthetic system pH value
With the adjustment of number of stages value, reaction process is divided into out kettle construction granular gradient, particle size stable maintains former and later two stages to carry out
Synthesis control, wherein particle size stable maintenance stage long period is successively run, and the powder granularity D50 in overflow slurry stablizes dimension
It holds within the scope of ± 1 μm of gap, and overflowing liquid alternately accesses subsequent two attached overflow kettles；
Continue long micro mist of eliminating in step 2 overflow kettle: two attached overflow kettles alternately connect the overflowing liquid in step 1, and wherein into
Row is continuous long to eliminate micro mist, and four kinds of solution are mainly added in purpose in the same manner, with reaction kettle process parameters range base
Originally under the same conditions, adjustment pH value makes micro mist is continuous to grow up to larger particles, obtains average grain diameter D50 at 8-13 μm after continuous length
Ball-shape nickel hydroxide cobalt aluminium powder somaplasm liquid；
The post-processing of step 3 powder: nickel cobalt aluminum hydroxide powder slurries obtained in step 2 are separated by solid-liquid separation to obtain powder, by powder
Material is added 80 DEG C of -100 DEG C of deionized waters and stirs into slurries, strong to slurries in the emulsion dispersion machine of rotor linear velocity 15-25m/s
Change is washed and is separated by solid-liquid separation, adds deionized water pulp and strengthen washing, and powder is placed in 90-120 DEG C after repeated multiple times washing and is done
Dry 20-24h in dry case, obtains the spherical nickel-cobalt aluminium positive electrode material precursor that average grain diameter D50 is 10-15 μm.
The molar concentration of the total metal ion of nickel cobalt mixing salt solution in the step 1 and step 2 is 1 ~ 3mol/L.
Aluminum salt solution Al in the step 1 and step 23+Concentration is 0.5-2mol/L.
Ni in the step 1 and step 22+、Co2+Reactor, mixed solution is added in mixing salt solution and aluminum salt solution cocurrent
Middle Ni2+、Co2+、Al3+Molar ratio be 100-x-y:x:y, 4≤x≤15,2≤y≤5.
The concentration of enveloping agent solution in the step 1 and step 2 is 2.5-4.5mol/L, which is
One or more of EDTA, ammonium hydroxide, EGTA, vulcanized sodium agents coordinate aqueous solution (several complexing agent mixed solutions, each other
Reaction cannot influence that effect is complexed), the volume additional amount of enveloping agent solution is the 0.1- of mixing salt solution volume additional amount
0.2 times.
The concentration of precipitant solution in the step 1 and step 2 is 5-10mol/L, which is hydroxide
(several precipitant mix solution, mutual is anti-for the aqueous solution of one or more of sodium, thiocarbamide, carbonyl diamide agents coordinate
Should cannot influence sedimentation effect), the volume additional amount of precipitant solution is 0.4-0.5 times of mixing salt solution volume additional amount.
Bottom liquid in the step 1 is the mixed solution of precipitant solution and enveloping agent solution.
It is opened in the step 1 the kettle construction granular gradient stage, regulation method mainly will open kettle phase system pH value and exist
Cyclic fluctuation is carried out in the range of 10.5-12.0, make synthetic system periodically go out micro mist, grow up, gradually form it is big or middle,
The grade distribution type granular gradient that little particle quantity is about 1:1:1, bulky grain, which is grown up, leads to the growth of average grain diameter D50, close in D50
When targeted particle size, due to overflow, going out the comprehensive function of micro mist, continued propagation, average grain diameter D50 can maintain ± 1 μm of range,
Into the particle size stable maintenance stage.
The particle size stable maintenance stage in the step 1, regulation method is mainly by system pH in the relatively narrow of 11.2-12.0
Fluctuation in range, maintains certain micro mist amount with making system period, average grain diameter D50 can long period continuously maintain target grain
Within the scope of the gap of diameter ± 1 μm, overflowing liquid alternately accesses subsequent two attached overflow kettles.
The continuous long elimination micro mist of overflowing liquid in the step 2, regulation method is mainly by the slurry system pH value of overflow kettle
0.2-0.5 is reduced compared with synthesis reactor, purpose mainly makes no longer occur new micro mist in system, and existing micro mist is continuous to grow up to larger
Grain, average grain diameter D0, D10 reach target call.
When carrying out the post-processing of powder in the step 3, it is separated by solid-liquid separation after the powder in reactor is released, then
80 DEG C or more deionized waters are added in powder and stir into slurries, the residue in powder granule are carried out by emulsion dispersion machine strong
Change washing, the high-speed rotating rotor of emulsion dispersion machine generates at least linear velocity of 15m/s or more, material and cuts in strong fluid power
It cuts, be reinforced dispensing laundry under liquid layer friction effect, material, to completely remove residue in powder, is filled by least four times circulations
Divide drying to carry out handling except iron again, obtains the nickel cobalt aluminium positive electrode material precursor of target call.
The predominating path of this method is coprecipitation wide size distribution ball-shape nickel hydroxide cobalt aluminium powder body in the reactor,
Synthesis process separates kettle construction granular gradient, particle size stable maintains two stages, carries out technique with different pH value process conditions
State modulator, overflowing liquid pass through synthesis again and eliminate micro mist, obtain wide size distribution nickel cobalt aluminum hydroxide powder, adopt after separation of solid and liquid
Remove in powder residue with the mode for strengthening washing and guarantee its dispersibility, be made after sufficiently dry average grain diameter D50 10 ~
15 μm of adjustable, tap density 2.0g/cm3Above nickel cobalt aluminium positive electrode material precursor.
Beneficial effects of the present invention: this preparation method can simply and effectively control the average grain diameter D50 of presoma 10
~ 15 μm of desired extent has spherical or spherical pattern, and large, medium and small grain composition effect is good, and tap density is higher, surface one
Secondary particle is in the spindle of uniform and delicate, and particle interior nickel, cobalt, aluminium element are evenly distributed, the powder granule after strengthening washing
Surface residue is few, good dispersion, and reactivity is high, be conducive in subsequent process with the mixing of lithium source and sintering.Meanwhile it is whole
Preparation process is simple, at low cost, suitable for industrial large-scale production nickel cobalt aluminium positive electrode material precursor.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the wide size distribution Ni that D50 made from the preparation process of embodiment 1 is 12 μm0.9Co0.08Al0.02(OH)2.02Anode
1000 times of scanning electron microscope (SEM) photographs of material precursor；
Fig. 3 is the wide size distribution Ni that D50 made from the preparation process of embodiment 1 is 12 μm0.9Co0.08Al0.02(OH)2.02Anode
4000 times of scanning electron microscope (SEM) photographs of material precursor；
Fig. 4 is the wide size distribution Ni that D50 made from the preparation process of embodiment 2 is 11 μm0.91Co0.06Al0.03(OH)2.03Just
1000 times of scanning electron microscope (SEM) photographs of pole material precursor；
Fig. 5 is the wide size distribution Ni that D50 made from the preparation process of embodiment 2 is 11 μm0.91Co0.06Al0.03(OH)2.03Just
4000 times of scanning electron microscope (SEM) photographs of pole material precursor.
Specific embodiment
The present invention is described further below in conjunction with Figure of description and specific embodiment.
Embodiment 1
A kind of wide size distribution Ni that D50 is 12 μm0.9Co0.08Al0.02(OH)2.02The preparation method of positive electrode material precursor, packet
Containing following steps:
(1) it first synthesizing spherical nickel cobalt aluminum hydroxide powder in the reactor: is accurately weighed according to elemental mole ratios Ni:Co=90:8
Nickel sulfate, cobaltous sulfate, and it is dissolved in the nickel cobalt metal mixed salting liquid that 2mol/L is configured in deionized water；Aluminum sulfate is weighed to be dissolved in
Deionized water, every liter of solution are added 100g piece alkali and are sufficiently stirred, and are finally configured to the Al of 0.5mol/L3+Salting liquid；According to element
Molar ratio Ni:Co:Al=90:8:2 accurately sets nickel cobalt mixing salt solution and aluminum salt solution flow, the complexing agent with 2.5mol/L
Solution, 5mol/L precipitant solution cocurrent be added to the reactor equipped with bottom liquid carry out liquid phase synthesis reaction.Reaction start and
Control temperature, in 0.15mol/L, opens kettle phase system pH value in 500rpm, complexing agent concentration in 58 DEG C, speed of agitator in the process
It is scheduled on 10.8 lower value, sintetics reunion is made to achieve the purpose that fast-growth.PH value carries out periodical adjustment later, it may be assumed that
When sintetics granularity D50 grows to 7 μm, system pH is improved to 11.7, during which testing laser granularity and viewing microscope, drink
Feelings control system pH value promotes speed until occurring and the comparable little particle of bulky grain quantity；PH value is reduced later to 11.0 left sides
The right side makes the large and small particle generated grow up；When sintetics granularity D50 grows to 9 μm, system pH is improved again to 11.7
Left and right, during which testing laser granularity and viewing microscope, as one sees fit control system pH value promote speed until the little particle occurred with
Amounts of particles big or middle forms the proportion of 1:1:1；PH value is reduced later to 11.2 or so, keeps the large, medium and small particle generated long
Greatly, when sintetics granularity D50 grows to 11 μm, system pH is improved again to 11.7 or so, during which testing laser granularity is simultaneously
Viewing microscope, control system pH value promotes speed up to the little particle of the equivalent amount occurred as one sees fit, forms preferable granularity
Gradient, into the particle size stable maintenance stage.The particle size stable maintenance stage regulates and controls method mainly by system pH in 11.2-11.7
Narrower range in fluctuation, maintain certain micro mist amount with making system period, average grain diameter D50 can long period continuously maintain
In the range of 11 ± 1 μm, overflowing liquid alternately accesses subsequent two attached overflow kettles.In above-mentioned reaction process, complexing is added
The nickel that the dosage of precipitant solution is 0.4 times is added in the dosage for the nickel cobalt metal mixed salting liquid that the dosage of agent solution is 0.1 times
The dosage of cobalt metal mixed salting liquid.
(2) the continuous long elimination micro mist of overflowing liquid: after slurry volume accounts for the 2/3 of kettle total measurement (volume) in overflow kettle, closing outflow valve, control
System temperature processed is in 58 DEG C, speed of agitator in 500rpm, complexing agent concentration in 0.15mol/L, and four kinds of addition is molten in the same manner
Liquid, regulation system pH value to 11.0 detect in laser particle size and observation optical microscopy control system and new micro mist no longer occur,
Make existing micro mist is continuous to grow up to larger particles, when average grain diameter D50 reaches 12 ± 1 μm, D0, D10 respectively reach > 1 μm, > 4 μm of mesh
Mark requires, and stops synthesis, and post-processing is entered after ageing.
(3) post-processing of powder: being separated by solid-liquid separation to obtain powder for wide size distribution powder obtained in step (2), then will
Powder is added 90 DEG C of deionized waters and stirs into slurries, by the emulsion dispersion machine of high-speed rotating rotor linear velocity 15m/s to slurry
Liquid, which is strengthened, to be washed and is separated by solid-liquid separation, adds deionized water pulp and strengthen washing, and powder is placed in 90 DEG C of drying boxes after washing repeatedly
Interior dry 20h, the spherical Ni that obtain average grain diameter D50 still be 12 μm0.9Co0.08Al0.02(OH)2.02Positive electrode material precursor, shape
Looks are as shown in Figure 2.
Spherical Ni made from the present embodiment0.9Co0.08Al0.02(OH)2.0The tap density of 2 positive electrode material precursors is 2.0g/
cm3, specific surface area 20m2/ g, sulfate radical residual quantity are 0.2%, and large, medium and small even particle distribution, compactedness is high, and surface is primary
Particle is in spindle, grows fine and close zero defect, carries out Surface scan to section after cutting to particle, and nickel, cobalt, aluminium element distribution are equal
It is even.
Embodiment 2
A kind of wide size distribution Ni that D50 is 11 μm0.91Co0.06Al0.03(OH)2.03The preparation method of positive electrode material precursor, should
Method carries out as steps described below:
(1) it first synthesizing spherical nickel cobalt aluminum hydroxide powder in the reactor: is accurately weighed according to elemental mole ratios Ni:Co=91:6
Nickel sulfate, cobaltous sulfate, and it is dissolved in the nickel cobalt metal mixed salting liquid that 1.5mol/L is configured in deionized water；It is molten to weigh aluminum sulfate
In deionized water, every liter of solution is added 100g piece alkali and is sufficiently stirred, and is finally configured to the Al of 0.5mol/L3+Salting liquid；According to member
Plain molar ratio Ni:Co:Al=91:6:3 accurately sets nickel cobalt mixing salt solution and aluminum salt solution flow, the complexing with 2.5mol/L
Agent solution, 5mol/L precipitant solution cocurrent be added to the reactor equipped with bottom liquid carry out liquid phase synthesis reaction.Reaction starts
And it controls temperature in the process and, in 0.15mol/L, opens kettle phase system pH in 450rpm, complexing agent concentration in 60 DEG C, speed of agitator
Value is scheduled on 11.0 lower value, and sintetics reunion is made to achieve the purpose that fast-growth.PH value carries out periodical adjustment later,
That is: it when sintetics granularity D50 grows to 6 μm, improves system pH to 11.6, during which testing laser granularity and observes micro-
Mirror, control system pH value promotes speed until occurring and the comparable little particle of bulky grain quantity as one sees fit；Reduce pH value extremely later
11.0 or so, so that the large and small particle generated is grown up；When sintetics granularity D50 grows to 8 μm, system pH is improved again
To 11.6 or so, during which testing laser granularity and viewing microscope, control system pH value promotes speed until what is occurred is small as one sees fit
Particle and big or middle amounts of particles form the proportion of 1:1:1；PH value is reduced later to 11.2 or so, makes large, medium and small generated
Grain is grown up, and when sintetics granularity D50 grows to 10 μm, improves system pH again to 11.7 or so, during which testing laser
Granularity and viewing microscope, control system pH value promotes speed up to the little particle of the equivalent amount occurred as one sees fit, is formed preferable
Granular gradient, into the particle size stable maintenance stage.Particle size stable maintenance stage regulation method mainly exists system pH
Fluctuation, maintains certain micro mist amount, average grain diameter D50 can long period with making system period in the narrower range of 11.2-11.6
In the range of continuously maintaining 10 ± 1 μm, overflowing liquid alternately accesses subsequent two attached overflow kettles.In above-mentioned reaction process
In, the dosage of precipitant solution is added in the dosage for the nickel cobalt metal mixed salting liquid that the dosage that enveloping agent solution is added is 0.1 times
For the dosage of 0.4 times of nickel cobalt metal mixed salting liquid.
(2) the continuous long elimination micro mist of overflowing liquid: after slurry volume accounts for the 2/3 of kettle total measurement (volume) in overflow kettle, closing outflow valve, control
System temperature processed is in 60 DEG C, speed of agitator in 450rpm, complexing agent concentration in 0.15mol/L, and four kinds of addition is molten in the same manner
Liquid, regulation system pH value to 11.0 detect in laser particle size and observation optical microscopy control system and new micro mist no longer occur,
Make existing micro mist is continuous to grow up to larger particles, when average grain diameter D50 reaches 11 ± 1 μm, D0, D10 respectively reach > 1 μm, > 4 μm of mesh
Mark requires, and stops synthesis, and post-processing is entered after ageing.
(3) post-processing of powder: being separated by solid-liquid separation to obtain powder for wide size distribution powder obtained in step (2), then will
Powder is added 90 DEG C of deionized waters and stirs into slurries, by the emulsion dispersion machine of high-speed rotating rotor linear velocity 15m/s to slurry
Liquid, which is strengthened, to be washed and is separated by solid-liquid separation, adds deionized water pulp and strengthen washing, and powder is placed in 90 DEG C of drying boxes after washing repeatedly
Interior drying for 24 hours, the spherical Ni that obtain average grain diameter D50 still be 11 μm0.91Co0.06Al0.03(OH)2.03Positive electrode material precursor, shape
Looks are as shown in Figure 3.
Spherical Ni made from the present embodiment0.91Co0.06Al0.03(OH)2.03The tap density of positive electrode material precursor is
2.0g/cm3, specific surface area 23m2/ g, sulfate radical residual quantity are 0.2%, and large, medium and small even particle distribution, compactedness is high, table
Face primary particle is in spindle, grows fine and close zero defect, carries out Surface scan, nickel, cobalt, aluminium element point to section after cutting to particle
Cloth is uniform.
Claims (10)
1. a kind of method of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor, which is characterized in that the party
Method carries out as steps described below:
Step 1: by Ni2+、Co2+Mixing salt solution and aluminum salt solution, enveloping agent solution, precipitant solution cocurrent are added and bottom liquid are housed
Reactor in, in 50 DEG C -75 DEG C, speed of agitator under the conditions of 300-600rpm, complexing agent concentration 0.15-0.3mol/L, lead to
The adjustment for carrying out different phase numerical value within the scope of 10-13 to synthetic system pH value is crossed, reaction process is divided into out kettle construction granularity
Gradient, particle size stable maintain former and later two stages to carry out synthesis control, and wherein particle size stable maintenance stage long period is successive
It runs, after the powder granularity D50 in overflow slurry is stably maintained within the scope of ± 1 μm of gap, and overflowing liquid alternately accesses
The attached overflow kettle of continuous two；
Step 2: two attached overflow kettles alternately connect the overflowing liquid in step 1, and carry out wherein continuous long to eliminate micro mist, mesh
Mainly in the same manner be added four kinds of solution, under conditions of essentially identical with reaction kettle process parameters range, adjust pH
Value makes micro mist is continuous to grow up to larger particles, obtains ball-shape nickel hydroxide cobalt aluminium powder of the average grain diameter D50 at 8-13 μm after continuous length
Somaplasm liquid；
Step 3: nickel cobalt aluminum hydroxide powder slurries obtained in step 2 being separated by solid-liquid separation to obtain powder, by 80 DEG C of powder addition-
100 DEG C of deionized waters stir into slurries, wash in the emulsion dispersion machine of rotor linear velocity 15-25m/s to slurries reinforcing and solid
Liquid separation plus deionized water pulp and reinforcing washing, are placed in drying in 90-120 DEG C of drying box for powder after repeated multiple times washing
20-24h obtains the spherical nickel-cobalt aluminium positive electrode material precursor that average grain diameter D50 is 10-15 μm.
2. a kind of side of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor as described in claim 1
Method, which is characterized in that the Ni in the step 1 and step 22+、Co2+The concentration of total metal ion is 1- in mixing salt solution
3mol/L, Ni2+、Co2+Mixing salt solution and aluminum salt solution cocurrent are added in the mixed solution formed after reactor, Ni2+、Co2+、
Al3+Molar ratio be 100-x-y:x:y, 4≤x≤15,2≤y≤5.
3. a kind of side of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor as described in claim 1
Method, which is characterized in that the aluminum salt solution Al in the step 1 and step 23+Concentration is 0.5-2mol/L.
4. a kind of side of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor as described in claim 1
Method, which is characterized in that the concentration of the enveloping agent solution in the step 1 and step 2 is 2.5-4.5mol/L, and the complexing agent is molten
Liquid is one or more of EDTA, ammonium hydroxide, EGTA, vulcanized sodium, tartaric acid aqueous solution, and the volume additional amount of enveloping agent solution is
0.1-0.2 times of mixing salt solution volume additional amount.
5. a kind of side of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor as described in claim 1
Method, which is characterized in that the concentration of the precipitant solution in the step 1 and step 2 is 5-10mol/L, which is
The aqueous solution of one or more of sodium hydroxide, thiocarbamide, carbonyl diamide, the volume additional amount of precipitant solution are that salt-mixture is molten
0.4-0.5 times of liquid product additional amount.
6. a kind of side of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor as described in claim 1
Method, which is characterized in that the bottom liquid in the step 1 is the mixed solution of precipitant solution and enveloping agent solution.
7. a kind of side of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor as described in claim 1
Method, which is characterized in that the kettle construction granular gradient stage is opened in the step 1, regulation method will mainly open kettle phase system pH
Value carries out cyclic fluctuation in the range of 10.5-12.0, and synthetic system is made periodically to go out micro mist, grow up, gradually form it is big,
In, little particle quantity be about 1:1:1 grade distribution type granular gradient, bulky grain, which is grown up, leads to the growth of average grain diameter D50, in D50
When close to targeted particle size, due to overflow, go out the comprehensive function of micro mist, continued propagation, average grain diameter D50 can maintain ± 1 μm
Range, into the particle size stable maintenance stage.
8. a kind of side of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor as claimed in claim 7
Method, which is characterized in that the particle size stable maintenance stage in the step 1, regulation method is mainly by system pH in 11.2-12.0
Narrower range in fluctuation, maintain certain micro mist amount with making system period, average grain diameter D50 can long period continuously maintain
Within the scope of the gap of target grain size ± 1 μm, overflowing liquid alternately accesses subsequent two attached overflow kettles.
9. a kind of side of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor as described in claim 1
Method, which is characterized in that the continuous long elimination micro mist of overflowing liquid in the step 2, regulation method is mainly by the slurries body of overflow kettle
It is pH value compared with synthesis reactor reduction 0.2-0.5, purpose mainly makes no longer occur new micro mist in system, and existing micro mist is continuous to be grown up to
Larger particles, average grain diameter D0, D10 reach target call.
10. a kind of side of continuous coprecipitation wide size distribution nickel cobalt aluminium positive electrode material precursor as described in claim 1
Method, which is characterized in that when carrying out the post-processing of powder in the step 3, carry out solid-liquid point after the powder in reactor is released
From 80 DEG C or more deionized waters then are added in powder and stir into slurries, by emulsion dispersion machine to the residual in powder granule
Object carries out reinforcing washing, and the high-speed rotating rotor of emulsion dispersion machine generates at least linear velocity of 15m/s or more, and material is strong
Dispensing laundry is reinforced under aquashear, liquid layer friction effect, material is residual in powder to completely remove by least four times circulations
Object is stayed, it is sufficiently dry to carry out handling except iron again, obtain the nickel cobalt aluminium positive electrode material precursor of target call.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931776A (en) * | 2019-12-24 | 2020-03-27 | 中南大学 | Preparation method of nickel-cobalt-manganese ternary positive electrode material precursor with multi-level distribution of particle sizes |
| CN111204821A (en) * | 2020-02-22 | 2020-05-29 | 华友新能源科技（衢州）有限公司 | Nickel-cobalt-manganese hydroxide with particle size in bimodal distribution and preparation method thereof |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244239A (en) * | 2011-05-27 | 2011-11-16 | 湖南长远锂科有限公司 | Method for preparing nickel cobalt aluminum serving as cathodic material of lithium ion battery |
| CN103178263A (en) * | 2013-02-21 | 2013-06-26 | 湖南桑顿新能源有限公司 | Method for preparing nickel cobalt lithium aluminate cathode material |
| CN103553152A (en) * | 2013-10-22 | 2014-02-05 | 金天能源材料有限公司 | High-density spherical nickel-cobalt-aluminum precursor material and preparation method thereof |
| CN104934595A (en) * | 2015-05-08 | 2015-09-23 | 广州锂宝新材料有限公司 | Methods for preparing nickel-cobalt-aluminum precursor material and nickel-cobalt-aluminum cathode material with gradient distribution of aluminum element |
| CN105489886A (en) * | 2016-01-11 | 2016-04-13 | 山东玉皇新能源科技有限公司 | Nickel-cobalt-aluminum ternary cathode material with high tap-density and preparation method of nickel-cobalt-aluminum ternary cathode material |
| CN106299347A (en) * | 2016-08-08 | 2017-01-04 | 天津巴莫科技股份有限公司 | Nickel cobalt aluminum ternary precursor and preparation method thereof and the positive electrode prepared and method |
| CN107316990A (en) * | 2017-05-26 | 2017-11-03 | 金川集团股份有限公司 | A kind of preparation method of cladded type nickel cobalt aluminium positive electrode material precursor |
| CN107915263A (en) * | 2017-08-31 | 2018-04-17 | 广东佳纳能源科技有限公司 | A kind of preparation method of small particle ternary anode material precursor |
| CN108264097A (en) * | 2016-12-31 | 2018-07-10 | 北京当升材料科技股份有限公司 | A kind of preparation method of anode material for lithium-ion batteries bulky grain presoma |
-
2019
- 2019-04-23 CN CN201910329884.8A patent/CN110028112B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244239A (en) * | 2011-05-27 | 2011-11-16 | 湖南长远锂科有限公司 | Method for preparing nickel cobalt aluminum serving as cathodic material of lithium ion battery |
| CN103178263A (en) * | 2013-02-21 | 2013-06-26 | 湖南桑顿新能源有限公司 | Method for preparing nickel cobalt lithium aluminate cathode material |
| CN103553152A (en) * | 2013-10-22 | 2014-02-05 | 金天能源材料有限公司 | High-density spherical nickel-cobalt-aluminum precursor material and preparation method thereof |
| CN104934595A (en) * | 2015-05-08 | 2015-09-23 | 广州锂宝新材料有限公司 | Methods for preparing nickel-cobalt-aluminum precursor material and nickel-cobalt-aluminum cathode material with gradient distribution of aluminum element |
| CN105489886A (en) * | 2016-01-11 | 2016-04-13 | 山东玉皇新能源科技有限公司 | Nickel-cobalt-aluminum ternary cathode material with high tap-density and preparation method of nickel-cobalt-aluminum ternary cathode material |
| CN106299347A (en) * | 2016-08-08 | 2017-01-04 | 天津巴莫科技股份有限公司 | Nickel cobalt aluminum ternary precursor and preparation method thereof and the positive electrode prepared and method |
| CN108264097A (en) * | 2016-12-31 | 2018-07-10 | 北京当升材料科技股份有限公司 | A kind of preparation method of anode material for lithium-ion batteries bulky grain presoma |
| CN107316990A (en) * | 2017-05-26 | 2017-11-03 | 金川集团股份有限公司 | A kind of preparation method of cladded type nickel cobalt aluminium positive electrode material precursor |
| CN107915263A (en) * | 2017-08-31 | 2018-04-17 | 广东佳纳能源科技有限公司 | A kind of preparation method of small particle ternary anode material precursor |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931776A (en) * | 2019-12-24 | 2020-03-27 | 中南大学 | Preparation method of nickel-cobalt-manganese ternary positive electrode material precursor with multi-level distribution of particle sizes |
| CN110931776B (en) * | 2019-12-24 | 2021-02-02 | 中南大学 | Preparation method of nickel-cobalt-manganese ternary positive electrode material precursor with multi-level distribution of particle sizes |
| CN111204821A (en) * | 2020-02-22 | 2020-05-29 | 华友新能源科技（衢州）有限公司 | Nickel-cobalt-manganese hydroxide with particle size in bimodal distribution and preparation method thereof |
| CN111600015A (en) * | 2020-07-27 | 2020-08-28 | 金驰能源材料有限公司 | Narrow-distribution small-granularity spherical nickel-cobalt-manganese hydroxide precursor and preparation method thereof |
| CN111600015B (en) * | 2020-07-27 | 2020-11-13 | 金驰能源材料有限公司 | Narrow-distribution small-granularity spherical nickel-cobalt-manganese hydroxide precursor and preparation method thereof |
| CN112174223A (en) * | 2020-08-27 | 2021-01-05 | 浙江美都海创锂电科技有限公司 | Preparation process of high-nickel NCA precursor |
| CN112591809A (en) * | 2020-12-29 | 2021-04-02 | 福建常青新能源科技有限公司 | Preparation method of NCA high-nickel ternary cathode material precursor |
| CN112591809B (en) * | 2020-12-29 | 2023-07-18 | 福建常青新能源科技有限公司 | Preparation method of NCA high-nickel ternary positive electrode material precursor |
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| CN113793925A (en) * | 2021-08-26 | 2021-12-14 | 广东芳源环保股份有限公司 | Wide-distribution micro-powder-free ternary precursor and preparation method thereof |
| CN113793925B (en) * | 2021-08-26 | 2023-06-06 | 广东芳源新材料集团股份有限公司 | Wide-distribution micropowder-free ternary precursor and preparation method thereof |
| CN115092976A (en) * | 2022-07-08 | 2022-09-23 | 金驰能源材料有限公司 | Preparation method of precursor with high specific surface area and high tap density |
| CN115092976B (en) * | 2022-07-08 | 2023-10-24 | 金驰能源材料有限公司 | Preparation method of precursor with high specific surface area and high tap density |
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