CN110190241A - A kind of preparation method of nickel cobalt manganese granular precursor - Google Patents
A kind of preparation method of nickel cobalt manganese granular precursor Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of nickel cobalt manganese presoma, specifically: the soluble-salt by soluble nickel salt respectively with soluble cobalt, soluble manganese salt and doping metals T is configured to nickel and cobalt solution, nickel manganese solution and nickel T solution, wherein the concentration of the nickel and cobalt solution is greater than the concentration of the nickel manganese solution, and the concentration of the nickel manganese solution is greater than the concentration of the nickel T solution；The nickel and cobalt solution and the nickel manganese solution are mixed, complexing agent is added to obtain mixed solution, and the mixed solution pH value is adjusted to 9-11.5 by the way that aqueous slkali is added；Then the nickel T solution is added to the mixed solution, is reacted under inert atmosphere, purity is high uniform to obtain particle, stable chemical performance nickel cobalt manganese granular precursor.The nickel cobalt manganese granular precursor that the present invention is prepared is reduced in gradient by core to surface, the relative amount of nickel element, and the relative amount of doped chemical increases in gradient.
Description
Technical field
The present invention relates to a kind of preparation methods of nickel cobalt manganese granular precursor, and in particular to a kind of liquid phase grade doping preparation
The method of nickel cobalt manganese granular precursor belongs to anode material of lithium battery preparation field.
Background technique
The problem of the generally existing structural stability difference of tertiary cathode material, numerous studies prove, are not reducing material excessively
Under the premise of chemical property, element doping is carried out on tertiary cathode material surface, it can be effectively by electrolyte and active material
Material isolation, avoids that side reaction occurs between the two, improves the stability of material.
Meanwhile its cycle performance can also be increased substantially by carrying out element doping to tertiary cathode material, and then promoted
The cruising ability of lithium ion battery.
Chinese Patent Application No. 2017107732466 discloses a kind of preparation side of nickel-cobalt-manganese ternary material for adulterating zinc
Method.In the patent, by nickel, cobalt, manganese and adulterate zinc compound mix, by wet-milling, plus lithium compound, plus ammonium hydroxide, ageing,
Dry predecessor has been prepared in cooling, drying and other steps.Dry predecessor is placed in oxygen atmosphere, using program liter
The tertiary cathode material for mixing zinc is made in warm therapy.The invention prepares the presoma of tertiary cathode material using the method that liquid phase mixes lithium
Grain.This method substantially increases the complexity of technique, while can only adulterate Zn-ef ficiency, and the scope of application is not wide.
Chinese Patent Application No. 201410462261 disclose a kind of grade doping anode material for lithium-ion batteries and its
Preparation method.In the patent, lithium source and granular precursor sintered product are impregnated in the solution of doped chemical, obtains to surface and covers
Have a product of doped chemical, then by the product and the lithium source blending for being not impregnated with solution, obtained after sintering the lithium of grade doping from
Sub- cell positive material.The invention doping method falls behind.Moreover, simple dipping is difficult to make doped chemical in granular precursor
Distribution gradient.Meanwhile doped chemical can only be wrapped in ternary precursor particle surface by this method in a manner of permeating, and be easy
Cause doped chemical in the enrichment of ternary precursor particle surface.
It can be seen that the prior art mainly using during preparing lithium salts by the method for solid phase method doped chemical into
Row element doping, this will cause doped chemical Local enrichment, interfere the homogeneity of product particle, reduce product stability, in turn
Material capacitance is improved to a certain extent.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of liquid phase grade doping preparation nickel cobalt manganese presoma, and this method can
By core to surface, the relative amount of nickel element reduces in gradient for preparation, and the relative amount of doped chemical is raised in gradient, grain
Degree is evenly distributed and can be used as providing the nickel cobalt manganese granular precursor of the positive electrode of high-capacitance.
The present invention provides a kind of method of liquid phase grade doping preparation nickel cobalt manganese presoma, the nickel cobalt manganese presomas
The structural formula of grain is NixCoyMnwTz(OH)2, wherein T is selected from one of Al, Mg, W, Zr, Ti, Y, Mo or Nb, and 0.8≤x
< 1,0 < y≤0.1,0 < w≤0.1,0.001 < z≤0.01, x+y+w+z=1 the described method comprises the following steps:
S1. the soluble-salt by soluble nickel salt respectively with soluble cobalt, soluble manganese salt and doping metals T is configured to nickel
Cobalt liquor, nickel manganese solution and nickel T solution, wherein the concentration of the nickel and cobalt solution is greater than the concentration of the nickel manganese solution, the nickel
The concentration of manganese solution is greater than the concentration of the nickel T solution；
S2. the nickel and cobalt solution and the nickel manganese solution are mixed, complexing agent is added to obtain mixed solution, and by adding
Enter aqueous slkali and the mixed solution pH value is adjusted to 9-11.5；
S3. then the nickel T solution is added to the mixed solution, is reacted under inert atmosphere, to obtain the nickel cobalt manganese
Granular precursor.
The nickel cobalt manganese granular precursor is reduced in gradient by core to surface, the relative amount of nickel element, doping metals T
The relative amount of element increases in gradient.
The partial size of the nickel cobalt manganese granular precursor is 5-18 μm.
The complexing agent is salt, and the concentration of the complexing agent is 1-15g/L.
The concentration of the complexing agent is 3-10g/L.
The concentration of the complexing agent is preferably 5-9g/L.
The feed rate of the complexing agent is 5-30L/h.
The salt is selected from S- carboxyethyl isothiuronium salts, benzyl chloropyridine salt, 1- ethyl-3-methylimidazole salt
Or one of propane sulfonic acid pyridiniujm.
The soluble nickel salt is selected from one of nickel sulfate, nickel nitrate or nickel acetate or a variety of.
The soluble cobalt is selected from one of cobaltous sulfate, cobalt nitrate or cobalt acetate or a variety of.
The solubility manganese salt is selected from one of manganese sulfate, manganese nitrate or manganese acetate or a variety of.
The soluble-salt of the doping metals T is one of sulfate, nitrate or acetate selected from doping metals T
Or it is a variety of.
The charging of the nickel and cobalt solution and the nickel manganese solution when mixing the nickel and cobalt solution and the nickel manganese solution
Flow is respectively 200-800L/h.
The concentration of the aqueous slkali is 25-200g/L, and the feed rate of the aqueous slkali is 15-35 L/h.
When being added the nickel T solution to the mixed solution, the feed rate of the nickel T solution is 40-55L/h.
The mass ratio of the nickel and cobalt solution, the nickel manganese solution and the nickel T solution is 10:4 ~ 6:0.5 ~ 2.
Total metal concentration Me is 60-130g/L.
Preferably, in S2, after reacting under inert atmosphere, the nickel cobalt manganese granular precursor is obtained after aged.
In S2, after reacting under inert atmosphere, the nickel cobalt manganese presoma is obtained after aged, centrifugation, washing, drying
Grain.
It is described reaction 60-80 DEG C at a temperature of carry out.
Reaction process described in S2 carries out under stirring conditions, and the frequency of stirring is 10-50Hz.
Preferably, the solid concentration in reaction process is 300-800g/L.
The present invention is a kind of preparation method of the nickel cobalt manganese presoma of liquid phase grade doping, the method by nickel and cobalt solution and
The mixing of nickel manganese solution is added complexing agent to obtain mixed solution, the mixed solution pH value is then adjusted to 9-11.5, is obtained
The colloid of hydroxide including nickel cobalt manganese and the mixed solution of nickel cobalt manganese ion.Nickel T solution is added under inert atmosphere
Reaction, to obtain nickel cobalt manganese granular precursor.The method can make nickel cobalt manganese ion and T ion with the hydroxide of nickel cobalt manganese
Colloid is that precipitation reaction occurs under alkaline condition for core, to obtain the nickel cobalt manganese of the splendid grade doping of particle uniformity
Granular precursor.
The method has the uniformity of reaction solution intermediate ion concentration when preparing the colloid of hydroxide of nickel cobalt manganese
Very high request.And in real industrial processes, in order to improve the production efficiency, production cost is reduced, reduces human factor pair
The influence of production, in solution concentration height, charging rate is fast, directly by nickel salt solution, cobalt salt solution in the case that mixing time is short
It is mixed with manganese salt solution, easily causes the problem that nickel ion, manganese ion or cobalt ions are excessively high in reaction kettle local concentration.Due to nickel
The solubility product of the hydroxide of cobalt manganese all very littles, adjusting pH value in this case is to be difficult to prepare uniform colloidal solid
's.Moreover, the solubility product of cobaltic hydroxide is especially small, and in the industrial production, the divalent cobalt in raw material is that have can
It can be oxidized to trivalent cobalt salt, therefore, during adjusting pH value, if there is the phenomenon that trivalent cobalt local concentration is excessively high,
It most likely results in trivalent cobalt and directly generates Co (OH)3Precipitating, so as to cause production failure.And it is big to prepare nickel ion concentration respectively
In the nickel and cobalt solution of concentration of cobalt ions, nickel ion concentration be greater than the nickel manganese solution of manganese ion concentration and nickel ion concentration be greater than T from
Then the nickel T solution of sub- concentration is mixed again, can reduce in mixed solution nickel cobalt manganese ion and T ion to the maximum extent in office
The case where portion is enriched with, so that uniform colloid can be prepared after adjusting pH value, and then it is splendid to prepare particle uniformity, first
The nickel cobalt manganese granular precursor for the grade doping that element is evenly distributed.
Relative to the technical solution that nickel salt solution, cobalt salt solution, manganese salt solution are directly mixed with the salting liquid of doped chemical,
The present invention uses the soluble-salt by soluble nickel salt respectively with soluble cobalt, soluble manganese salt and doping metals T to be configured to
Nickel and cobalt solution, nickel manganese solution and the nickel T solution of gradient concentration, then nickel and cobalt solution, nickel manganese solution are first mixed, add complexing
Evengranular nickel cobalt manganese granular precursor has been prepared in the technical solution that agent is reacted with pH adjusting agent.Meanwhile this hair
It is bright to use salt as complexing agent, the splendid nickel cobalt manganese granular precursor of particle uniformity has been prepared, has existed between the two
Apparent synergistic effect.
Compared with the existing technology, beneficial effects of the present invention are as follows:
1, the nickel cobalt manganese granular precursor that the present invention is prepared is by core to surface, and nickel element relative amount reduces in gradient, T
Element relative amount increases in gradient.
2, the preparation method of nickel cobalt manganese granular precursor of the present invention can be directly by doped chemical appendix in presoma, can
The uniform gradient distribution of doped chemical is effectively ensured, prevents doped chemical enrichment.
3, the preparation method of the nickel cobalt manganese granular precursor of the present invention, can be prepared nickel cobalt under liquid-phase condition
Manganese presoma.In the preparation process, reaction process is controllable, and the granular precursor uniformity of generation is splendid.
4, the splendid grade doping nickel cobalt manganese granular precursor of particle uniformity can be prepared in the present invention.Using the particle as
Raw material can save before mixing lithium sintering, the process of the particle refinement and homogenization of presoma, and the impurity for avoiding process generation is mixed
Enter presoma, to greatly improve the operability and practicability of mixed lithium anode material sintering process, improves battery material
Purity has ensured the electrochemistry quality of material.
5, it is miscellaneous to mix the battery material obtained after lithium sintering for the grade doping nickel cobalt manganese granular precursor that the present invention is prepared
Matter content is low, thus first charge-discharge capacity is high, stable chemical performance.
Detailed description of the invention
Fig. 1 is the SEM photograph for the nickel cobalt manganese granular precursor that embodiment 1 is prepared.
Fig. 2 is nickel cobalt manganese presoma individual particle that embodiment 1 is prepared into the element point obtained after line scan
Cloth schematic diagram.Abscissa is the centre of sphere element relative amount that the corresponding element relative amount of 6.5 μm of points is particle in Fig. 2, and horizontal
The constituent content at coordinate both ends corresponds to the constituent content of particle surface.As can be seen from the figure the nickel that the present embodiment 1 is prepared
Cobalt manganese granular precursor is reduced in gradient by core to surface, the relative amount of nickel element.
Fig. 3 is nickel cobalt manganese presoma individual particle that embodiment 1 is prepared into the element point obtained after line scan
Cloth schematic diagram.Abscissa is the centre of sphere element relative amount that the corresponding element relative amount of 6.5 μm of points is particle in Fig. 2, and horizontal
The constituent content at coordinate both ends corresponds to the constituent content of particle surface.As can be seen from the figure the nickel that the present embodiment 1 is prepared
Cobalt manganese granular precursor is increased in gradient by core to surface, the relative amount of aluminium element.
Specific embodiment
Present invention work is further illustrated below with reference to embodiment, but invention is not limited to specific embodiment.
The embodiment of the present invention proposes a kind of preparation method of nickel cobalt manganese granular precursor, comprising the following steps:
Step 1: the soluble-salt by soluble nickel salt respectively with soluble cobalt, soluble manganese salt and doping metals T is configured to
Nickel and cobalt solution, nickel manganese solution and nickel T solution；The concentration of the nickel and cobalt solution is greater than nickel manganese solution, the concentration of the nickel manganese solution
Greater than nickel T solution；
Step 2: after nickel and cobalt solution and nickel manganese solution are mixed, complexing agent is added, solution ph is adjusted to 9-11.5, then
Nickel T solution is added, is reacted under inert atmosphere, obtains the nickel cobalt manganese granular precursor.
The diameter characterization instrument of the nickel cobalt manganese granular precursor is laser particle analyzer.
It is respectively 10% that D10, D50 and D90, which respectively indicate the granule content calculated since maximum particle diameter to these particle size values,
50%, 90%.
SPAN=(D90-D10)/D50。
After the nickel cobalt manganese granular precursor mixes lithium, sintering obtains anode material of lithium battery.
Lithium ion battery can be prepared using the anode material of lithium battery.
The available discharge capacity data for the first time of electrical performance testing are carried out to the lithium ion battery being prepared.
The specific preparation process of the presoma is as follows:
Embodiment 1
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 5:0.6；Sulphur
The concentration of sour nickel manganese solution is 32g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 9g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, aluminium element concentration
Raised nickel cobalt manganese granular precursor in gradient.
Comparative example 1
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 1.5:1；Sulphur
The concentration of sour nickel manganese solution is 32g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 9g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
Nickel cobalt manganese granular precursor is dried to obtain at DEG C.
The nickel and cobalt solution that comparative example 1 is closer to using nickel cobalt and nickel manganese ion concentration, the nickel cobalt manganese forerunner being prepared
Body grain diameter is larger, broad particle distribution.This is because divalent cobalt is possible to be oxidized to trivalent cobalt in process of production.And
The ionic product of cobaltic hydroxide is very small, and when this makes that trivalent concentration of cobalt ions is slightly biased high in solution, that is, it is heavy to generate
It forms sediment, and then generates the nickel cobalt manganese granular precursor of greater particle size.
Embodiment 2
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 5:0.6；Sulphur
The concentration of sour nickel manganese solution is 32g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 1g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of aluminium element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 3
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 5:0.6；Sulphur
The concentration of sour nickel manganese solution is 32g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 2g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of aluminium element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 4
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 5:0.6；Sulphur
The concentration of sour nickel manganese solution is 32g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 12g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of aluminium element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 5
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 5:0.6；Sulphur
The concentration of sour nickel manganese solution is 32g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 14g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of aluminium element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 6
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 5:0.6；Sulphur
The concentration of sour nickel manganese solution is 40g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 3g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of aluminium element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 7
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 5:0.6；Sulphur
The concentration of sour nickel manganese solution is 40g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 5g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of aluminium element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 8
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 5:0.6；Sulphur
The concentration of sour nickel manganese solution is 40g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 7g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of aluminium element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 9
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and aluminum sulfate respectively
With nickel sulfate aluminum solutions；Wherein the concentration of sulfuric acid nickel and cobalt solution is 50g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 5:0.6；Sulphur
The concentration of sour nickel manganese solution is 40g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.4；Nickel sulfate aluminum solutions concentration is 6g/
The mass ratio of L, nickel sulfate and aluminum sulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 10g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate aluminum solutions into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate aluminium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of aluminium element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 10
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made with cobaltous sulfate, manganese sulfate and sulfuric acid tungsten respectively in nickel sulfate in proportion
With nickel sulfate tungsten solution；Wherein the concentration of sulfuric acid nickel and cobalt solution is 70g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 4:0.6；Sulphur
The concentration of sour nickel manganese solution is 32g/L, and the mass ratio of nickel sulfate and manganese sulfate is 4.5:0.4；Nickel sulfate tungsten solution concentration is 7g/
The mass ratio of L, nickel sulfate and sulfuric acid tungsten is 8:0.05.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 750L/h flow, nickel sulfate manganese solution is added with 380L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 8g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 11.5, then with the flow of 48L/h be added nickel sulfate tungsten solution into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:6 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate tungsten:
2, total metal concentration in mixed solution is 80g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 800g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of wolfram element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 11
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and magnesium sulfate respectively
With sulfuric acid Mg-Ni solution；Wherein the concentration of sulfuric acid nickel and cobalt solution is 45g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 3:0.5；Sulphur
The concentration of sour nickel manganese solution is 22g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2:0.3；Sulfuric acid Mg-Ni solution concentration is 6g/L,
The mass ratio of nickel sulfate and magnesium sulfate is 7:0.03.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 650L/h flow, nickel sulfate manganese solution is added with 580L/h flow
Enter reaction kettle, the propane sulfonic acid pyridine salt solution of concentration 7g/L is then added with the flow of 10L/h, is added with the flow of 35L/h
Entering the sodium hydroxide solution of concentration 180g/L to solution ph is 9.8, then with the flow of 48L/h be added sulfuric acid Mg-Ni solution into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:6 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate magnesium:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of magnesium elements
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 12
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and titanium sulfate respectively
With nickel sulfate titanium solution；Wherein the concentration of sulfuric acid nickel and cobalt solution is 45g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 7:1；Sulfuric acid
The concentration of nickel manganese solution is 22g/L, and the mass ratio of nickel sulfate and manganese sulfate is 3.5:0.3；Nickel sulfate titanium solution concentration is 6g/L,
The mass ratio of nickel sulfate and titanium sulfate is 5:0.04.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 250L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the 1- ethyl-3-methylimidazole salting liquid of concentration 6g/L is added, with the flow of 10L/h then with the stream of 28L/h
Sodium hydroxide solution to the solution ph that concentration 25g/L is added in amount is 10.8, and it is molten that sulfuric acid NiTi then is added with the flow of 48L/h
Liquid is reacted.Wherein, by the control to pump time, make the mass ratio of sulfuric acid nickel cobalt, nickel sulfate manganese and sulfuric acid NiTi
10:4.5:0.8 total metal concentration in mixed solution is 62g/L.Protective atmosphere in reaction process is nitrogen, reaction temperature
It is 65 DEG C.Reaction stirring stirring frequency controls 30Hz, and solid content controls 500g/L；After the reaction was completed, by ageing, be centrifuged, wash
It washs, and being dried to obtain partial size at 80 DEG C is 5-18 μm, by core to surface, the relative amount of nickel element reduces in gradient,
The relative amount of titanium elements raised nickel cobalt manganese presoma in gradient.
Embodiment 13
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made in nickel sulfate in proportion with cobaltous sulfate, manganese sulfate and molybdenum trisulfate respectively
With nickel sulfate molybdenum solution；Wherein the concentration of sulfuric acid nickel and cobalt solution is 45g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 8:1；Sulfuric acid
The concentration of nickel manganese solution is 22g/L, and the mass ratio of nickel sulfate and manganese sulfate is 2.5:0.3；Nickel sulfate molybdenum solution concentration is 6g/L,
The mass ratio of nickel sulfate and molybdenum trisulfate is 0.5:0.007.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 350L/h flow, nickel sulfate manganese solution is added with 280L/h flow
Enter reaction kettle, the benzyl chloropyridine salting liquid of concentration 5g/L is then added with the flow of 10L/h, is added with the flow of 28L/h
Entering the sodium hydroxide solution of concentration 25g/L to solution ph is 10.8, then with the flow of 48L/h be added nickel sulfate molybdenum solution into
Row reaction.Wherein, by the control to pump time, make the mass ratio 10:5 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate molybdenum:
1, total metal concentration in mixed solution is 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.Instead
Stirring frequency control 30Hz should be stirred, solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in 80
It is 5-18 μm that partial size is dried to obtain at DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, the phase of molybdenum element
To content raised nickel cobalt manganese presoma in gradient.
Embodiment 14
Sulfuric acid nickel and cobalt solution, nickel sulfate manganese solution is made with cobaltous sulfate, manganese sulfate and sulfuric acid niobium respectively in nickel sulfate in proportion
With nickel sulfate niobium solution；Wherein the concentration of sulfuric acid nickel and cobalt solution is 45g/L, and the mass ratio of nickel sulfate and cobaltous sulfate is 8:1；Sulfuric acid
The concentration of nickel manganese solution is 22g/L, and the mass ratio of nickel sulfate and manganese sulfate is 4:0.3；Nickel sulfate niobium solution concentration is 6g/L, sulphur
The mass ratio of sour nickel and sulfuric acid niobium is 7:0.08.
By pumping mode respectively by sulfuric acid nickel and cobalt solution with 450L/h flow, nickel sulfate manganese solution is added with 680L/h flow
Enter reaction kettle, the S- carboxyethyl isothiuronium salts solution of concentration 3g/L is added, with the flow of 10L/h then with the flow of 28L/h
Sodium hydroxide solution to the solution ph that concentration 25g/L is added is 10.8, and nickel sulfate niobium solution then is added with the flow of 48L/h
It is reacted.Wherein, by the control to pump time, make the mass ratio 10 of sulfuric acid nickel cobalt, nickel sulfate manganese and nickel sulfate niobium:
5:1, total metal concentration in mixed solution are 60g/L.Protective atmosphere in reaction process is nitrogen, and reaction temperature is 75 DEG C.
Reaction stirring stirring frequency controls 30Hz, and solid content controls 500g/L；After the reaction was completed, by ageing, centrifugation, washing, and in
It is 5-18 μm that partial size is dried to obtain at 80 DEG C, and by core to surface, the relative amount of nickel element reduces in gradient, niobium element
Relative amount raised nickel cobalt manganese presoma in gradient.
The test data for the nickel cobalt manganese presoma being prepared in 1. embodiment of table and comparative example is as shown in the table:
It is can be found that from upper table:
Relative to comparative example 1, the partial size that particle has been prepared in embodiment 1 is smaller, the nickel cobalt of the adulterated al of narrower particle size distribution
Manganese granular precursor.This is because divalent cobalt is possible to be oxidized to trivalent cobalt comparative example 1 during the preparation process.And it is cobaltic
The ionic product of hydroxide is very small, when this makes that trivalent concentration of cobalt ions is slightly biased high in solution, that is, generates precipitating, Jin Ersheng
At the nickel cobalt manganese granular precursor of greater particle size.
Embodiment 2-14 is using salt as complexing agent, and the partial size that particle has been prepared is smaller, narrower particle size distribution
The nickel cobalt manganese granular precursor and Doped Tungsten of adulterated al, magnesium, titanium, molybdenum, niobium nickel cobalt manganese granular precursor.
Claims (10)
1. a kind of preparation method of nickel cobalt manganese granular precursor, the structural formula of the nickel cobalt manganese granular precursor is NixCoyMnwTz
(OH)2, wherein T be selected from one of Al, Mg, W, Zr, Ti, Y, Mo or Nb, and 0.8≤x < 1,0 < y≤0.1,0 < w≤
0.1,0.001 < z≤0.01, x+y+w+z=1 the described method comprises the following steps:
It is molten that soluble nickel salt with the soluble-salt of soluble cobalt, soluble manganese salt and doping metals T is configured to nickel cobalt respectively
Liquid, nickel manganese solution and nickel T solution, wherein the mass ratio of nickel salt and cobalt salt is 2-8:0.1-1；Nickel salt and the mass ratio of manganese salt are 2-
8:0.1-1；And the mass ratio of the soluble-salt of nickel salt and doping metals T is 2-8:0.01-0.1；The nickel and cobalt solution it is dense
Degree is greater than the concentration of the nickel manganese solution, and the concentration of the nickel manganese solution is greater than the concentration of the nickel T solution；
The nickel and cobalt solution and the nickel manganese solution are mixed, complexing agent is added to obtain mixed solution, and by the way that alkali is added
The mixed solution pH value is adjusted to 9-11.5 by solution；
Then the nickel T solution is added to the mixed solution, is reacted under inert atmosphere, to obtain the nickel cobalt manganese forerunner
Body particle.
2. the preparation method of nickel cobalt manganese granular precursor according to claim 1, it is characterised in that:
The complexing agent is salt, and the concentration of the complexing agent is 1-15g/L.
3. the preparation method of nickel cobalt manganese granular precursor according to claim 1, it is characterised in that:
The concentration of the nickel and cobalt solution is greater than 40 g/L and is less than 80g/L,
The concentration of the nickel manganese solution is 20-40g/L,
The concentration of the nickel T solution is 5-10g/L.
4. the preparation method of nickel cobalt manganese granular precursor according to any one of claim 1 to 3, it is characterised in that:
The soluble nickel salt is selected from one of nickel sulfate, nickel nitrate or nickel acetate or a variety of；
The soluble cobalt is selected from one of cobaltous sulfate, cobalt nitrate or cobalt acetate or a variety of；
The solubility manganese salt is selected from one of manganese sulfate, manganese nitrate or manganese acetate or a variety of；
The soluble-salt of the doping metals T is one of sulfate, nitrate or acetate selected from doping metals T or more
Kind.
5. the preparation method of nickel cobalt manganese granular precursor according to any one of claim 1 to 3, it is characterised in that:
The feed rate of the nickel and cobalt solution and the nickel manganese solution when mixing the nickel and cobalt solution and the nickel manganese solution
Respectively 200-800L/h.
6. the preparation method of nickel cobalt manganese granular precursor according to any one of claim 1 to 3, it is characterised in that:
The concentration of the aqueous slkali is 25-200g/L, and the feed rate of the aqueous slkali is 15-35 L/h.
7. the preparation method of nickel cobalt manganese granular precursor according to any one of claim 1 to 3, it is characterised in that:
When being added the nickel T solution to the mixed solution, the feed rate of the nickel T solution is 40-55L/h.
8. the preparation method of nickel cobalt manganese granular precursor according to any one of claim 1 to 3, it is characterised in that:
The mass ratio of the nickel and cobalt solution, the nickel manganese solution and the nickel T solution is 10:4 ~ 6:0.5 ~ 2.
9. the preparation method of nickel cobalt manganese granular precursor according to any one of claim 1 to 3, it is characterised in that:
It is described reaction 60-80 DEG C at a temperature of carry out.
10. the preparation method of nickel cobalt manganese granular precursor according to claim 2, it is characterised in that:
The salt is selected from S- carboxyethyl isothiuronium salts, benzyl chloropyridine salt, 1- ethyl-3-methylimidazole salt or third
One of alkyl sulfonic acid pyridiniujm.
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