CN113651372A - Discontinuous growth preparation method of high-sphericity twinning-particle-free precursor - Google Patents
Discontinuous growth preparation method of high-sphericity twinning-particle-free precursor Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a discontinuous growth preparation method of a precursor with high sphericity and without twinning particles. In the precursor intermittent coprecipitation process, the pH value in the growth stage is strictly controlled between the critical pH value and the pH value at which the particles are gradually dispersed. The prepared precursor particles have high sphericity, uniform particles and narrow particle size distribution, and the twinning particle phenomenon is avoided.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a discontinuous growth preparation method of a precursor with high sphericity and without twinning particles.
Background
The discontinuous method for preparing the precursor with small particle size often faces the phenomenon of agglomeration growth. At the initial stage of particle nucleation, the nuclei tend to grow in an agglomerated state due to the large specific surface area. 2 and more nuclei agglomerate and grow together to produce agglomerated particles, and particles grown by only two nuclei agglomerate are called twin particles. Agglomeration can be avoided by adjusting the process parameters, but twinning is difficult to eliminate. Twin particles with a particle size within 5 microns can be observed by SEM that after the particles continuously grow to be more than 5 microns, gaps among the twin particles are gradually filled, the sphericity of the particles is better and better, and the twin particles disappear. The precursor with large particle size and twin particles gradually disappear along with the increase of the particle size, the twin ball phenomenon is basically avoided, and the product with small particle size often faces the twin ball phenomenon, and the twin ball influences the sphericity and uniformity of secondary particles, so that the uniformity of the anode material is influenced, and the storage and circulation performance is further influenced. The preparation of products with high sphericity and without twinning particles is technically difficult.
The technical proposal disclosed in the patent with the publication number of CN108025925B adopts a high-rotating-speed oxygen-free atmosphere in the nucleation stage to prepare the nickel-manganese-containing composite hydroxide with small particle size and narrow particle size distribution and high sphericity. However, from the SEM images provided therein, it can be seen that the prepared product has a poor sphericity of the particles, all being agglomerated growing particles, and the description proposed for preparing a composite hydroxide having a narrow particle size distribution with a high sphericity is not accurate.
The technical scheme disclosed in the patent with publication number CN106745331B adopts an ammonia complexing system, and is matched with an additive to disperse crystal nuclei under a high pH value, so that a precursor with good dispersibility and sphericity and a particle size of 2-3 mu m is prepared. However, as can be seen from the SEM images provided by the method, the sphericity of the particles is poor, half of the particles are twin particles, and half of the particles are particles grown by agglomeration of more than three cores, and the preparation method of the particles does not solve the problem of the twin particles.
The technical scheme disclosed in the patent with publication number CN108946827B adopts an ammonia nitrogen-free complexing system, the D50 of the prepared precursor can reach below 2.0 mu m, the particles keep high dispersibility, and the SEM image provided by the particle can show that the dispersibility is better, but a part of twin particles still exist.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a discontinuous method for growing and preparing nickel-cobalt-manganese hydroxide with high sphericity and without twin particles.
In order to achieve the purpose, the invention adopts the following technical scheme.
The discontinuous preparation method of the precursor of the anode material comprises the following steps:
step S1, according to chemical formula NixCoyM1-x-y(OH)2Preparing a metal salt solution, wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.3, and M is any one or more of Al, Zn, Fe, Zr, Yb, Mg, Mn and Ti; preparing a precipitator solution and a complexing agent solution.
And step S2, preparing a reaction kettle bottom liquid.
Step S3, adding the metal salt solution, the precipitator solution and the complexing agent solution into a reaction kettle with a base solution in a cocurrent manner to carry out coprecipitation reaction; after adding the metal salt solution for a period of time, reducing the pH value of the reaction system until no new nucleus is generated, and then increasing the pH value of the reaction system to a value between the critical value and the pH value when the particles are gradually dispersed within a certain time range, and entering the particle growth process.
In the coprecipitation reaction process, the form of the particles follows the change trend of agglomeration, gradual dispersion, particle adsorption and continuous seed crystal, the change trend of the form of the particles is determined by microscope observation, and the pH value when the particles are adsorbed is a critical value.
The pH value is always maintained in a pH value range which is lower than the critical pH value and higher than the gradual dispersion of the particles in the particle growth process, preferably the pH value is close to the critical pH value in the growth process, and the reaction is stopped after the particles grow to the target particle size.
And S4, aging, washing, drying and screening the solid phase obtained by solid-liquid separation of the reaction slurry obtained in the step S3 to obtain the nickel-cobalt-manganese hydroxide precursor with high sphericity and without twin particles.
In the coprecipitation process of the precursor of the cathode material, factors such as temperature, alkalinity and the like can influence the nucleation and growth processes, but the factors such as temperature, alkalinity and the like are not described too much in the invention, and the factors can be conventional parameters in the process of preparing the precursor by using a coprecipitation method by a person skilled in the art. The invention focuses on the regulation of the pH value.
Further, in the preparation method, the total concentration of metal ions in the nickel-cobalt-manganese mixed metal salt solution is 1.5-3 mol/L.
Furthermore, in the preparation method, the concentration of the complexing agent solution is 2-10mol/L, and the concentration of the precipitator solution is 2-11 mol/L.
Further, in the preparation method, the pH value of the base solution is 10-13, and the alkalinity is 1-40 g/L.
Further, in the above preparation method, the pH value of the reaction system is lowered after 10-60min of adding the metal salt solution, and the pH value of the reaction system is raised to between the critical value and the pH value when the particles are gradually dispersed within the range of 40-720 min.
In the coprecipitation process, the nucleation reaction is performed under a nitrogen atmosphere, that is, the reaction until no new nuclei are generated is performed under a nitrogen atmosphere.
During the co-precipitation, the particles adsorb when the pH of the reaction system is raised to a critical pH, because the particles in the reaction system reduce the surface energy by adsorption, providing nucleation energy.
The pH value of the discontinuous growth method of the precursor of the lithium battery anode material is generally lower than that of the continuous growth method, the continuous growth method needs continuous seed extraction and nucleation, the discontinuous growth method cannot seed extraction in the growth period, and when the pH value is higher, the system seed extraction is carried out, and the particle size distribution is widened. The pH value of the discontinuous method growth is gradually increased, the dispersibility among the particles is better and better, when the pH value is increased to the seed-removing pH value, the system can not seed, the seed can be removed only when a critical pH value is reached, the critical pH value is higher than the pH value of the seed, when the pH value of the discontinuous method growth exceeds the critical pH value, the system can seed, the critical pH value is influenced by the pH value and the nucleation amount of the bottom liquid of the initial synthesis tank, the critical pH value is determined by microscope observation, this is because as the pH is increased, the morphology of the particles follows a trend of agglomeration-gradual break-up-adsorption-deseeding, as long as the pH at which the particles adsorb is found, the pH value is the critical pH value, the growth pH value is controlled in the range of being lower than the critical pH value and higher than the gradually dispersed pH value, and the nickel-cobalt-manganese hydroxide precursor product with high sphericity and without twin particles can be obtained.
Compared with the prior art, the precursor particles prepared by the method have high sphericity, uniform particles and narrow particle size distribution, and the twinning particle phenomenon is avoided.
Drawings
Fig. 1 is a pH variation trend chart during precursor coprecipitation.
Fig. 2 is an SEM image of the precursor prepared in example 1, wherein a is a SEM image at a magnification of 5000, and b is a SEM image at a magnification of 1000.
FIG. 3 is a graph showing the particle size distribution of the precursor prepared in example 1.
Fig. 4 is an SEM image of the precursor prepared in example 2, wherein a is a SEM image at a magnification of 5000, and b is a SEM image at a magnification of 1000.
Fig. 5 is an SEM image of the precursor prepared in the comparative example, where a is a SEM image by 5000 times and b is a SEM image by 1000 times.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
In the coprecipitation process of the precursor of the positive electrode material, the control of the pH value is the key point.
As shown in fig. 1, the initial pH of the bottom solution of the reaction vessel may be higher than the critical pH or lower than the critical pH. This is because the initial pH of the reaction kettle bottom is affected by the amount of alkali added. An initial pH above the critical pH is high pH nucleation and an initial pH below the critical pH is low pH nucleation. Whether the nucleation is carried out at a high pH value or a low pH value, the bottom liquid of the reaction kettle is reduced to the lower pH value within 10-60 minutes, and the pH value is increased again within 40-720 minutes. According to the change trend of particle morphology from agglomeration, gradual dispersion, particle adsorption and seed extraction, the pH value of the particles when the particles are adsorbed is determined to be the critical pH value under a microscope. The growth stage of the precursor is between the critical pH value and the pH value at which the particles are gradually dispersed, and the pH value is close to the critical pH value in the preferable growth process, so that the nickel-cobalt-manganese hydroxide precursor product with high sphericity and without twin particles can be obtained.
Example 1:
preparing a nickel-cobalt-manganese metal salt solution with the total metal ion concentration of 2mol/L, a sodium hydroxide solution with the concentration of 10.8mol/L and an ammonia water solution with the concentration of 5mol/L according to the molar ratio of nickel, cobalt and manganese metal ions in the precursor of 7:0.5: 2.5. Deionized water is added into a reaction kettle, the stirring speed is controlled at 500r/min, the temperature is raised to 60 ℃, an ammonia water solution of a complexing agent is added, the concentration of the ammonia water is adjusted to 8g/l, and 800 ml of a sodium hydroxide solution is added. The initial pH of the bottom of the reaction vessel was 11.64. Introducing mixed metal solution, precipitator solution and complexing agent solution into the bottom liquid of the reaction kettle, after 30min, reducing the pH value of the reaction system to 11.34, after 60min, gradually increasing the pH value, observing and determining by a microscope that the critical pH value is 11.93, the pH value of gradually dispersed particles is 11.70, controlling the pH value in the whole growth period between 11.72 and 11.92, preferably between 11.82 and 11.92, when the particle size of slurry reaches 4.1 microns, discharging the slurry in a synthesis tank, carrying out solid-liquid separation, aging, washing, drying and screening a solid product to obtain the Ni with high sphericity and no twins particles0.7Co0.05Mn0.25(OH)2A precursor material.
FIG. 1 is a graph of the trend of pH change, which is used to guide the regulation of pH.
FIG. 2 is a scanning electron micrograph of the precursor prepared in example 1. As can be seen from the figure, the precursor has a high sphericity and is free of twinning particles.
FIG. 3 shows Ni in example 10.7Co0.05Mn0.25(OH)2The particle size distribution of the precursor is narrow.
The BET of the product was 10.87m2(g, TD 1.79 g/m)3D50 is 4.08. mu.m.
Example 2:
preparing a nickel-cobalt-manganese metal salt solution with the total metal ion concentration of 2mol/L, a sodium hydroxide solution with the concentration of 10.8mol/L and an ammonia water solution with the concentration of 6mol/L according to the molar ratio of nickel, cobalt and manganese metal ions in the precursor of 6:2: 2. Deionized water is added into a reaction kettle, the stirring speed is controlled at 500r/min, the temperature is raised to 55 ℃, complexing agent ammonia water is added, the concentration of the ammonia water is adjusted to 10g/l, and 500 ml of sodium hydroxide solution is added. The initial pH of the bottom of the reaction vessel was 11.31. Introducing mixed metal solution, precipitator solution and complexing agent solution into the bottom liquid of the reaction kettle, reducing the pH value to 11.11 after 30min, gradually increasing the pH value after 60min, determining the critical pH point to be 11.42 through microscope continuous observation, the pH value of gradually dispersed particles to be 11.15, controlling the pH value in the whole growth period to be between 11.18 and 11.41, preferably between 11.30 and 11.41, discharging the material in a synthesis tank when the particle size of the slurry reaches 4.0 microns, performing solid-liquid separation, aging, washing, drying and screening the solid product to obtain the Ni with high sphericity and no twin particles0.6Co0.2Mn0.2(OH)2A precursor material.
FIG. 4 is a scanning electron micrograph of the precursor prepared in example 2. As can be seen from the figure, the precursor has high sphericity, twin particles are not generated, and the sphericity of the particles is high; the secondary particles have good dispersibility; the BET of the product was 12.58m2(g), TD is 1.75g/m3D50 is 3.89 μm.
Comparative example:
preparing a nickel-cobalt-manganese metal salt solution with the total metal ion concentration of 2mol/L, a sodium hydroxide solution with the concentration of 10.8mol/L and an ammonia water solution with the concentration of 6mol/L according to the molar ratio of nickel, cobalt and manganese metal ions in the precursor of 6:2: 2. Deionized water is added into a reaction kettle, the stirring speed is controlled at 500r/min, the temperature is raised to 55 ℃, complexing agent ammonia water is added, the concentration of the ammonia water is adjusted to 10g/l, and 500 ml of sodium hydroxide solution is added.The initial pH of the bottom of the reaction vessel was 11.31. Introducing a mixed metal solution, a precipitator solution and a complexing agent solution into a reaction kettle bottom solution, reducing the pH to 11.11 after 30min, gradually increasing the pH after 60min, increasing the pH to 11.15 of the point where particles begin to disperse, reducing the point where the particles gradually disperse along with the growth of the particles, controlling the pH value in the whole growth period between 11.18 and 11.30, not searching a critical pH point, only ensuring that the particles observed under a microscope are in a dispersed state in the whole growth process, discharging the slurry when the particle size of the slurry reaches 4.0 microns, carrying out solid-liquid separation in a synthesis tank, aging, washing, drying and screening a solid product to obtain Ni0.6Co0.2Mn0.2(OH)2A precursor material.
Fig. 5 is a scanning electron micrograph of a precursor prepared in the comparative example. As can be seen from the figure, the overall sphericity of the particles is slightly poor, twin particles (the twin particles are particles in a circle) are contained, the sphericity is poor, the twin particles are mostly elliptical, and grooves can be formed among the particles; the secondary particles have better dispersibility; the BET of the product was 13.28m2(g), TD is 1.69g/m3D50 is 3.97. mu.m.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A discontinuous method for preparing a precursor is characterized by comprising the following steps:
step S1, according to chemical formula NixCoyM1-x-y(OH)2Preparing a metal salt solution, wherein x is more than 0.3 and less than 1, y is more than 0 and less than 0.3, and M is any one or more of Al, Zn, Fe, Zr, Yb, Mg, Mn and Ti; preparing a precipitator solution and a complexing agent solution;
step S2, preparing a reaction kettle bottom liquid;
step S3, adding the metal salt solution, the precipitator solution and the complexing agent solution into a reaction kettle with a base solution in a cocurrent manner to carry out coprecipitation reaction; after adding the metal salt solution for a period of time, reducing the pH value of the reaction system until no new nucleus is generated, and then increasing the pH value of the reaction system to a value between the critical value and the pH value when the particles are gradually dispersed; stopping the reaction after the particles grow to the target particle size;
and S4, after solid-liquid separation is carried out on the reaction slurry obtained in the step S3, the solid phase is aged, washed, dried and screened to obtain the nickel-cobalt-manganese hydroxide precursor with high sphericity and without twin particles.
2. The method of claim 1, wherein the total concentration of metal ions in the nickel-cobalt-manganese mixed metal salt solution is 1.5 to 3 mol/L; the concentration of the complexing agent solution is 2-10mol/L, and the concentration of the precipitator solution is 2-11 mol/L.
3. The method of claim 1, wherein the base solution has a pH of 10 to 13 and a basicity of 1 to 40 g/L.
4. The preparation method of claim 1, wherein the pH of the reaction system is lowered after 10 to 60min from the addition of the metal salt solution, and then the pH of the reaction system is raised to between the critical value and the pH at which the particles are gradually dispersed within a range of 40 to 720 min.
5. The method according to claim 1, wherein the reaction until no new nuclei are produced is carried out under a nitrogen atmosphere.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024088271A1 (en) | 2022-10-26 | 2024-05-02 | 河南科隆新能源股份有限公司 | Multilayer annular hole nickel-cobalt-aluminum precursor, preparation method for precursor and positive electrode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010008486A (en) * | 1999-07-01 | 2001-02-05 | 정몽규 | assembling machine for negative electrode plate of Ni-MH battery and assembling process therefor |
| CN103746111A (en) * | 2014-01-28 | 2014-04-23 | 天津先众科技有限公司 | Monocrystal Ni-Co-Mn battery positive pole material and preparing method thereof |
| CN111276689A (en) * | 2020-02-16 | 2020-06-12 | 四川新锂想能源科技有限责任公司 | Preparation method of nano porous ternary precursor |
| CN111883767A (en) * | 2020-07-31 | 2020-11-03 | 合肥国轩高科动力能源有限公司 | Preparation process of particle high-dispersion nickel-cobalt-manganese ternary precursor |
| CN112441627A (en) * | 2020-11-13 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for inhibiting twin crystals of nickel-cobalt-manganese ternary precursor |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010008486A (en) * | 1999-07-01 | 2001-02-05 | 정몽규 | assembling machine for negative electrode plate of Ni-MH battery and assembling process therefor |
| CN103746111A (en) * | 2014-01-28 | 2014-04-23 | 天津先众科技有限公司 | Monocrystal Ni-Co-Mn battery positive pole material and preparing method thereof |
| CN111276689A (en) * | 2020-02-16 | 2020-06-12 | 四川新锂想能源科技有限责任公司 | Preparation method of nano porous ternary precursor |
| CN111883767A (en) * | 2020-07-31 | 2020-11-03 | 合肥国轩高科动力能源有限公司 | Preparation process of particle high-dispersion nickel-cobalt-manganese ternary precursor |
| CN112441627A (en) * | 2020-11-13 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for inhibiting twin crystals of nickel-cobalt-manganese ternary precursor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024088271A1 (en) | 2022-10-26 | 2024-05-02 | 河南科隆新能源股份有限公司 | Multilayer annular hole nickel-cobalt-aluminum precursor, preparation method for precursor and positive electrode material |
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