CN114014384B - Method for preparing ternary precursor material with wide particle size distribution - Google Patents
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- 239000002245 particle Substances 0.000 title claims abstract description 90
- 238000009826 distribution Methods 0.000 title claims abstract description 52
- 239000002243 precursor Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 239000000243 solution Substances 0.000 claims abstract description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 27
- 239000012266 salt solution Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229940053662 nickel sulfate Drugs 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for preparing a ternary precursor material with wide particle size distribution, and belongs to the technical field of technical lithium battery materials. The method for preparing the ternary precursor material with wide particle size distribution comprises the following steps: mixing the reaction base solution with mixed metal salt solution, sodium hydroxide solution and ammonia water solution for reaction under the stirring state, wherein the pH value of the reaction is 10.5-11.4, the reaction temperature is controlled to be 55-65 ℃, and the concentration of the ammonia water is maintained to be 11.5-15.5 g/L during the reaction; when D50 is more than or equal to 9 mu m and less than or equal to 13 mu m, K90 is more than or equal to 0.8, small-particle-size precursor particles with D90 is more than or equal to 5 mu m are added at a time, then the pH value of the reaction is reduced by 0.5-1.0 within 10min, the pH value is stabilized, and the reaction is continued until the particle size distribution is restored to a normal curve. The invention widens the particle size distribution, and the particle size distribution is in a normal distribution state; the peak-making material is low in price; saving equipment, time and cost.
Description
Technical Field
The invention relates to a method for preparing a ternary precursor material with wide particle size distribution, and belongs to the technical field of technical lithium battery materials.
Background
The new energy automobile can reduce carbon emission, and the new energy of a hybrid electric automobile, a plug-in hybrid electric automobile, a pure electric automobile and the like all need to be loaded with lithium ion batteries as electric driving devices. The ternary material has high energy density and good multiplying power performance, and becomes a main positive electrode material of the current power battery. However, the conventional ternary material cannot meet the requirements of battery manufacturers on high energy density and high cycle characteristics of the power battery.
The primary particles and the secondary spherical particles of the ternary precursor material with wide particle size distribution have a certain gap, gaps are smaller between the particles, higher tap density can be provided, and the energy density of the positive electrode material is relatively higher. The narrow-granularity ternary precursor material has better uniformity and high output power and high circulation characteristics, but the structural characteristics determine that the tap density is improved only to a limited extent.
How does the particle size distribution be controlled over a wide range? The method has important significance for preparing ternary precursor materials with smaller gaps, high tap density and relatively higher energy density. At present, by means of adjusting parameters in the production process, the particle size distribution of the product is difficult to change, and the technical difficulty is high. For example, by adjusting the temperature to change the particle size distribution, the pH adjustment is affected, becomes insensitive, and is not controlled precisely, and the surface of the obtained material particles is rough and not smooth, although the particle size distribution is widened. In order to obtain a ternary precursor material with wide particle size distribution, the prior art adopts precursor products with different particle size distribution, and then selects a plurality of precursor products to be mixed according to a certain proportion according to the requirement of customers so as to meet the requirement of the particle size distribution.
In the process of synthesizing the high-nickel precursor, the CN111908517A is prepared by mechanically mixing precursor particles with small particle size and intermediate particle size to prepare the precursor particles by an intermittent method, and aims to maintain the Span in a wider range by adopting the mode in the particle growth process, and the collision of the particles in a reaction system plays a role in buffering due to the existence of the large and small particles, so that the cracking of the particles in the synthesis process is avoided. The scheme is that small and medium particles are intermittently doped in the synthesis process so as to maintain wide particle size distribution. However, firstly, preparing a small-particle-diameter precursor and a medium-particle-diameter precursor respectively by adopting a solid extractor batch method, carrying out solid-liquid separation to obtain small-particle-diameter precursor particles and medium-particle-diameter precursor particles, controlling the Span of the small-particle-diameter precursor particles to be 0.8-1.2, controlling the Span of the medium-particle-diameter precursor particles to be 0.6-1.0, and mixing the two particles until the Span is the highest, thus reaching 1.5. The process operation is very complex and the cost is high.
Disclosure of Invention
The invention aims to provide a method for preparing a ternary precursor material with wide particle size distribution.
To achieve the object of the present invention, the method for preparing a ternary precursor material with a broad particle size distribution includes:
a. mixing the reaction base solution with a mixed metal salt solution, a sodium hydroxide solution and an ammonia solution for reaction under the stirring state, wherein the pH value of the reaction is 10.5-11.4, the temperature of the reaction is controlled to be 55-65 ℃, and the concentration of the ammonia water is maintained to be 11.5-15.5 g/L during the reaction;
b. when D50 is more than or equal to 9 mu m and less than or equal to 13 mu m and K90 is more than or equal to 0.8, small-particle-size precursor particles with the D90 being less than or equal to 5 mu m are added at one time, then the pH value of the reaction is reduced by 0.5 to 1.0 within 10min, the pH value is stabilized, and the reaction is continued until the particle size distribution is restored to a normal curve;
wherein the addition amount of the small-particle-diameter precursor particles is 4-8 wt.%, preferably 5-6 wt.% of the solid content in the reaction system;
preferably, the mixed metal salt solution, sodium hydroxide solution and ammonia solution are fed at such a rate that the residence time thereof is maintained for 8 to 9 hours.
The pH value of the reaction is reduced by 0.5 to 1.0 within 10min, the pH value is stabilized, and the particles can continue to resume growing.
In a specific embodiment, the pH of the reaction of step a is from 10.5 to 11.
In a specific embodiment, the mixed metal salt solution in the step a is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate.
In one embodiment, the total metal concentration of the mixed metal salt solution in step a is 2 to 4mol/L.
In one embodiment, the molar ratio of nickel, cobalt and manganese in the mixed metal salt solution is 5:2:3 or 6:2:2 or 8:1:1.
In a specific embodiment, the stirring speed in step a is 400-600 rpm, preferably 450-600 rpm.
In one embodiment, the concentration of the aqueous ammonia solution is 100 to 200g/L, preferably 100 to 160g/L.
In one embodiment, the concentration of the sodium hydroxide solution is 4 to 6mol/L.
In a specific embodiment, the reaction base solution is ammonia water with the concentration of 12.5-14.5 g/L; the volume of the reaction base solution is preferably 20% -40% of the total volume of the solution after the final reaction is completed.
And after the final reaction is completed, the total volume of the solution, namely the total volume of the slurry in the reaction kettle. In one embodiment, the amount of base fluid is generally selected based on the volume of the reactor, and the base fluid volume is generally 20-40% of the volume of the reactor. For example: and (3) adding 3L of base solution into a 10L reaction kettle, wherein the volume of the base solution is 30% of that of the reaction kettle.
In a specific embodiment, small-particle-size precursor particles are added at one time when K90 is more than or equal to 0.6 and less than or equal to 0.8 in the step b.
The beneficial effects are that:
1. in the reaction production stage, the invention changes the environment of a reaction system by a specific method, so that the particle size distribution is widened, and the particle size distribution is in a normal distribution state;
2. the peak-making substance material can be normally obtained through a conventional way, and has low price;
3. the peak-making method is convenient in process, and can be carried out by adding the reaction system once in a certain time without influencing the normal production activity;
4. the effect of adjusting the particle size distribution is remarkable, and the K90 of the product can be adjusted from 0.65 to 1.40;
5. the Markov particle size distribution curve of the product accords with a normal curve, and no abrupt peak exists;
6. compared with the conventional means, the method saves more equipment and time, does not need to use batch mixing equipment, and only needs to use a set of crystallization reaction kettles for reaction equipment, thereby greatly saving purchase cost and arrangement place.
Drawings
FIG. 1 is a Markov diagram of the product of example 1.
FIG. 2 is an SEM image before peaking in example 3.
FIG. 3 is an SEM image after peaking of example 3.
Fig. 4 is a markov diagram of the product of example 3.
Detailed Description
To achieve the object of the present invention, the method for preparing a ternary precursor material with a broad particle size distribution includes:
a. mixing the reaction base solution with a mixed metal salt solution, a sodium hydroxide solution and an ammonia solution for reaction under the stirring state, wherein the pH value of the reaction is 10.5-11.4, the temperature of the reaction is controlled to be 55-65 ℃, and the concentration of the ammonia water is maintained to be 11.5-15.5 g/L during the reaction;
b. when D50 is more than or equal to 9 mu m and less than or equal to 13 mu m and K90 is more than or equal to 0.8, small-particle-size precursor particles with the D90 being less than or equal to 5 mu m are added at one time, then the pH value of the reaction is reduced by 0.5 to 1.0 within 10min, the pH value is stabilized, and the reaction is continued until the particle size distribution is restored to a normal curve;
wherein the addition amount of the small-particle-diameter precursor particles is 4-8 wt.%, preferably 5-6 wt.% of the solid content in the reaction system;
preferably, the mixed metal salt solution, sodium hydroxide solution and ammonia solution are fed at such a rate that the residence time thereof is maintained for 8 to 9 hours.
The pH value of the reaction is reduced by 0.5 to 1.0 within 10min, the pH value is stabilized, and the particles can continue to resume growing.
In a specific embodiment, the pH of the reaction of step a is from 10.5 to 11.
In a specific embodiment, the mixed metal salt solution in the step a is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate.
In one embodiment, the total metal concentration of the mixed metal salt solution in step a is 2 to 4mol/L.
In one embodiment, the molar ratio of nickel, cobalt and manganese in the mixed metal salt solution is 5:2:3 or 6:2:2 or 8:1:1.
In a specific embodiment, the stirring speed in step a is 400-600 rpm, preferably 450-600 rpm.
In one embodiment, the concentration of the aqueous ammonia solution is 100 to 200g/L, preferably 100 to 160g/L.
In one embodiment, the concentration of the sodium hydroxide solution is 4 to 6mol/L.
In a specific embodiment, the reaction base solution is ammonia water with the concentration of 12.5-14.5 g/L; the volume of the reaction base solution is preferably 20% -40% of the total volume of the solution after the final reaction is completed.
And after the final reaction is completed, the total volume of the solution, namely the total volume of the slurry in the reaction kettle. In one embodiment, the amount of base fluid is generally selected based on the volume of the reactor, and the base fluid volume is generally 20-40% of the volume of the reactor. For example: and (3) adding 3L of base solution into a 10L reaction kettle, wherein the volume of the base solution is 30% of that of the reaction kettle.
In a specific embodiment, small-particle-size precursor particles are added at one time when K90 is more than or equal to 0.6 and less than or equal to 0.8 in the step b.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
Preparing nickel sulfate, cobalt sulfate and manganese sulfate solution, wherein the total metal concentration of the solution is 2mol/L, the molar ratio of nickel to cobalt to manganese is 5:2:3, and mixing to obtain mixed metal salt solution; preparing a sodium hydroxide solution as a precipitant solution, wherein the concentration is 6mol/L; preparing an ammonia water solution as a complexing agent solution for standby, wherein the ammonia concentration of the solution is 150g/L; the experiment adopts a 10L reaction kettle, the liquid amount of the bottom liquid is 3L, the ammonia concentration of the reaction bottom liquid is 13.5+/-1 g/L, the reaction bottom liquid is added into the reaction kettle, and then stirring is started, and the rotating speed is 450rpm. Then, the above mixed salt solution, sodium hydroxide solution and ammonia solution were added by peristaltic pump to react, wherein the addition rates of the mixed metal salt solution, sodium hydroxide and ammonia solution were controlled to be maintained for 8 hours at their residence times. The pH value is kept at 10.5 during the reaction, the reaction temperature is 55 ℃, and the ammonia concentration is controlled to be 13.5+/-2 g/L.
After a period of reaction. As shown in the following table, d50=9.76 μm, particle size distribution k90=0.8. At this time, small precursor crystal particles with the particle diameter D90 of less than or equal to 5 mu m are added into the system, the proportion is 5wt.% of the solid content of the slurry in the existing reaction kettle, and in the experiment, the addition amount is determined to be 20g through calculation. And then, immediately adjusting the flow rate of the alkali liquor, adjusting the pH value to 9.9 in 8 minutes, stabilizing the pH value, and recovering the growth of the particles until the particle size distribution is recovered to a normal curve. The test results showed that K90 increased from 0.8 to 1.4 before and after peaking. It can be seen from fig. 1 that the malvern particle size distribution curve of the product conforms to a normal curve without sharp peaks.
Table 1 example 1 particle size distribution
| D10 | D50 | D90 | K90 | |
| Before peak formation | 5.89 | 9.76 | 13.70 | 0.80 |
| After peak formation | 3.85 | 8.71 | 16.02 | 1.40 |
Note that: k90 = (D90-D10)/D50
Example 2
Preparing nickel sulfate, cobalt sulfate and manganese sulfate solution, wherein the total metal concentration of the solution is 4mol/L, the molar ratio of nickel to cobalt to manganese is 6:2:2, and mixing to obtain mixed metal salt solution; preparing a sodium hydroxide solution as a precipitant solution, wherein the concentration is 4mol/L; preparing an ammonia water solution as a complexing agent solution for standby, wherein the ammonia concentration of the solution is 100g/L; the experiment adopts a 10L reaction kettle, the liquid amount of the bottom liquid is 2L, the ammonia concentration of the reaction bottom liquid is 13.5+/-1 g/L, the reaction bottom liquid is added into the reaction kettle, and then stirring is started, and the rotating speed is 600rpm. Then, the mixed salt solution, the sodium hydroxide solution and the ammonia solution are added by peristaltic pumps to react, wherein the addition rates of the mixed metal salt solution, the sodium hydroxide solution and the ammonia solution are based on the retention time of 9 hours. The pH value is kept at 11.4 during the reaction, the reaction temperature is 65 ℃, and the ammonia concentration is controlled to be 13.5+/-2 g/L.
After a period of reaction. As shown in the following table, d50=13.02 μm, and particle size distribution k90=0.78. At this time, small crystal particles of the precursor having a particle diameter D90.ltoreq.5 μm were added to the system in a proportion of 8wt.% based on the solid content of the slurry in the existing reaction vessel, and in this experiment, the addition was calculated to be 23.6g. And then, immediately adjusting the flow rate of the alkali liquor, adjusting the pH value to 10.5 for 10min, stabilizing the pH value, and recovering the growth of the particles until the particle size distribution is recovered to a normal curve. The test results showed that K90 increased from 0.78 to 1.35 before and after peaking.
TABLE 2 example 2 particle size distribution
| D10 | D50 | D90 | K90 | |
| Before peak formation | 7.85 | 13.02 | 18.02 | 0.78 |
| After peak formation | 5.91 | 10.31 | 19.86 | 1.35 |
Example 3
Preparing nickel sulfate, cobalt sulfate and manganese sulfate solution, wherein the total metal concentration of the solution is 2mol/L, the molar ratio of nickel to cobalt to manganese is 8:1:1, and mixing to obtain mixed metal salt solution; preparing a sodium hydroxide solution as a precipitant solution, wherein the concentration is 4mol/L; preparing an ammonia water solution as a complexing agent solution for standby, wherein the ammonia concentration of the solution is 200g/L; the experiment adopts a 10L reaction kettle, the liquid amount of the bottom liquid is 4L, the ammonia concentration of the reaction bottom liquid is 13.5+/-1 g/L, the reaction bottom liquid is added into the reaction kettle, and then stirring is started, and the rotating speed is 550rpm. Then adding the mixed salt solution, the sodium hydroxide solution and the ammonia water solution by peristaltic pumps, wherein the feeding rates of the mixed metal salt solution, the sodium hydroxide solution and the ammonia water solution are based on the retention time of 8.5 h. The pH value is kept at 11.4 during the reaction, the reaction temperature is 65 ℃, and the ammonia concentration is controlled to be 13.5+/-2 g/L.
After a period of reaction. As shown in the following table, d50=9.04 μm and k90=0.65, the SEM image of the product is shown in fig. 2, and the particle size of the particles is relatively uniform. At this time, small crystal particles of the precursor having a particle diameter D90.ltoreq.5 μm were added to the system in a proportion of 6wt.% based on the solid content of the slurry in the existing reaction vessel, and in this experiment, the addition was calculated to be 15.9g. And then, immediately adjusting the flow rate of the alkali liquor, adjusting the pH value to 10.4 in 10min, stabilizing the pH value, and recovering the growth of the particles until the particle size distribution is recovered to a normal curve, wherein the SEM image of the product is shown in figure 3, and the particle size distribution of the particles is wide. The test results showed that K90 increased from 0.65 to 1.33 before and after peaking. It can be seen from fig. 4 that the malvern particle size distribution curve of the product conforms to a normal curve without sharp peaks.
TABLE 3 example 3 particle size distribution
| D10 | D50 | D90 | K90 | |
| Before peak formation | 6.04 | 9.04 | 11.94 | 0.65 |
| After peak formation | 4.14 | 7.6 | 14.27 | 1.33 |
Claims (12)
1. A method for preparing a ternary precursor material with wide particle size distribution, which is characterized by comprising the following steps:
a. mixing the reaction base solution with a mixed metal salt solution, a sodium hydroxide solution and an ammonia solution under a stirring state for reaction, wherein the pH value of the reaction is 10.5-11.4, the temperature of the reaction is controlled to be 55-65 ℃, the concentration of the ammonia water is maintained to be 11.5-15.5 g/L during the reaction, the mixed metal salt solution in the step a is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, and the total metal concentration of the mixed metal salt solution in the step a is 2-4 mol/L;
b. when D50 which is more than or equal to 9 mu m and less than or equal to 13 mu m and K90 which is more than or equal to 0.6 and less than or equal to 0.8, small-particle-size precursor particles with D90 which is more than or equal to 5 mu m are added at one time, then the pH value of the reaction is reduced by 0.5 to 1.0 within 10min, the pH value is stabilized, and the reaction is continued until the particle size distribution is restored to a normal curve;
wherein the addition amount of the small-particle-diameter precursor particles is 4-8 wt.% of the solid content in the reaction system.
2. The method for preparing a ternary precursor material with wide particle size distribution according to claim 1, wherein the addition amount of the small-particle-size precursor particles is 5-6 wt.% of the solid content in the reacted system.
3. The method for preparing a ternary precursor material with broad particle size distribution according to claim 1 or 2, wherein the feed rates of the mixed metal salt solution, sodium hydroxide solution and ammonia solution are maintained for 8-9 h at the residence time.
4. The method for preparing a broad particle size distribution ternary precursor material according to claim 1, wherein the pH of the reaction in step a is 10.5-11.
5. The method of preparing a broad particle size distribution ternary precursor material according to claim 1, wherein the molar ratio of nickel, cobalt, manganese in the mixed metal salt solution is 5:2:3 or 6:2:2 or 8:1:1.
6. The method for preparing a broad particle size distribution ternary precursor material according to claim 1 or 2, wherein the rotational speed of stirring in step a is 400-600 rpm.
7. The method for preparing a ternary precursor material with a broad particle size distribution according to claim 6, wherein the stirring speed in step a is 450-600 rpm.
8. The method for preparing a broad particle size distribution ternary precursor material according to claim 1 or 2, wherein the concentration of the aqueous ammonia solution is 100-200 g/L.
9. The method for preparing a broad particle size distribution ternary precursor material according to claim 8, wherein the concentration of the aqueous ammonia solution is 100-160 g/L.
10. The method for preparing a ternary precursor material with a broad particle size distribution according to claim 1 or 2, wherein the concentration of the sodium hydroxide solution is 4-6 mol/L.
11. The method for preparing a ternary precursor material with wide particle size distribution according to claim 1 or 2, wherein the reaction base solution is ammonia water with a concentration of 12.5-14.5 g/L.
12. The method for preparing a ternary precursor material with wide particle size distribution according to claim 11, wherein the volume of the reaction base solution is 20% -40% of the total volume of the solution after the final reaction is completed.
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