CN114044544A - Method for preparing wide-particle-size-distribution ternary precursor material by oxidation method - Google Patents
Method for preparing wide-particle-size-distribution ternary precursor material by oxidation method Download PDFInfo
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- 238000009826 distribution Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002243 precursor Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 239000000243 solution Substances 0.000 claims abstract description 80
- 239000002245 particle Substances 0.000 claims abstract description 74
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 66
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 29
- 239000012266 salt solution Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229940044175 cobalt sulfate Drugs 0.000 claims description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229940053662 nickel sulfate Drugs 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 32
- 239000002585 base Substances 0.000 description 16
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 238000002360 preparation method Methods 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
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 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
- 239000011164 primary particle Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for preparing a ternary precursor material with wide particle size distribution by an oxidation method, belonging to the technical field of lithium battery materials. The method for preparing the ternary precursor material with wide particle size distribution by the oxidation method comprises the following steps: mixing the reaction base solution with a mixed metal salt solution, a sodium hydroxide solution and an ammonia water solution under stirring for reaction, 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 the particle size distribution D50 is not less than 7 mu m and not more than 12 mu m and the particle size distribution K90 is not more than 0.8, adding the peak-forming gas at one time, then reducing the pH value of the reaction by 1.0-1.5 within 10min, stabilizing the pH value, and continuing the reaction until the particle size distribution returns 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 substance is cheap; 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 by an oxidation method, belonging to the technical field of lithium battery materials.
Background
The new energy automobile can reduce carbon emission, and new energy such as hybrid electric vehicles, plug-in hybrid electric vehicles and pure electric vehicles need to be loaded with lithium ion batteries as electric driving devices. The ternary material has become the main anode material of the current power battery because of high energy density and good rate performance. However, the traditional ternary material cannot meet the requirements of battery manufacturers on high energy density and high cycle performance of the power battery.
The primary particles and the secondary spherical particles of the ternary precursor material with wide particle size distribution have certain difference, the gaps generated between the particles are smaller, higher tap density can be provided, and the energy density of the anode material is relatively higher. The narrow-granularity ternary precursor material has the characteristics of high output power and high cycle, and the increase of the tap density is limited due to the structural characteristics.
How to control the distribution of the particle size distribution in a wide range? The method has important significance for preparing the ternary precursor material with smaller gap, high tap density and relatively higher energy density. At the present stage, depending on the adjustment of parameters in the production process, it is difficult to change the particle size distribution of the product, and the technical difficulty is high, for example, the particle size distribution is changed by adjusting the temperature, although the particle size distribution is widened, the pH adjustment is affected, the pH adjustment becomes insensitive and inaccurate, and the obtained material particles have rough surfaces and are not smooth. At present, in order to obtain a ternary precursor material with wide particle size distribution, the prior art firstly obtains precursor products with different particle size distributions, and then selects a plurality of precursor products to mix according to a certain proportion according to the requirements of customers so as to meet the requirements of particle size distribution.
CN111908517A, the invention discloses that in the process of synthesizing a high nickel precursor, precursor particles with small and medium particle sizes are mechanically mixed for intermittent preparation, aiming at maintaining the Span in a wider range in the process of particle growth by adopting the mode, and the collision of particles in a reaction system plays a role in buffering due to the existence of large and small particles, thereby avoiding the cracking of the particles in the synthesis process. The scheme is that in the synthesis process, small and medium particles are intermittently doped to maintain wide particle size distribution. However, a small-particle-size precursor and a medium-particle-size precursor are prepared respectively by adopting a solid-liquid extraction intermittent method, solid-liquid separation is carried out to obtain small-particle-size precursor particles and medium-particle-size precursor particles, the particle size Span of the small-particle-size precursor particles is controlled to be 0.8-1.2, the particle size Span of the medium-particle-size precursor particles is controlled to be 0.6-1.0, and the maximum particle size Span can reach 1.5 after the two particles are mixed. The process operation is very complicated and the cost is high.
CN109244450A discloses a preparation method of a high-compaction high-capacity lithium manganate composite positive electrode material for blending ternary materials, which comprises the following steps: step 1, preparing a lithium manganate positive electrode material with small particles and narrow particle size distribution; step 2, preparing a lithium manganate positive electrode material with large particles and wide particle size distribution; and 3, mixing the lithium manganate anode materials with the sizes and the particle size distributions. According to the invention, two manganese sources and lithium sources with different particle size distributions are finely controlled, the growth effect of crystal grains under high-temperature reaction is fully considered, two wide and narrow positive electrode materials are respectively prepared, and finally the positive electrode materials are mixed according to a certain proportion, so that the defect of insufficient compaction of a single material is solved, and the appearance defect caused by conventional secondary grading is avoided, so that the obtained 1C gram of positive electrode material has the capacity of 122-125 mAh/g, and the compaction density of 3.15g/cm3The above positive electrode material. Large-particle and small-particle raw materials need to be prepared respectively, sieved and mixed, and the process is complex and high in cost.
Disclosure of Invention
The invention aims to provide a method for preparing a ternary precursor material with wide particle size distribution by an oxidation method.
In order to achieve the purpose of the invention, the method for preparing the ternary precursor material with wide particle size distribution by the oxidation method comprises the following steps:
a. mixing the reaction base solution with a mixed metal salt solution, a sodium hydroxide solution and an ammonia water solution under a stirring state for reaction, 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;
b. when D50 is more than or equal to 7 microns and less than or equal to 12 microns and K90 is more than or equal to 0.8, adding peak-forming gas at one time, then reducing the pH value of the reaction by 1.0-1.5 within 10min, stabilizing the pH value, and continuing the reaction until the particle size distribution returns to a normal curve;
wherein the peak-making gas is at least one of air, oxygen or ozone, and the addition amount of the peak-making gas is 1-5 per mill of the volume of the reacted slurry;
preferably, the feeding speed of the mixed metal salt solution, the sodium hydroxide solution and the ammonia water solution is kept for 9-10 hours by the retention time.
The air is conventional air, and the concentration of oxygen in the air is about 21%.
In one specific embodiment, the addition amount of the air is 4-5 per mill of the volume of the reacted slurry; the addition amount of the oxygen is 1-2 per mill of the volume of the reacted slurry; the addition amount of the ozone is 0.5-1 per mill of the volume of the reacted slurry.
In a specific embodiment, the pH of the reaction in the step a is 10.5-11.
In a specific embodiment, the mixed metal salt solution in step a is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate.
In a specific embodiment, the total metal concentration of the mixed metal salt solution in the step a is 2-4 mol/L.
In a specific embodiment, the mixed metal salt solution has a nickel to cobalt to manganese molar ratio of 5:2:3 or 6:2:2 or 8:1: 1.
In a specific embodiment, the rotation speed of the stirring in the step a is 450-600 rpm.
In one embodiment, the concentration of the ammonia water solution is 150-200 g/L, preferably 150-180 g/L.
In a specific embodiment, the concentration of the sodium hydroxide solution is 4-6 mol/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 bottom liquid is preferably 20 to 40 percent of the total volume of the solution after the final reaction is completed.
And finally, after the reaction is completed, the total volume of the solution is the total volume of the slurry in the reaction kettle. In one embodiment, the amount of the base solution is generally selected according to the volume of the reaction kettle, and the volume of the base solution is generally 20-40% of the volume of the reaction kettle. For example: and 3L of base solution is added into a 10L reaction kettle, and the volume of the base solution is 30 percent of the volume of the reaction kettle.
Has the advantages that:
1. the peak-making material can be normally obtained through a conventional way, and is low in price;
2. the peak making method has convenient process, only needs to be added into a reaction system at one time within a certain time, and does not influence the normal production activity;
3. the effect of adjusting the particle size distribution is remarkable, and the product K90 can be adjusted from 0.64 to 1.34;
4. the Malvern particle size distribution curve of the product conforms to a normal curve without a sharp peak;
5. compared with the conventional means, the method saves equipment and time, does not need batch mixing equipment, only needs one set of crystallization reaction kettle as reaction equipment, and greatly saves the purchase cost and the arrangement site.
Drawings
FIG. 1 is an SEM photograph of example 3 before peak making.
FIG. 2 is an SEM photograph of the peak-making of example 3.
Detailed Description
In order to achieve the purpose of the invention, the method for preparing the ternary precursor material with wide particle size distribution by the oxidation method comprises the following steps:
a. mixing the reaction base solution with a mixed metal salt solution, a sodium hydroxide solution and an ammonia water solution under a stirring state for reaction, 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;
b. when D50 is more than or equal to 7 microns and less than or equal to 12 microns and K90 is more than or equal to 0.8, adding peak-forming gas at one time, then reducing the pH value of the reaction by 1.0-1.5 within 10min, stabilizing the pH value, and continuing the reaction until the particle size distribution returns to a normal curve;
wherein the peak-making gas is at least one of air, oxygen or ozone, and the addition amount of the peak-making gas is 1-5 per mill of the volume of the reacted slurry;
preferably, the feeding speed of the mixed metal salt solution, the sodium hydroxide solution and the ammonia water solution is kept for 9-10 hours by the retention time.
The air is conventional air, and the concentration of oxygen in the air is about 21%.
In one specific embodiment, the addition amount of the air is 4-5 per mill of the volume of the reacted slurry; the addition amount of the oxygen is 1-2 per mill of the volume of the reacted slurry; the addition amount of the ozone is 0.5-1 per mill of the volume of the reacted slurry.
In a specific embodiment, the pH of the reaction in the step a is 10.5-11.
In a specific embodiment, the mixed metal salt solution in step a is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate.
In a specific embodiment, the total metal concentration of the mixed metal salt solution in the step a is 2-4 mol/L.
In a specific embodiment, the mixed metal salt solution has a nickel to cobalt to manganese molar ratio of 5:2:3 or 6:2:2 or 8:1: 1.
In a specific embodiment, the rotation speed of the stirring in the step a is 450-600 rpm.
In one embodiment, the concentration of the ammonia water solution is 150-200 g/L, preferably 150-180 g/L.
In a specific embodiment, the concentration of the sodium hydroxide solution is 4-6 mol/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 bottom liquid is preferably 20 to 40 percent of the total volume of the solution after the final reaction is completed.
And finally, after the reaction is completed, the total volume of the solution is the total volume of the slurry in the reaction kettle. In one embodiment, the amount of the base solution is generally selected according to the volume of the reaction kettle, and the volume of the base solution is generally 20-40% of the volume of the reaction kettle. For example: and 3L of base solution is added into a 10L reaction kettle, and the volume of the base solution is 30 percent of the volume of the reaction kettle.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Preparing a solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total metal concentration of the solution is 2mol/L, and the molar ratio of nickel to cobalt to manganese is 5:2:3, and mixing to obtain a mixed metal salt solution; preparing a sodium hydroxide solution as a precipitator solution with the concentration of 5.2 mol/L; preparing an ammonia water solution as a complexing agent solution for later use, wherein the ammonia concentration of the solution is 150 g/L; A10L reaction kettle is adopted in the experiment, and the bottom liquid amount is 3L. The reaction bottom solution was 3L of a solution having an ammonia concentration of 13.5 g/L. 2L of reaction base solution is added into the reaction kettle, and then stirring is started at the rotating speed of 450 rpm. The mixed salt solution, sodium hydroxide solution and aqueous ammonia solution were then added by a peristaltic pump to react, wherein the feed rate of the mixed salt solution, sodium hydroxide, aqueous ammonia solution was maintained for 9 hours at its residence time. 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 certain period of reaction time. As shown in the table below, D50 was 11.97 μm, and particle size distribution K90 was 0.64. At the moment, air is injected into the system rapidly by a syringe, and the volume of the air is 5 per mill of the volume of the slurry in the existing reaction kettle. In this experiment, the volume of the slurry in the reaction kettle is 6.5L, so the volume of the injected air is 32.5 mL. And then immediately adjusting the flow rate of the alkali liquor, adjusting the pH value to 9.3 within 7min, stabilizing the pH value, and recovering the growth of particles until the particle size distribution is recovered to a normal curve. The test result shows that K90 is increased from 0.64 to 1.33 before and after peak making;
table 1 example 1 particle size distribution
| D10 | D50 | D90 | K90 | |
| Before peak making | 8.17 | 11.97 | 15.83 | 0.64 |
| After peak making | 5.68 | 7.77 | 16.02 | 1.33 |
Note: k90 ═ D90-D10/D50
Example 2
Preparing a solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total metal concentration of the solution is 4mol/L, the molar ratio of nickel to cobalt to manganese is 8:1:1, and mixing to obtain a mixed metal salt solution; preparing a sodium hydroxide solution as a precipitator solution with the concentration of 4 mol/L; preparing an ammonia water solution as a complexing agent solution for later use, wherein the ammonia concentration of the solution is 180 g/L; A10L reaction kettle is adopted in the experiment, and the bottom liquid amount is 4L. The reaction bottom solution was 4L of a solution having an ammonia concentration of 13.5 g/L. 2L of the reaction base solution was added to the reaction vessel, and then stirring was started at 580 rpm. The mixed salt solution, sodium hydroxide solution and aqueous ammonia solution were then added by a peristaltic pump to react, wherein the feed rate of the mixed salt solution, sodium hydroxide, aqueous ammonia solution was maintained for 9.5 hours at its residence time. The pH value is kept at 11.2 during the reaction, the reaction temperature is 60 ℃, and the ammonia concentration is controlled to be 13.5 +/-2 g/L.
After a certain period of reaction time. As shown in the table below, D50 was 7.18 μm, and particle size distribution K90 was 0.72. At the moment, a needle cylinder is used for quickly injecting oxygen into the system, and the volume of the oxygen is 2 per mill of the volume of the slurry in the existing reaction kettle. For this experiment, the volume of oxygen injected was calculated to be 10.2 mL. And then immediately adjusting the flow rate of the alkali liquor, adjusting the pH value to 10.2 within 8min, stabilizing the pH value, and recovering the growth of particles until the particle size distribution is recovered to a normal curve. The test results show that K90 increases from 0.72 to 1.34 before and after peak formation.
Table 2 example 2 particle size distribution
| D10 | D50 | D90 | K90 | |
| Before peak making | 4.59 | 7.18 | 9.78 | 0.72 |
| After peak making | 3.21 | 4.95 | 9.85 | 1.34 |
Example 3
Preparing a solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the total metal concentration of the solution is 2.9mol/L, and the molar ratio of nickel to cobalt to manganese is 6:2:2, and mixing to obtain a mixed metal salt solution; preparing a sodium hydroxide solution as a precipitator solution with the concentration of 6 mol/L; preparing an ammonia water solution as a complexing agent solution for later use, wherein the ammonia concentration of the solution is 200 g/L; A10L reaction kettle is adopted in the experiment, and the bottom liquid amount is 2L. The reaction bottom liquid was 2L of a solution having an ammonia concentration of 13.5 g/L. 2L of reaction base liquid is added into the reaction kettle, and then stirring is started at the rotating speed of 600 rpm. The mixed salt solution, sodium hydroxide solution and aqueous ammonia solution were then added by a peristaltic pump to react, wherein the feed rate of the mixed salt solution, sodium hydroxide, aqueous ammonia solution was maintained for 10 hours at its residence time. 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 certain period of reaction time. As shown in the table below, D50 was 10.47 μm, and particle size distribution K90 was 0.71. At the moment, a syringe is used for quickly injecting ozone into the system, and the volume of the ozone is 1 per mill of the volume of the slurry in the existing reaction kettle. For this experiment, the volume of ozone injected was calculated to be 5.5 mL. And then immediately adjusting the flow rate of the alkali liquor, adjusting the pH value to 10.0 after 8min, stabilizing the pH value, and recovering the growth of particles until the particle size distribution is recovered to a normal curve. The test results show that K90 increases from 0.71 to 1.26 before and after peak formation.
Table 3 example 3 particle size distribution
| D10 | D50 | D90 | K90 | |
| Before peak making | 6.78 | 10.47 | 14.19 | 0.71 |
| After peak making | 4.58 | 7.81 | 14.45 | 1.26 |
Comparative example 1
Preparing nickel sulfate, cobalt sulfate and manganese sulfate solutions, wherein the total metal concentration of the solutions is 2.5mol/L, the molar ratio of nickel to cobalt to manganese is 8:1:1, and mixing to obtain mixed metal salt solutions; preparing a sodium hydroxide solution as a precipitator solution with the concentration of 5 mol/L; preparing an ammonia water solution as a complexing agent solution for later use, wherein the ammonia concentration of the solution is 169 g/L; A10L reaction kettle is adopted in the experiment, and the bottom liquid amount is 2L. The reaction bottom liquid was 2L of a solution having an ammonia concentration of 13.5 g/L. 2L of reaction base liquid is added into the reaction kettle, and then stirring is started at the rotating speed of 600 rpm. The mixed salt solution, sodium hydroxide solution and aqueous ammonia solution were then added by a peristaltic pump to react, wherein the feed rate of the mixed salt solution, sodium hydroxide, aqueous ammonia solution was maintained for 9 hours at its residence time. The pH value is kept at 11.3 during the reaction, the reaction temperature is 65 ℃, and the ammonia concentration is controlled to be 13.5 +/-2 g/L.
After a certain period of reaction time. As shown in the table below, D50 was 10.47 μm, and particle size distribution K90 was 0.71. At the moment, a needle cylinder is used for quickly injecting oxygen into the system, and the volume of the oxygen is 5 per mill of the volume of the slurry in the existing reaction kettle. For this experiment, the volume of oxygen injected was calculated to be 26 mL. Thereafter, the color of the slurry was observed to change from green to black, the slurry was heavily oxidized, and the experiment failed.
Table 4 comparative example 1 particle size distribution
| D10 | D50 | D90 | K90 | |
| Before peak making | 6.10 | 9.42 | 12.88 | 0.72 |
| After peak making | — | — | — | — |
Claims (10)
1. The method for preparing the ternary precursor material with wide particle size distribution by the oxidation method is characterized by comprising the following steps of:
a. mixing the reaction base solution with a mixed metal salt solution, a sodium hydroxide solution and an ammonia water solution under a stirring state for reaction, 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;
b. when D50 is more than or equal to 7 microns and less than or equal to 12 microns and K90 is more than or equal to 0.8, adding peak-forming gas at one time, then reducing the pH value of the reaction by 1.0-1.5 within 10min, stabilizing the pH value, and continuing the reaction until the particle size distribution returns to a normal curve;
wherein the peak-making gas is at least one of air, oxygen or ozone, and the addition amount of the peak-making gas is 1-5 per mill of the volume of the reacted slurry;
preferably, the feeding speed of the mixed metal salt solution, the sodium hydroxide solution and the ammonia water solution is kept for 9-10 hours by the retention time.
2. The method for preparing the ternary precursor material with the wide particle size distribution by the oxidation method according to claim 1, wherein the addition amount of the air is 4-5 per mill of the volume of the reacted slurry; the addition amount of the oxygen is 1-2 per mill of the volume of the reacted slurry; the addition amount of the ozone is 0.5-1 per mill of the volume of the reacted slurry.
3. The method for preparing the ternary precursor material with the wide particle size distribution by the oxidation method according to claim 1 or 2, wherein the pH of the reaction in the step a is 10.5-11.
4. The oxidation method for preparing a wide particle size distribution ternary precursor material according to claim 1 or 2, wherein the mixed metal salt solution in step a is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate.
5. The method for preparing the ternary precursor material with the wide particle size distribution by the oxidation method according to claim 1 or 2, wherein the total metal concentration of the mixed metal salt solution in the step a is 2-4 mol/L.
6. The oxidation process for preparing a broad particle size distribution ternary precursor material according to claim 5, wherein the mixed metal salt solution has a molar ratio of nickel to cobalt to manganese of 5:2:3 or 6:2:2 or 8:1: 1.
7. The method for preparing the ternary precursor material with the wide particle size distribution by the oxidation method according to claim 1 or 2, wherein the stirring speed in the step a is 450-600 rpm.
8. The method for preparing the ternary precursor material with the wide particle size distribution through the oxidation method according to claim 1 or 2, wherein the concentration of the ammonia water solution is 150-200 g/L, and preferably 150-180 g/L.
9. The method for preparing the ternary precursor material with the wide particle size distribution through the oxidation method according to claim 1 or 2, wherein the concentration of the sodium hydroxide solution is 4-6 mol/L.
10. The method for preparing the ternary precursor material with the wide particle size distribution through the oxidation method according to claim 1 or 2, wherein the reaction base solution is ammonia water with the concentration of 12.5-14.5 g/L; the volume of the reaction bottom liquid is preferably 20 to 40 percent of the total volume of the solution after the final reaction is completed.
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