CN116354412A - Preparation method of doped ternary precursor for improving sphericity of large particles - Google Patents
Preparation method of doped ternary precursor for improving sphericity of large particles Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 60
- 239000002245 particle Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000013078 crystal Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 32
- 239000008139 complexing agent Substances 0.000 claims abstract description 29
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004005 microsphere Substances 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 239000012716 precipitator Substances 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- 238000000975 co-precipitation Methods 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000010413 mother solution Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 238000001000 micrograph Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000011437 continuous method Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C01P2004/32—Spheres
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Abstract
The invention discloses a preparation method of a doped ternary precursor for improving sphericity of large particles, which comprises the following steps: s1, preparing nickel-cobalt-manganese mixed salt solution, a precipitator, a complexing agent and zirconia microsphere suspension; s2, preparing crystal nucleus slurry; s3, setting flow according to the product requirement proportion, continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitator, the complexing agent, the zirconia microsphere suspension and the crystal nucleus slurry into a reaction kettle, and regulating the flow of the precipitator, the complexing agent and the crystal nucleus slurry according to the test condition to stabilize the reaction atmosphere and continuously reacting until the precursor product with the required particle size is obtained. The advantages are that: 1) The zirconia microsphere suspension is added to participate in the coprecipitation process of the precursor, so that the particle sphericity of the large-particle ternary precursor product is obviously improved on the premise of not influencing a reaction system. 2) By adding the crystal nucleus slurry at the same time of coprecipitation feeding, the sphericity of the whole particle of the product can be further improved, and the ratio of the small particle product with new nucleation can be reduced.
Description
Technical Field
The invention relates to a lithium battery production technology, in particular to a lithium battery anode material ternary precursor production technology.
Background
As one of the main bodies of new energy, lithium ion batteries are receiving attention because of their small size, high capacity, low price, and the like. With the rapid development of industry, the performance requirements of lithium ion batteries are also increasing. The performance of lithium ion batteries is primarily dependent on the ternary cathode material, and ternary precursors are the main factors affecting the ternary cathode material. In order to obtain the ternary positive electrode material with good cycle performance, high capacity, good ploidy and low price, the improvement of the performance of the ternary precursor is the primary focus. The ternary positive electrode material has excellent electrochemical performance, good thermal stability and lower production cost, is rising in the lithium battery industry, and is a powerful competitor for next-generation lithium ion and battery positive electrode materials. However, compared with LCoO, the conductivity is lower and the high rate performance is poor. In addition, the tap density is low, the volume energy density is influenced, in order to pursue high energy density, the precursor end is optimized, the tap density of the precursor is improved, and the compaction density of the positive electrode material can be improved, so that the energy density of the battery is improved. However, the high impact factor of the tap density is the sphericity of the particles, and the high sphericity of the particles can correspondingly improve the tap density. Large-particle products produced by the traditional continuous method generally have the conditions of low sphericity of large particles, poor sphericity of small particles and even no sphericity.
Chinese patent CN110040T9OA discloses a high sphericity nickel-manganese ternary precursor and a preparation method thereof, wherein hard microspheres are added, and under the action of strong stirring, the collision frequency and the collision times of a nickel-manganese ternary precursor product in the growth process are increased, so that the small-particle nickel-manganese ternary precursor is promoted to be formed into high sphericity in a shorter growth time, natural sedimentation is utilized after the reaction is finished, and the suspension and slurry of the hard microspheres are separated, thereby obtaining the high sphericity nickel-cobalt-manganese ternary precursor. The method is a batch reaction, cannot continuously produce, and needs to periodically stop the reaction and divide the seed crystal and the particles into high parts, so that the production efficiency is low, and the growth period is very short when preparing the precursor with small particle size, so that the production practicability is low.
Disclosure of Invention
In order to improve the overall particle sphericity of the large-particle precursor product and solve the problem of low sphericity of the large-particle product produced by a general continuous method, thereby improving the electrochemical performance of the positive electrode material and realizing continuous production, the invention provides a preparation method of the doped ternary precursor for improving the sphericity of the large particles.
The technical scheme adopted by the invention is as follows: the preparation process of doped ternary precursor with high granularity includes the step of adding zirconia microsphere suspension during coprecipitation reaction.
As a further improvement of the present invention, the step of adding a crystal nucleus slurry at the time of the coprecipitation reaction is also included.
As a further improvement of the invention, the zirconia microsphere suspension is formed by mixing deionized water and zirconia with the granularity of 80-120 mu m, and the zirconia concentration in the zirconia microsphere suspension is 80-120 g/L.
The preparation method of the ternary precursor can be implemented according to the following steps:
s1, preparing nickel-cobalt-manganese mixed salt solution, a precipitator, a complexing agent and zirconia microsphere suspension;
s2, preparing crystal nucleus slurry;
s3, preparing a required base solution by using a mother solution in a second reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring rate and the temperature in the kettle stably controlled at process required values, adjusting the pH value and the ammonia concentration of the base solution to the process required values, setting flow according to the product required proportion, continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitator, the complexing agent, the zirconia microsphere suspension and the crystal nucleus slurry into the second reaction kettle, and adjusting the flow of the precipitator, the complexing agent and the crystal nucleus slurry according to the test condition to stabilize the reaction atmosphere and continuously reacting until the precursor product with the required particle size is obtained.
In the above method, the crystal nucleus slurry may be prepared as follows:
A. preparing a required base solution by using a mother solution in a first reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring rate and the temperature in the kettle stably controlled at process required values, and regulating the pH value and the ammonia concentration of the base solution to the process required values;
B. and setting flow according to the product requirement proportion, continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitator and the complexing agent into the first reaction kettle, regulating the flow of the precipitator and the complexing agent according to the test condition to stabilize the reaction atmosphere, and continuously reacting until the crystal nucleus slurry with the required particle size is obtained.
More preferably, in the above method, the precipitant is preferably sodium hydroxide solution having a NaOH concentration of 3 to 15 mol/L; the complexing agent is preferably NH 3 Ammonia water solution with concentration of 0.1-1.0 mol/L.
More preferably, the concentration of metal ions in the nickel-cobalt-manganese mixed salt solution is 1.5-2.5 mol/L.
The invention also discloses a ternary precursor which is prepared by the method.
More preferably, the ternary precursor of the invention satisfies Ni: co: mn=x: y:1-x-y, wherein 0.8.ltoreq.x.ltoreq. 0.9,0.03.ltoreq.y.ltoreq.0.10.
The beneficial effects of the invention are as follows: 1) Experiments show that the particle sphericity of the large-particle ternary precursor product is obviously improved on the premise of not influencing a reaction system by adding the zirconia microsphere suspension to participate in the coprecipitation process of the precursor. 2) Experiments show that the invention can further improve the overall particle sphericity of the product and reduce the ratio of small particle products newly nucleated in a growth kettle by adding crystal nucleus slurry at the same time of coprecipitation feeding. 3) The control range of ammonia concentration and pH in the continuous output process can be not adjusted (the change of the morphology of primary particles caused by fluctuation of ammonia and pH in the process is effectively avoided), and the granularity of the product is controlled by adjusting the flow of crystal nucleus. The process has stable production process and high consistency of particle morphology, avoids the condition of inconsistent primary particle morphology among batches frequently occurring in the general continuous method product, and has good continuous stability of batch indexes. 4) High production efficiency, continuous reaction output and high yield. 5) Compared with the organic grinding ball particles such as polystyrene, the method reduces the separation process, directly dopes at the wet end, provides higher uniformity for positive electrode lithium mixing sintering, effectively reduces the mixing non-uniformity of doping at the positive electrode end, and has higher binding energy after doping at the precursor end compared with doping at the positive electrode material end.
Drawings
Fig. 1 is a process flow diagram of the present invention.
FIG. 2 is an electron microscope image of the crystal nuclei and precursor products of example one; wherein (a) is a crystal nucleus electron microscope image, and (b) is a precursor product electron microscope image.
FIG. 3 is an electron microscope image of the nucleus and precursor product of example two; wherein (c) is a crystal nucleus electron microscope image, and (d) is a precursor product electron microscope image.
FIG. 4 is an electron microscope image of the crystal nuclei and precursor products of comparative example one; wherein (e) is a crystal nucleus electron microscope image, and (f) is a precursor product electron microscope image.
FIG. 5 is an electron microscope image of the crystal nuclei and precursor products of comparative example two; and (g) is an electron microscope image of the precursor product. The invention is further illustrated by the following examples.
Embodiment one:
the nickel-cobalt-manganese ternary precursor product is produced according to the following steps:
(1) According to Ni: co: mn=89:4:7, preparing sulfate of nickel cobalt manganese into 2.0mol/L mixed salt solution by pure water;
(2) Preparing NaOH precipitant into sodium hydroxide solution with concentration of 5mol/L by deionized water;
(3) Diluting the ammonia water solution into 0.8mol/L ammonia water solution by deionized water for standby;
(4) Preparing zirconia with the granularity of 80-120 mu m into zirconia microsphere suspension with the granularity of 100g/L by deionized water;
(5) Preparing crystal nucleus slurry: preparing a required base solution by using a mother solution in a first reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 900rpm, controlling the temperature in the kettle at 60 ℃, adjusting the pH control range of the base solution to 11.80-11.90 and the ammonia concentration control range of the base solution to 0.3-0.35mol/L; and (3) setting flow according to the product requirement proportion in the step (1), continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitator and the complexing agent into the first reaction kettle, regulating the flow of the precipitator and the complexing agent according to the test condition to stabilize the reaction atmosphere, and continuously reacting until the crystal nucleus slurry with the crystal nucleus particle size of 3.5 mu m is obtained.
(6) And (3) preparing a required base solution by using a mother solution in a second reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 800rpm, controlling the temperature in the kettle at 60 ℃, adjusting the pH control range of the base solution to 11.80-11.90 and the ammonia concentration control range of the base solution to 0.3-0.35mol/L, setting the flow according to the required proportion of the product in the step (1), continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitant, the complexing agent, the zirconium oxide microsphere suspension and the crystal nucleus slurry into the second reaction kettle, and adjusting the flow of the precipitant, the complexing agent and the crystal nucleus slurry to stabilize the reaction atmosphere according to the test condition, and continuously reacting until the precursor product is obtained.
The morphology of the obtained crystal nucleus and the morphology of the precursor product particles are shown in figure 2.
Embodiment two:
the nickel-cobalt-manganese ternary precursor product is produced according to the following steps:
(1) According to Ni: co: the ratio of Mn=84:6:10 is that the sulfate of nickel cobalt manganese is prepared into 1.7mol/L mixed salt solution by pure water;
(2) Preparing NaOH precipitant into 9mol/L sodium hydroxide solution by deionized water;
(3) Diluting the ammonia water solution into 0.5mol/L ammonia water solution by deionized water for standby;
(4) Preparing zirconia with the granularity of 80-120 mu m into zirconia microsphere suspension with the granularity of 100g/L by deionized water;
(5) Preparing crystal nucleus slurry: preparing a required base solution by using a mother solution in a first reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 900rpm, controlling the temperature in the kettle at 60 ℃, adjusting the pH control range of the base solution to 11.60-11.80, and controlling the ammonia concentration of the base solution to 0.2-0.25mol/L; and (3) setting flow according to the product requirement proportion in the step (1), continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitator and the complexing agent into the first reaction kettle, regulating the flow of the precipitator and the complexing agent according to the test condition to stabilize the reaction atmosphere, and continuously reacting until the crystal nucleus slurry with the crystal nucleus particle size of 3.1 mu m is obtained.
(6) And (3) preparing a required base solution by using a mother solution in a second reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 800rpm, controlling the temperature in the kettle at 60 ℃, adjusting the pH control range of the base solution to 10.50-10.80 and the ammonia concentration control range of the base solution to 0.2-0.25mol/L, setting the flow according to the required proportion of the product in the step (1), continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitant, the complexing agent, the zirconium oxide microsphere suspension and the crystal nucleus slurry into the second reaction kettle, and adjusting the flow of the precipitant, the complexing agent and the crystal nucleus slurry to stabilize the reaction atmosphere according to the test condition, and continuously reacting until the precursor product is obtained.
The morphology of the obtained crystal nucleus and the morphology of the precursor product particles are shown in figure 3.
Comparative example one:
this comparative example is a control experiment of example one, which was performed under the same conditions and procedure as example one, except that: the specific steps of the method are as follows:
(1) According to Ni: co: mn=89:4:7, preparing sulfate of nickel cobalt manganese into 2.0mol/L mixed salt solution by pure water;
(2) Preparing NaOH precipitant into sodium hydroxide solution with concentration of 5mol/L by deionized water;
(3) Diluting the ammonia water solution into 0.8mol/L ammonia water solution by deionized water for standby;
(4) Preparing crystal nucleus slurry: preparing a required base solution by using a mother solution in a first reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 900rpm, controlling the temperature in the kettle at 60 ℃, adjusting the pH control range of the base solution to 11.80-11.90 and the ammonia concentration control range of the base solution to 0.3-0.35mol/L; and (3) setting flow according to the product requirement proportion in the step (1), continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitator and the complexing agent into the first reaction kettle, regulating the flow of the precipitator and the complexing agent according to the test condition to stabilize the reaction atmosphere, and continuously reacting until the crystal nucleus slurry with the crystal nucleus particle size of 3.5 mu m is obtained.
(5) And (3) preparing a required base solution by using a mother solution in a second reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 800rpm, controlling the temperature in the kettle at 60 ℃, adjusting the pH control range of the base solution to 11.80-11.90 and the ammonia concentration control range of the base solution to 0.3-0.35mol/L, continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitator, the complexing agent and the crystal nucleus slurry into the second reaction kettle according to the required proportion of the product in the step (1), and adjusting the flow of the precipitator, the complexing agent and the crystal nucleus slurry according to the test condition to stabilize the reaction atmosphere and continuously reacting until the precursor product is obtained.
The morphology of the obtained crystal nucleus and the morphology of the precursor product particles are shown in figure 4.
Comparative example two:
this comparative example is a control experiment of example one, which was performed under the same conditions and procedure as example one, except that: the preparation and addition of the crystal nucleus slurry are not included, and the specific steps are as follows:
(1) According to Ni: co: mn=89:4:7, preparing sulfate of nickel cobalt manganese into 2.0mol/L mixed salt solution by pure water;
(2) Preparing NaOH precipitant into sodium hydroxide solution with concentration of 5mol/L by deionized water;
(3) Diluting the ammonia water solution into 0.8mol/L ammonia water solution by deionized water for standby;
(4) Preparing zirconia with the granularity of 80-120 mu m into zirconia microsphere suspension with the granularity of 100g/L by deionized water;
(5) And (3) preparing a required base solution by using a mother solution in a second reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring speed at 800rpm, controlling the temperature in the kettle at 60 ℃, adjusting the pH control range of the base solution to 11.80-11.90 and the ammonia concentration control range of the base solution to 0.3-0.35mol/L, setting the flow according to the required proportion of the product in the step (1), continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitant, the complexing agent and the zirconia microsphere suspension into the second reaction kettle, and adjusting the flow of the precipitant and the complexing agent according to the test condition to stabilize the reaction atmosphere and continuously reacting until the precursor product is obtained.
The morphology of the obtained crystal nucleus and the morphology of the precursor product particles are shown in figure 5.
Table 1 comparison of the morphology of the nuclei and the morphology of the precursor product particles for each of the examples and comparative examples
As can be seen from fig. 2, fig. 3, and the morphology of the crystal nucleus and the morphology of the precursor product particles in the first and second embodiments in table 1, the method of the present invention can be used to prepare a nickel-cobalt-manganese ternary precursor product with high particle sphericity.
As can be seen from fig. 2, fig. 4 and a comparison between the first embodiment and the first comparative example in table 1, the first embodiment significantly improves the overall sphericity of the large-particle precursor product and solves the problem of low sphericity of the large-particle product produced by the continuous method by adding the suspension of zirconia microspheres during the coprecipitation reaction based on the scheme of the first comparative example.
As can be seen from fig. 2, 5 and a comparison of the first and second examples in table 1, the first example further improves the overall particle sphericity of the precursor product and significantly reduces the fraction of newly nucleated small particle products in the growth reactor by adding the crystal nucleus slurry during the coprecipitation reaction based on the second example.
Claims (9)
1. The preparation method of the doped ternary precursor for improving the sphericity of large particles is characterized by comprising the following steps of: comprising the step of adding zirconia microsphere suspension during coprecipitation reaction.
2. The method for preparing the doped ternary precursor for improving sphericity of large particles according to claim 1, wherein the method comprises the following steps: and a step of adding a crystal nucleus slurry during the coprecipitation reaction.
3. The method for preparing the doped ternary precursor for improving sphericity of large particles according to claim 1, wherein the method comprises the following steps: the zirconia microsphere suspension is formed by mixing deionized water and zirconia with the granularity of 80-120 mu m, and the zirconia concentration in the zirconia microsphere suspension is 80-120 g/L.
4. The method for preparing the doped ternary precursor for improving the sphericity of large particles according to claim 2, which is characterized by comprising the following steps:
s1, preparing nickel-cobalt-manganese mixed salt solution, a precipitator, a complexing agent and zirconia microsphere suspension;
s2, preparing crystal nucleus slurry;
s3, preparing a required base solution by using a mother solution in a second reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring rate and the temperature in the kettle stably controlled at process required values, adjusting the pH value and the ammonia concentration of the base solution to the process required values, setting flow according to the product required proportion, continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitator, the complexing agent, the zirconia microsphere suspension and the crystal nucleus slurry into the second reaction kettle, and adjusting the flow of the precipitator, the complexing agent and the crystal nucleus slurry according to the test condition to stabilize the reaction atmosphere and continuously reacting until the precursor product with the required particle size is obtained.
5. The method for preparing the doped ternary precursor for improving sphericity of large particles according to claim 4, wherein the method comprises the following steps: the crystal nucleus slurry is prepared according to the following steps:
A. preparing a required base solution by using a mother solution in a first reaction kettle, introducing nitrogen to perform air replacement, opening stirring and heating, keeping the stirring rate and the temperature in the kettle stably controlled at process required values, and regulating the pH value and the ammonia concentration of the base solution to the process required values;
B. and setting flow according to the product requirement proportion, continuously adding the nickel-cobalt-manganese mixed salt solution, the precipitator and the complexing agent into the first reaction kettle, regulating the flow of the precipitator and the complexing agent according to the test condition to stabilize the reaction atmosphere, and continuously reacting until the crystal nucleus slurry with the required particle size is obtained.
6. The method for preparing the doped ternary precursor for improving sphericity of large particles according to claim 4 or 5, wherein the method comprises the following steps: the precipitant is sodium hydroxide solution with NaOH concentration of 3-15 mol/L; the complexing agent is NH 3 Ammonia water solution with concentration of 0.1-1.0 mol/L.
7. The method for preparing the doped ternary precursor for improving sphericity of large particles according to claim 4 or 5, wherein the method comprises the following steps: the concentration of metal ions in the nickel-cobalt-manganese mixed salt solution is 1.5-2.5 mol/L.
8. A ternary precursor produced by the process for producing a doped ternary precursor of increased sphericity of large particles according to any one of claims 1 to 7.
9. The ternary precursor according to claim 8, which satisfies Ni: co: mn=x: y:1-x-y, where 0.8 +.ltoreq. 0.9,0.03 +.ltoreq.y +.ltoreq.0.10.
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