CN114804229A - High-nickel ternary precursor and preparation method thereof - Google Patents
High-nickel ternary precursor and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 39
- 239000002243 precursor Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 42
- 239000011261 inert gas Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 239000012716 precipitator Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000000203 mixture Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011164 primary particle Substances 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000000087 stabilizing 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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
A high nickel ternary precursor with a chemical formula of Ni x Co y Mn z M k (OH) 2 The preparation method comprises the following steps: firstly, preparing a metal mixed solution of Ni, Co and Mn; preparing sodium hydroxide or potassium hydroxide solution as a precipitator; preparing an ammonia water solution as a complexing agent; preparing an M salt solution, wherein the M salt is one or more of Zr salt, Al salt, La salt, W salt and Mo salt; secondly, introducing nitrogen or inert gas, and adding the metal mixed solution, the precipitator, the complexing agent and the M salt solution into the kettle for coprecipitation; the particle size of the slurry is increased to D50 1 The introduction of nitrogen or inert gas is suspended, and the nitrogen or inert gas starts to be introduced at a distance of 0.2-0.4 m 3 Introducing mixed gas of oxygen and nitrogen at a flow rate of/h, and stopping feeding liquid when the granularity of the slurry grows to a target granularity D50; and thirdly, carrying out filter pressing, washing and drying on the coprecipitation product to obtain the high-nickel ternary precursor. The precursor can stabilize the structure of the anode material and improve the cycle performance. The electrochemical performance is good, and the lithium ion diffusion is facilitated, and the ion transmission efficiency is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a high-nickel ternary precursor and a preparation method thereof.
Background
The high-nickel ternary cathode material becomes a research hotspot by virtue of the advantages of high specific capacity, low cost, excellent safety and the like, and is considered to be a lithium ion power battery cathode material with great application prospect.
However, as the content of nickel element in the ternary positive electrode material increases, the structural stability thereof becomes poor, and the capacity decays too fast during charge and discharge. In addition, high-nickel ternary cathode materials are mostly secondary particles, and volume expansion is easy to occur in the charging and discharging process, so that internal stress of the materials is overlarge, primary particles are crushed and fall off, and the capacity is rapidly attenuated. In the high-nickel ternary cathode material, the lithium ion transmission path is longer, so that the transmission efficiency of lithium ions is reduced, and the rate performance is influenced.
Therefore, the preparation of the high-nickel ternary precursor with a compact inner core and a loose outer layer and emitted from the inner core is the key for improving the electrochemical performance of the high-nickel ternary cathode material.
Disclosure of Invention
The invention aims to provide a high-nickel ternary precursor and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention on the product level is as follows:
a high nickel ternary precursor with a chemical formula of Ni x Co y Mn z M k (OH) 2 Wherein, M element is one or more of Zr, Al, La, W and Mo, x is more than or equal to 0.80 and less than 0.96, y is more than or equal to 0.04 and less than 0.20, z is more than or equal to 0.04 and less than 0.20, k is more than 0.001 and less than or equal to 0.004, and x + y + z + k = 1.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, D50 is 13-16 um, and the tap density is 1.7-1.9 g/cm 3 The specific surface area is 12-16 m 2 /g。
In order to achieve the purpose, the technical scheme adopted by the invention in the aspect of the method is as follows:
a preparation method of a high-nickel ternary precursor comprises the following steps:
preparing a metal mixed solution of Ni, Co and Mn, wherein the total molar concentration of Ni, Co and Mn is 1.8-2.4 mol/L;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-12 mol/L as a precipitator;
preparing an ammonia water solution with the concentration of 1.5-3.5 mol/L as a complexing agent;
preparing an M salt solution, wherein the M salt is one or more of Zr salt, Al salt, La salt, W salt and Mo salt;
step two, keeping the stirring of the reaction kettle open, introducing nitrogen or inert gas with the flow of 0.5-0.9 m 3 Continuously adding the metal mixed solution, the precipitator, the complexing agent and the M salt solution in the step one into a reaction kettle at the flow rate of 200-800 mL/min respectively to perform coprecipitation reaction;
when the slurry of the reaction kettle grows to D50 1 When the nitrogen or inert gas is not introduced, the nitrogen or inert gas is not introduced until the nitrogen or inert gas is introduced, and the nitrogen or inert gas starts to be introduced in an amount of 0.2-0.4 m 3 Introducing mixed gas of oxygen and nitrogen at a flow rate of/h, wherein the volume ratio of the oxygen to the nitrogen is 1: 6-1: 3, and stopping feeding liquid when the granularity of the slurry grows to a target granularity D50;
and step three, carrying out filter pressing, washing and drying on the coprecipitation product in the step two to obtain the high-nickel ternary precursor.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, in the step one, the concentration of the M salt is 0.01-0.04 mol/L.
2. In the scheme, in the second step, the ratio of the flow rate of the metal mixed solution to the flow rate of the M salt solution satisfies 1: 1-4: 1.
3. In the scheme, in the second step, the pH value in the reaction process is kept at 11.00-11.80, the concentration of the complexing agent in the slurry in the reaction kettle is 0.3-0.5 mol/L, the synthesis temperature is kept at 50-70 ℃, and the rotating speed of the reaction kettle is 350-600 r/min.
4. In the scheme, in the step two, D50 1 Is 4-6 um, D50 1 The particle size of the nano-particles is 25-50% of the target particle size D50.
5. In the above scheme, the chemical formula of the precursor is Ni x Co y Mn z M k (OH) 2 Wherein, M element is one or more of Zr, Al, La, W and Mo, x is more than or equal to 0.80 and less than 0.96, y is more than or equal to 0.04 and less than 0.20, z is more than or equal to 0.04 and less than 0.20, k is more than 0.001 and less than or equal to 0.004, and x + y + z + k = 1.
6. In the scheme, D50 is 13-16 um, and the tap density is 1.7-1.9 g/cm 3 The specific surface area is 12-16 m 2 The density is 3.78-3.85 g/cm 3 。
The working principle and the advantages of the invention are as follows:
1. according to the invention, an M element is doped in the process of preparing the high-nickel ternary precursor, wherein the M element is one or more of Zr, Al, La, W and Mo. The doping of the M element can stabilize the structure of the anode material, relieve the volume effect in the lithium desorption process and improve the cycle performance. The quantitative doping of the M element is realized by controlling the ratio of the flow of the metal liquid to the flow of the M salt solution to meet 1: 1-4: 1, the doping amount of the M element is too small to achieve the purpose of stabilizing the structure of the anode material, and the capacity is reduced due to too high doping amount.
2. The method comprises the steps of introducing nitrogen or inert gas into the process of preparing the high-nickel ternary precursor, wherein the flow rate is 0.5-0.9 m 3 And h, continuously adding the metal liquid, the precipitator, the complexing agent and the M salt solution in the step one into the reaction kettle at the flow rate of 200-800 mL/min respectively for coprecipitation reaction, and allowing the slurry in the reaction kettle to grow to D50 when the particle size of the slurry grows 1 When the nitrogen or inert gas is not introduced, the nitrogen or inert gas is not introduced until the nitrogen or inert gas is introduced, and the nitrogen or inert gas starts to be introduced in an amount of 0.2-0.4 m 3 Introducing mixed gas of oxygen and nitrogen at a flow rate of/h, wherein the volume ratio of the oxygen to the nitrogen meets 1: 6-1: 3, and stopping liquid inlet when the growth reaches a target granularity D50. Protective gas is introduced at the initial stage to prevent the oxidation of the precursor, so that a compact kernel can be formed, the kernel can provide a stable skeleton for the subsequent growth of secondary particles, and the cracking of the high-nickel ternary precursor in the growth process can be prevented. When the slurry particle size of the reaction kettle grows to D50 1 During the process, the introduction of the protective gas is suspended, the mixed gas of oxygen and nitrogen is introduced, and the introduction of the oxygen can realize the introduction of Co 2+ 、Mn 2+ The primary particles are oxidized and refined, so that the primary particles grow directionally along the compact kernel, and meanwhile, the looseness among the primary particles is ensuredAnd (4) sex. The loosening among the primary particles can relieve the volume expansion in the lithium ion de-intercalation process, increase the contact area with the electrolyte and improve the electrochemical performance. The directional growth of primary particles is beneficial to the diffusion of lithium ions, and the ion transmission efficiency is improved.
3. According to the invention, the volume ratio of oxygen to nitrogen in the mixed gas is controlled to meet 1: 6-1: 3, so that the quantitative oxidation of the precursor is realized. The oxygen content is too low, so that insufficient oxidation is easily caused, and the outer layer is too compact, so that the lithium ion transmission is not facilitated; too high an oxygen content may result in Co 2+ 、Mn 2+ Over oxidation, the outer layer is too loose, the primary particles grow disorderly, and the electrical performance is reduced.
4. The method has the advantages of reliable process, simplicity, easy operation and easy industrial production.
Drawings
FIG. 1 is a sectional electron micrograph of a precursor prepared in example 1 of the present invention;
FIG. 2 is a sectional electron micrograph of a precursor prepared in comparative example 3 of the present invention;
FIG. 3 is a sectional electron micrograph of the precursor prepared in example 2 of the present invention.
Detailed Description
The invention is further described with reference to the following figures and examples:
the present disclosure will be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the disclosure may be shown and described, and which, when modified and varied by the techniques taught herein, can be made by those skilled in the art without departing from the spirit and scope of the disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including, but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
Example 1:
a high-nickel ternary precursor and a preparation method thereof comprise the following steps:
preparing a metal mixed solution of Ni, Co and Mn, wherein the total molar concentration of Ni, Co and Mn is 2mol/L, and the molar ratio of Ni, Co and Mn is 85:5: 10;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 10mol/L as a precipitator; preparing an ammonia water solution with the concentration of 2.5mol/L as a complexing agent; preparing a La salt solution, wherein the concentration of the La salt is 0.02 mol/L;
step two, keeping the stirring of the reaction kettle open, introducing nitrogen or inert gas with the flow of 0.5-0.9 m 3 Continuously adding the metal mixed solution, the precipitator, the complexing agent and the La salt solution in the step one into a reaction kettle at the flow rate of 200-800 mL/min respectively for coprecipitation reaction, wherein the ratio of the flow of the metal mixed solution to the flow of the La salt solution meets 2.5: 1;
when the slurry of the reaction kettle grows to D50 1 4.83um, the introduction of nitrogen or inert gas is suspended, and the nitrogen or inert gas starts to be introduced in an amount of 0.2-0.4 m 3 Introducing mixed gas of oxygen and nitrogen at a flow rate of/h, wherein the volume ratio of the oxygen to the nitrogen meets 1:4, and stopping liquid inlet when the growth reaches a target particle size D50 of 14.56 microns;
the pH value in the reaction process is kept at 11.00-11.80, the concentration of the complexing agent in the slurry in the reaction kettle is 0.35mol/L, the synthesis temperature is maintained at 55 ℃, and the rotating speed of the reaction kettle is 350-600 r/min.
And step three, carrying out filter pressing, washing and drying on the coprecipitation product in the step two to obtain the high-nickel ternary precursor. The chemical formula of the product is Ni 0.85 Co 0.05 Mn 0.096 La 0.004 (OH) 2 D50 is 14.56um, and the tap density is 1.79g/cm 3 The specific surface area is 15.5m 2 (iv) g, true density 3.81g/cm 3 The relevant data are shown in Table 1.
Comparative example 1:
the difference from example 1 is that the ratio of the flow rate of the metal mixed solution to the flow rate of the La salt solution in step two is different, and the La salt solution is not added in this comparative example 1, and the rest is exactly the same as example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 2:
the difference from example 1 is that the ratio of the flow rate of the metal mixed solution to the flow rate of the La salt solution in step two is different, the ratio of the flow rate of the metal liquid to the flow rate of the La salt solution in comparative example 2 is 0.5:1, and the rest is the same as example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 3:
the difference from example 1 is that the volume ratio of oxygen to nitrogen in step two is different, and the volume ratio of oxygen to nitrogen in comparative example 3 is 1:8, and the rest is identical to example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Comparative example 4:
the difference from example 1 is that the volume ratio of oxygen to nitrogen in step three is different, and the volume ratio of oxygen to nitrogen in comparative example 4 is 1:1, and the rest is identical to example 1. The obtained precursor was washed and dried, and the relevant data are shown in table 1.
Example 2:
a high-nickel ternary precursor and a preparation method thereof comprise the following steps:
preparing a metal mixed solution of Ni, Co and Mn, wherein the total molar concentration of Ni, Co and Mn is 2mol/L, and the molar ratio of Ni, Co and Mn is 90:5: 5;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 10mol/L as a precipitator; preparing an ammonia water solution with the concentration of 2.5mol/L as a complexing agent; preparing a W salt solution, wherein the concentration of the W salt is 0.02 mol/L;
step two, keeping the stirring of the reaction kettle open, introducing nitrogen or inert gas, wherein the flow is 0.5-0.9 m 3 Continuously adding the metal mixed solution, the precipitator, the complexing agent and the W salt solution in the step one into a reaction kettle at the flow rate of 200-800 mL/min respectively for coprecipitation reaction, wherein the metal mixed solution isThe ratio of the flow rate to the flow rate of the W salt solution meets 2.5: 1;
when the slurry of the reaction kettle grows to D50 1 The nitrogen or inert gas is stopped to be introduced into the reactor to be 5.76um, and the nitrogen or inert gas starts to be introduced into the reactor at a distance of 0.2-0.4 m 3 Introducing mixed gas of oxygen and nitrogen at a flow rate of/h, wherein the volume ratio of the oxygen to the nitrogen meets 1:4, and stopping liquid inlet when the growth reaches a target particle size D50 of 15.21 um;
the pH value in the reaction process is kept at 11.00-11.80, the concentration of the complexing agent in the slurry in the reaction kettle is 0.35mol/L, the synthesis temperature is maintained at 55 ℃, and the rotating speed of the reaction kettle is 350-600 r/min.
And step three, carrying out filter pressing, washing and drying on the coprecipitation product in the step two to obtain the high-nickel ternary precursor. The chemical formula of the product is Ni 0.90 Co 0.05 Mn 0.096 W 0.004 (OH) 2 D50 is 15.21um, and the tap density is 1.85g/cm 3 The specific surface area is 12.5m 2 G, true density of 3.79g/cm 3 The relevant data are shown in table 1.
Table 1 shows data on the products obtained in the examples and comparative examples
Comparing the examples in Table 1 with the comparative data for each pair shows that: the doping amount of La element and the volume ratio of oxygen to nitrogen are D50 1 And D50, the structure of the cathode material can be stabilized by a proper amount of La element, and the first discharge capacity is improved.
Fig. 1, 2 and 3 are sectional views of the high nickel ternary precursors prepared in example 1, comparative example 3 and example 2, respectively, and it can be seen from the views that the inner cores of the high nickel ternary precursors prepared in example 1 and example 2 are dense, the outer layers are loose and porous, and the primary particles exhibit radial growth. The high-nickel ternary precursor prepared in the comparative example 3 is relatively compact in interior and is not beneficial to the transmission of lithium ions.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A high-nickel ternary precursor is characterized in that: has a chemical formula of Ni x Co y Mn z M k (OH) 2 Wherein, M element is one or more of Zr, Al, La, W and Mo, x is more than or equal to 0.80 and less than 0.96, y is more than or equal to 0.04 and less than 0.20, z is more than or equal to 0.04 and less than 0.20, k is more than 0.001 and less than or equal to 0.004, and x + y + z + k = 1.
2. A precursor according to claim 1, wherein: d50 is 13-16 um, and the tap density is 1.7-1.9 g/cm 3 The specific surface area is 12-16 m 2 The density is 3.78-3.85 g/cm 3 。
3. A preparation method of a high-nickel ternary precursor is characterized by comprising the following steps: the method comprises the following steps:
preparing a metal mixed solution of Ni, Co and Mn, wherein the total molar concentration of Ni, Co and Mn is 1.8-2.4 mol/L;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-12 mol/L as a precipitator;
preparing an ammonia water solution with the concentration of 1.5-3.5 mol/L as a complexing agent;
preparing an M salt solution, wherein the M salt is one or more of Zr salt, Al salt, La salt, W salt and Mo salt;
step two, keeping the stirring of the reaction kettle open, introducing nitrogen or inert gas with the flow of 0.5-0.9 m 3 Continuously adding the metal mixed solution, the precipitator, the complexing agent and the M salt solution in the step one into a reaction kettle at the flow rate of 200-800 mL/min respectively to perform coprecipitation reaction;
when the slurry of the reaction kettle grows to D50 1 When the nitrogen or inert gas is not introduced, the nitrogen or inert gas is not introduced until the nitrogen or inert gas is introduced, and the nitrogen or inert gas starts to be introduced in an amount of 0.2-0.4 m 3 The mixture of oxygen and nitrogen is introduced at the flow rate of/hSynthesizing gas, wherein the volume ratio of the oxygen to the nitrogen is 1: 6-1: 3, and stopping feeding liquid when the granularity of the slurry grows to a target granularity D50;
and step three, carrying out filter pressing, washing and drying on the coprecipitation product in the step two to obtain the high-nickel ternary precursor.
4. The production method according to claim 3, characterized in that: in the first step, the concentration of the M salt is 0.01-0.04 mol/L.
5. The production method according to claim 3, characterized in that: in the second step, the ratio of the flow rate of the metal mixed solution to the flow rate of the M salt solution is 1: 1-4: 1.
6. The production method according to claim 3, characterized in that: in the second step, the pH value in the reaction process is kept at 11.00-11.80, the concentration of the complexing agent in the slurry in the reaction kettle is 0.3-0.5 mol/L, the synthesis temperature is kept at 50-70 ℃, and the rotating speed of the reaction kettle is 350-600 r/min.
7. The production method according to claim 3, characterized in that: in step two, D50 1 Is 4-6 um, D50 1 The particle size of the nano-particles is 25-50% of the target particle size D50.
8. The production method according to claim 3, characterized in that: the chemical formula of the precursor is Ni x Co y Mn z M k (OH) 2 Wherein, M element is one or more of Zr, Al, La, W and Mo, x is more than or equal to 0.80 and less than 0.96, y is more than or equal to 0.04 and less than 0.20, z is more than or equal to 0.04 and less than 0.20, k is more than 0.001 and less than or equal to 0.004, and x + y + z + k = 1.
9. The method of claim 8, wherein: d50 is 13-16 um, and the tap density is 1.7-1.9 g/cm 3 The specific surface area is 12-16 m 2 The density per gram is 3.78 to 3.85g/cm 3 。
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| CN114804229B CN114804229B (en) | 2023-11-14 |
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