CN114751467B - Aging method for directionally improving specific surface area of nickel-cobalt-manganese ternary precursor - Google Patents
Aging method for directionally improving specific surface area of nickel-cobalt-manganese ternary precursor Download PDFInfo
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- CN114751467B CN114751467B CN202210472387.5A CN202210472387A CN114751467B CN 114751467 B CN114751467 B CN 114751467B CN 202210472387 A CN202210472387 A CN 202210472387A CN 114751467 B CN114751467 B CN 114751467B
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- 239000002243 precursor Substances 0.000 title claims abstract description 50
- 230000032683 aging Effects 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 23
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 62
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000005273 aeration Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000009423 ventilation Methods 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000005070 sampling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- 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
-
- 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
Abstract
The invention relates to the field of ternary precursors, in particular to an aging method for directionally improving the specific surface area of a nickel-cobalt-manganese ternary precursor, which comprises the following steps of: (1) Adding an alkali solution into the nickel-cobalt-manganese ternary precursor slurry, and controlling the concentration of OH < - > in the nickel-cobalt-manganese ternary precursor slurry to be 0.2mol/L-0.5 mol/L; (2) At a aeration rate of 0.1m per cubic meter of slurry 3 /h‑1m 3 And (3) introducing air into the slurry obtained in the step (2) at the air-introducing speed of/h, wherein the air-introducing time is 0.5-10 h. Adding a specific amount of alkaline solution into the aging slurry and introducing air, so that the aging slurry can serve as an oxidant to accelerate the aging rate, and the surface morphology of ternary precursor particles in an aging system can be controlled by controlling the ventilation rate and the ventilation time to prepare the ternary precursor particles which simultaneously meet the TD of more than or equal to 1.8g/cm 3 、BET≥12m 3 And (3) the ternary precursor finished product of/g is obtained, so that the energy density and the charge and discharge performance of the finally obtained ternary lithium ion battery are improved.
Description
Technical Field
The invention relates to the field of ternary precursors, in particular to an aging method for directionally improving the specific surface area of a nickel-cobalt-manganese ternary precursor.
Background
In recent years, with the wide application of rechargeable batteries in electric automobiles, there is a high demand for energy density and charge and discharge performance. In order to improve the energy density and charge and discharge performance of the ternary lithium ion battery, the ternary precursor material is required to have both high Tap Density (TD) and high specific surface area (BET), but the ternary precursor obtained by the existing preparation method is difficult to have both high Tap Density (TD) and high specific surface area (BET) characteristics.
Among the existing preparation methods, the most commonly used method is a batch coprecipitation method, which generally includes coprecipitation reaction, aging,Washing, drying and the like. When the ternary precursor is synthesized by the conventional batch method, the process conditions of coprecipitation reaction are controlled to control the particle size, tap density, specific surface area and the like of the ternary precursor material, and the precursor prepared by the conventional method is usually used for preparing the ternary precursor when TD reaches 1.8g/cm 3 Above, the BET is generally much lower than 12m 3 /g。
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides an aging method for directionally improving the specific surface area of a nickel-cobalt-manganese ternary precursor, which comprises the following steps:
an aging method for directionally improving specific surface area of a nickel-cobalt-manganese ternary precursor comprises the following steps:
(1) Adding an alkali solution into the nickel-cobalt-manganese ternary precursor slurry, and controlling the total alkalinity in the nickel-cobalt-manganese ternary precursor slurry to be between 0.2mol/L and 0.5mol/L;
(2) At a aeration rate of 0.1m per cubic meter of slurry 3 /h-1m 3 And (3) introducing air into the slurry obtained in the step (2) at the air-introducing speed of/h, wherein the air-introducing time is 0.5-10 h.
Specifically, the concentration of the alkaline solution added in the step (1) is 8mol/L to 12mol/L.
Specifically, the step (1) further comprises controlling the stirring rate of the slurry to be 80rpm-150rpm.
Specifically, the aeration rate in the step (2) is 0.3m 3 /h-0.8m 3 /h。
Specifically, the ventilation time in the step (2) is 1h-5h.
The invention has the beneficial effects that:
(1) The alkaline solution with specific quantity is added into the aging slurry, so that the oxidation rate of the ternary precursor slurry can be accelerated, and the aging time is shortened; air is introduced into the aging system, so that the three-element precursor particle can serve as an oxidant to accelerate the aging rate, and the surface morphology of the three-element precursor particle in the aging system can be controlled by controlling the ventilation rate and the ventilation time;
(2) The aging method disclosed by the invention can effectively improve the NCM ternary precursor materialThe specific surface area of the material is prepared to meet the requirement that the TD is more than or equal to 1.8g/cm 3 、BET≥12m 2 And (3) the ternary precursor finished product of/g is obtained, so that the energy density and the charge and discharge performance of the finally obtained ternary lithium ion battery are improved.
Drawings
FIG. 1 is an SEM image of an NCM ternary precursor prior to aging in accordance with the present invention;
FIG. 2 is an SEM image of an NCM ternary precursor after aging using the disclosed aging method.
Detailed Description
The invention will now be described in detail with reference to figures 1-2 and the detailed description. The embodiments shown below do not limit the inventive content described in the claims in any way. The whole contents of the constitution shown in the following examples are not limited to the solution of the invention described in the claims.
An aging method for directionally improving specific surface area of a nickel-cobalt-manganese ternary precursor comprises the following steps:
(1) Adding an alkali solution, which can be sodium hydroxide solution or other alkaline solutions, into the nickel-cobalt-manganese ternary precursor slurry, and controlling the total alkalinity in the nickel-cobalt-manganese ternary precursor slurry to be between 0.2mol/L and 0.5mol/L, and specifically can be 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L; the stirring rate of the slurry is controlled to be 80rpm-150rpm, and specifically 80rpm, 90rpm, 100rpm, 120rpm, 140rpm, or 150rpm;
(2) At a aeration rate of 0.1m per cubic meter of slurry 3 /h-1m 3 Aeration rate/h air is introduced into the slurry obtained in the step (2) for 0.5-10 h, and the specific aeration rate can be 0.1m 3 /h、0.3m 3 /h、0.5m 3 /h、0.7m 3 /h、0.8m 3 /h、0.9m 3 /h, or 1m 3 The aeration time may be 0.5h, 1h, 2h, 3h, 5h, 8h, or 10h.
Example 1
A batch of slurry was synthesized by the method, and after sampling from the slurry and washing and drying the sample, the TD of the sample was 1.86g/L and the BET was 8.2m 2 And/g. Will be put onTransferring the slurry to an aging tank, adding 300L of 10mol/L alkali solution into the slurry, and controlling the total c (OH) - ) The stirring speed of the aging tank is 100rpm, which is 0.3 mol/L. The total volume of the slurry in the aging tank is 10-30m 3 At 3m 3 Introducing air into the slurry in the aging tank for 5 hours at the rate of/h, separating, washing and drying the aged slurry to obtain an NCM ternary precursor product, and detecting to obtain the NCM ternary precursor product: TD 1.84g/L, BET 12.2m 2 /g。
Example 2
Synthesizing a batch of slurry by adopting a method, sampling from the slurry, washing and drying the sample, transferring the slurry to an aging tank, adding 200L of 10mol/L alkali solution into the slurry, and controlling the total c (OH) of the slurry - ) The stirring speed of the aging tank is 100rpm, which is 0.2 mol/L. The total volume of the slurry in the aging tank is 10-30m 3 At 5m 3 Introducing air into the slurry in the aging tank for 5 hours at the rate of/h, separating, washing and drying the aged slurry to obtain an NCM ternary precursor product, and detecting to obtain the NCM ternary precursor product: TD 1.85g/L, BET 12.4m 2 /g。
Example 3
Synthesizing a batch of slurry by adopting a method, sampling from the slurry, washing and drying the sample, transferring the slurry to an aging tank, adding 500L of 10mol/L alkali solution into the slurry, and controlling the total c (OH) of the slurry - ) The stirring speed of the aging tank is 100rpm, which is 0.5 mol/L. The total volume of the slurry in the aging tank is 10-30m 3 At 5m 3 Introducing air into the slurry in the aging tank for 5 hours at the rate of/h, separating, washing and drying the aged slurry to obtain an NCM ternary precursor product, and detecting to obtain the NCM ternary precursor product: TD 1.85g/L, BET 13.1m 2 /g。
Example 4
Synthesizing a batch of slurry by adopting a method, sampling from the slurry, washing and drying the sample, transferring the slurry to an aging tank, adding 500L of 10mol/L alkali solution into the slurry, and controlling the total c (OH) of the slurry - ) The stirring speed of the aging tank is 100rpm, which is 0.5 mol/L. The total volume of the slurry in the aging tank is 10-30m 3 At 3m 3 Introducing air into the slurry in the aging tank for 5 hours at the rate of/h, separating, washing and drying the aged slurry to obtain an NCM ternary precursor product, and detecting to obtain the NCM ternary precursor product: TD 1.85g/L, BET 12.8m 2 /g。
Example 5
Synthesizing a batch of slurry by adopting a method, sampling from the slurry, washing and drying the sample, transferring the slurry to an aging tank, adding 500L of 10mol/L alkali solution into the slurry, and controlling the total c (OH) of the slurry - ) The stirring speed of the aging tank is 100rpm, which is 0.5 mol/L. The total volume of the slurry in the aging tank is 10-30m 3 At 5m 3 Introducing air for 3 hours into the slurry in the aging tank at the speed of/h, separating, washing and drying the aged slurry to obtain an NCM ternary precursor product, and detecting to obtain the NCM ternary precursor product: TD 1.85g/L, BET 12.7m 2 /g。
As shown in fig. 1-2, SEM observation is performed on the NCM ternary precursor materials before and after aging in the embodiment of the present invention, respectively, and it is found that after aging by the aging method disclosed in the present invention, the wrinkles on the surface of the NCM ternary precursor become more, the texture becomes thinner, and the specific surface area increases.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. An aging method for directionally improving specific surface area of a nickel-cobalt-manganese ternary precursor is characterized by comprising the following steps of:
(1) Adding an alkali solution into the nickel-cobalt-manganese ternary precursor slurry, controlling the stirring speed of the slurry to be 80-150 rpm, and controlling the total alkalinity in the nickel-cobalt-manganese ternary precursor slurry to be 0.2-0.5 mol/L;
(2) At a aeration rate of 0.1m per cubic meter of slurry 3 /h-1m 3 Air is introduced into the slurry obtained in the step (2) at the air-introducing speed of/h, the air-introducing time is 0.5h-10h, and the tap density TD is more than or equal to 1.8g/cm 3 、BET≥12m 2 /g nickel cobalt manganese ternary precursor.
2. The aging method for directionally increasing the specific surface area of the ternary nickel-cobalt-manganese precursor according to claim 1, wherein the concentration of the alkaline solution added in the step (1) is 8mol/L-12mol/L.
3. The aging method for directionally increasing the specific surface area of a nickel-cobalt-manganese ternary precursor according to claim 1, wherein the aeration rate in the step (2) is 0.3m 3 /h-0.8m 3 /h。
4. The aging method for directionally increasing the specific surface area of the ternary nickel-cobalt-manganese precursor according to claim 1, wherein the ventilation time in the step (2) is 1h-5h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006136050A1 (en) * | 2005-06-20 | 2006-12-28 | Shenzhen Bak Battery Co., Ltd | A multicomponent composite lithium oxide containing nickel and cobalt, a method for producing the same, the use thereof as a positive electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| CN109761288A (en) * | 2019-04-09 | 2019-05-17 | 金驰能源材料有限公司 | A kind of preparation method of spherical nickel cobalt manganese persursor material |
| CN112645392A (en) * | 2021-03-11 | 2021-04-13 | 金驰能源材料有限公司 | Laminated high-density sphere-like cobalt oxyhydroxide precursor and preparation method thereof |
| CN113526569A (en) * | 2021-06-17 | 2021-10-22 | 福建常青新能源科技有限公司 | Preparation method of ternary material precursor and material prepared by preparation method |
| CN113651367A (en) * | 2021-07-29 | 2021-11-16 | 广东佳纳能源科技有限公司 | Nickel-cobalt-manganese ternary precursor material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006136050A1 (en) * | 2005-06-20 | 2006-12-28 | Shenzhen Bak Battery Co., Ltd | A multicomponent composite lithium oxide containing nickel and cobalt, a method for producing the same, the use thereof as a positive electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| CN109761288A (en) * | 2019-04-09 | 2019-05-17 | 金驰能源材料有限公司 | A kind of preparation method of spherical nickel cobalt manganese persursor material |
| CN112645392A (en) * | 2021-03-11 | 2021-04-13 | 金驰能源材料有限公司 | Laminated high-density sphere-like cobalt oxyhydroxide precursor and preparation method thereof |
| CN113526569A (en) * | 2021-06-17 | 2021-10-22 | 福建常青新能源科技有限公司 | Preparation method of ternary material precursor and material prepared by preparation method |
| CN113651367A (en) * | 2021-07-29 | 2021-11-16 | 广东佳纳能源科技有限公司 | Nickel-cobalt-manganese ternary precursor material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 锂离子电池正极材料镍钴铝酸锂前驱体制备工艺研究;栾沂铭;《中国优秀硕士学位论文全文数据库 工程科技I辑》(第7期);第47-52页 * |
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