CN115159591A - Preparation method of primary large-particle lithium-rich manganese-based precursor - Google Patents
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- 239000011572 manganese Substances 0.000 title claims abstract description 30
- 239000002243 precursor Substances 0.000 title claims abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 29
- 239000002245 particle Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000008139 complexing agent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000012716 precipitator Substances 0.000 claims abstract description 11
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 11
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 11
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 11
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 150000002696 manganese Chemical class 0.000 claims abstract description 3
- 150000002815 nickel Chemical class 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000011164 primary particle Substances 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 102220043159 rs587780996 Human genes 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 50
- 239000012266 salt solution Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910001437 manganese ion Inorganic materials 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 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
-
- 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
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- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
- C01P2006/11—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 Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a primary large-particle lithium-rich manganese-based precursor and a preparation method thereof, and the method comprises the following steps: preparing a solution A with a certain proportion of nickel salt and manganese salt, and adding a certain amount of complexing agent and surfactant into the solution A; preparing solution B from sodium hydroxide and sodium pyrophosphate according to a certain molar ratio, and using the solution B as a precipitator. And introducing the solution A and the solution B into a reaction kettle containing protective atmosphere, controlling the pH to be 11-12, the temperature to be 40-55 ℃, rotating speed to be 600-750rpm, and obtaining a lithium-rich manganese-based precursor with a primary large-particle accumulated spherical structure after aging, centrifugation, drying and sieving. Experimental results show that the lithium-rich manganese-based precursor prepared by the method has a small specific surface, high tap density and compacted density, and is beneficial to improving the energy density of the material and the cycle stability under the conditions of high temperature and high pressure.
Description
Technical Field
The invention relates to the technical field of battery materials, and relates to a preparation method of a primary large-particle lithium-rich manganese-based precursor.
Background
The lithium ion battery has the characteristics of high energy density, long cycle life, no memory effect and the like, and is widely applied to the aspects of 3C, medical equipment and the like. The lithium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode material of the lithium ion battery is generally considered to be a main reason for limiting the capacity of the lithium battery so as to limit the driving mileage of the electric vehicle.
At present, in the first charge and discharge process of a lithium ion battery, the first charge and discharge efficiency of a ternary material is not high due to the cation mixed discharge effect and the change of the surface microstructure of the material; meanwhile, in a wide voltage range, the ternary material and the organic electrolyte generate violent side reactions, so that the impedance of the battery in the charging and discharging processes is increased, and the electrochemical performance of the material is reduced.
Chinese patent CN 112158889A discloses a method for mass production of a single crystal cobalt-free lithium-rich manganese-based binary material precursor, which adopts sodium hydroxide as a precipitator and ammonia water as a complexing agent to prepare a nickel-manganese binary precursor.
Disclosure of Invention
The invention aims to provide a primary large-particle lithium-rich manganese-based precursor and a preparation method thereof, hopefully, the lithium-rich manganese-based precursor with a special shape is prepared by the method, and further, the cycle performance and the energy density of a lithium ion battery are improved. The specific scheme is as follows:
a preparation method of a primary large-particle lithium-rich manganese-based precursor comprises the following steps:
a. dissolving nickel salt and manganese salt in deionized water to obtain a solution, and adding a complexing agent and a surfactant to obtain a solution A; the surfactant is sodium dodecyl sulfate;
b. preparing solution B from sodium hydroxide and sodium pyrophosphate as a precipitator;
c. introducing the solution A and the solution B into a reaction kettle containing protective atmosphere, controlling the pH value to be 11-12 and the temperature to be 40-55 ℃;
d. stopping feeding, performing certain aging, performing centrifugal washing, vacuum drying, and sieving to obtain a primary large-particle lithium-rich manganese-based precursor;
the prepared primary large-particle lithium-rich manganese-based precursor has the advantages that the primary particles are thick and long, the thickness is 0.8-1.2um, and the length is 2-3um. General formula is Ni x Mn 1-x (OH) 2 。
The prepared primary large-particle lithium-rich manganese-based precursor has the D50=5-7um and the tap density of 1.7-1.9g/cm 3 Loose packed 1.2-1.6g/cm 3 . Due to the precursor being built up from larger primary particles.
In the step a, the complexing agent is citric acid, and the concentration of the complexing agent is 1-2g/L.
The concentration of the surfactant in the step a is 0.04g/L-0.08g/L.
In the step b, the molar ratio of sodium hydroxide to sodium pyrophosphate is 10:1-30:1.
in the step b, the concentration of the precipitator is 5-8mol/L.
The precursor prepared by the process has larger primary particles, and the large primary particles are beneficial to improving the tap density and the compaction density of the lithium-rich manganese-based material and increasing the energy density of the material. And the specific surface area is more than 40 percent smaller than that of the common secondary particle material, which is beneficial to improving the cycling stability of the material under the conditions of high temperature and high pressure.
The invention adopts a precipitator prepared from sodium hydroxide and sodium pyrophosphate and sodium dodecyl sulfate as a surfactant; sodium hydroxide is used as strong base, sodium pyrophosphate has buffering and dispersing functions, and the stability of the growth environment of the crystal can be ensured in the reaction; the sodium dodecyl sulfate can enable the crystal to develop towards a two-dimensional sheet direction to generate a sheet shape, and finally the crystal grows into a thick strip shape under the comprehensive action; the primary particles obtained by the method are thick and long-strip-shaped, and the large primary particles are beneficial to improving the tap density and the compacted density of the lithium-rich manganese-based material and increasing the energy density of the material.
Drawings
FIG. 1 is a graph of particle size distribution for the material prepared in example 1;
FIG. 2 is a low magnification SEM photograph of the material prepared in example 1;
FIG. 3 is a high power SEM image of the material prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
Example 1
1. Dissolving nickel sulfate and manganese sulfate in deionized water to prepare a salt solution with the concentration of 1.6mol/L, wherein the molar ratio of nickel ions to manganese ions in the salt solution is 1:3,
2. adding citric acid with the concentration of 1.4g/L into the solution as a complexing agent, and adding 0.07g/L sodium dodecyl sulfate as a surfactant to obtain solution A.
3. Mixing sodium hydroxide and sodium pyrophosphate according to a molar ratio of 20:1 to prepare a solution B with the concentration of 6mol/L as a precipitator.
4. And (3) enabling the solution A and the solution B to flow into a 50L reaction kettle containing a nitrogen atmosphere in a concurrent manner, wherein 40L of bottom liquid is obtained, the concentration of the complexing agent citric acid in the bottom liquid is 1.4g/L, the pH value is controlled to be 11.7, the temperature is 40 ℃, and the rotating speed is 750rpm. Wherein the flow rate of the solution A is 1.5L/h, and the flow rate of the solution B is 0.6L/h.
5. Stopping feeding after the particle size reaches 6um, aging for 10h, performing centrifugal washing, vacuum drying, and sieving to obtain a lithium-rich manganese-based precursor with primary particles being thick and long-strip-shaped, the thickness of 0.8-1.2um, and the length of 2-3um.
Example 2
1. Dissolving nickel sulfate and manganese sulfate in deionized water to prepare a salt solution with the concentration of 1.6mol/L, wherein the molar ratio of nickel ions to manganese ions in the salt solution is 1:3.
2. adding citric acid with the concentration of 1.4g/L into the solution as a complexing agent, and adding 0.07g/L sodium dodecyl sulfate as a surfactant to obtain solution A.
3. Sodium hydroxide and sodium pyrophosphate are mixed according to a molar ratio of 30:1 to prepare a solution B with the concentration of 6mol/L as a precipitator.
4. And (3) enabling the solution A and the solution B to flow into a 50L reaction kettle containing a nitrogen atmosphere in a cocurrent mode, wherein the bottom solution is 40L, the concentration of a complexing agent citric acid in the bottom solution is 1.4g/L, the pH value is controlled to be 11.7, the temperature is 45 ℃, and the rotating speed is 750rpm. Wherein, the flow rate of the solution A is 1.5L/h, and the flow rate of the solution B is 0.6L/h.
5. Stopping feeding after the particle size reaches 6um, aging for 10h, performing centrifugal washing, vacuum drying, and sieving to obtain a lithium-rich manganese-based precursor with primary particles being thick and long-strip-shaped, the thickness of 0.8-1.2um, and the length of 2-3um.
Example 3
1. Dissolving nickel sulfate and manganese sulfate in deionized water to prepare a salt solution with the concentration of 1.6mol/L, wherein the molar ratio of nickel ions to manganese ions in the salt solution is 1:3.
2. adding citric acid with the concentration of 1.4g/L as a complexing agent into the solution, and adding 0.07g/L sodium dodecyl sulfate as a surfactant to obtain a solution A.
3. Sodium hydroxide and sodium pyrophosphate are added according to a molar ratio of 10:1 preparing solution B with the concentration of 6mol/L as a precipitator.
4. And (3) enabling the solution A and the solution B to flow into a 50L reaction kettle containing a nitrogen atmosphere in a cocurrent mode, wherein the bottom solution is 40L, the concentration of a complexing agent citric acid in the bottom solution is 1.4g/L, the pH value is controlled to be 11.7, the temperature is 40 ℃, and the rotating speed is 750rpm. Wherein, the flow rate of the solution A is 1.5L/h, and the flow rate of the solution B is 0.6L/h.
5. Stopping feeding after the particle size reaches 6um, aging for 10h, performing centrifugal washing, vacuum drying, and sieving to obtain a lithium-rich manganese-based precursor with primary particles being thick and long-strip-shaped, the thickness of 0.8-1.2um, and the length of 2-3um.
Example 4
1. Dissolving nickel sulfate and manganese sulfate in deionized water to prepare a salt solution with the concentration of 1.6mol/L, wherein the molar ratio of nickel ions to manganese ions in the salt solution is 1:3.
2. adding citric acid with the concentration of 1.4g/L as a complexing agent into the solution, and adding 0.02g/L sodium dodecyl sulfate as a surfactant to obtain a solution A.
3. Mixing sodium hydroxide and sodium pyrophosphate according to a molar ratio of 20:1 preparing solution B with the concentration of 6mol/L as a precipitator.
4. And (3) enabling the solution A and the solution B to flow into a 50L reaction kettle containing a nitrogen atmosphere in a cocurrent mode, wherein the bottom solution is 40L, the concentration of a complexing agent citric acid in the bottom solution is 1.4g/L, the pH value is controlled to be 11.7, the temperature is 40 ℃, and the rotating speed is 750rpm. Wherein, the flow rate of the solution A is 1.5L/h, and the flow rate of the solution B is 0.6L/h.
5. Stopping feeding after the particle size reaches 6um, aging for 10h, performing centrifugal washing, vacuum drying, and sieving to obtain a lithium-rich manganese-based precursor with primary particles being thick and long-strip-shaped, the thickness of 0.8-1.2um, and the length of 2-3um.
Comparative example 1
1. Dissolving nickel sulfate and manganese sulfate in deionized water to prepare a salt solution with the concentration of 1.6mol/L, wherein the molar ratio of nickel ions to manganese ions in the salt solution is 1:3.
2. adding citric acid with the concentration of 1.4g/L into the solution as a complexing agent to obtain a solution A.
3. Sodium hydroxide is prepared into solution B with the concentration of 6mol/L and used as a precipitator.
4. And (3) enabling the solution A and the solution B to flow into a 50L reaction kettle containing a nitrogen atmosphere in a cocurrent mode, wherein the bottom solution is 40L, the concentration of a complexing agent citric acid in the bottom solution is 1.4g/L, the pH value is controlled to be 11.7, the temperature is 40 ℃, and the rotating speed is 750rpm. Wherein, the flow rate of the solution A is 1.5L/h, and the flow rate of the solution B is 0.6L/h.
5. Stopping feeding after the particle size reaches 6 mu m, aging for 10 hours, carrying out centrifugal washing, vacuum drying and sieving to obtain the lithium-rich manganese-based precursor with the thickness of 0.3-0.4 mu m and the length of 0.8-1 mu m of primary particles.
The experimental results are as follows: see table 1:
table 1 shows the properties of examples and comparative examples
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Tap (g/cm) 3 ) | 1.87 | 1.75 | 1.78 | 1.72 | 1.62 |
| Loose pack (g/cm) 3 ) | 1.52 | 1.45 | 1.42 | 1.40 | 0.91 |
| Scale (m) 2 /g) | 16.1 | 25.3 | 26.7 | 27.9 | 35.4 |
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (6)
1. A preparation method of a primary large-particle lithium-rich manganese-based precursor is characterized by comprising the following steps:
a. dissolving nickel salt and manganese salt in deionized water to obtain a solution, and adding a complexing agent and a surfactant to obtain a solution A; the surfactant is sodium dodecyl sulfate;
b. preparing solution B from sodium hydroxide and sodium pyrophosphate as a precipitator;
c. introducing the solution A and the solution B into a reaction kettle containing protective atmosphere, controlling the pH to be 11-12 and the temperature to be 40-55 ℃;
d. stopping feeding, performing certain aging, performing centrifugal washing, vacuum drying, and sieving to obtain a primary large-particle lithium-rich manganese-based precursor;
the primary particles of the prepared primary large-particle lithium-rich manganese-based precursor are thick and long-strip-shaped, the thickness of the primary particles is 0.8-1.2um, and the length of the primary particles is 2-3um.
2. The method for preparing a primary large-particle lithium-rich manganese-based precursor according to claim 1, wherein: the prepared primary large-particle lithium-rich manganese-based precursor has the D50=5-7um and the tap density of 1.7-1.9g/cm 3 Loose packed 1.2-1.6g/cm 3 。
3. The method for preparing a primary large-particle lithium-rich manganese-based precursor according to claim 1, wherein the method comprises the following steps: in the step a, the complexing agent is citric acid, and the concentration of the complexing agent is 1-2g/L.
4. The method for preparing a primary large-particle lithium-rich manganese-based precursor according to claim 1, wherein: the concentration of the surfactant in the step a is 0.04g/L-0.08g/L.
5. The method for preparing a primary large-particle lithium-rich manganese-based precursor according to claim 1, wherein: in the step b, the molar ratio of sodium hydroxide to sodium pyrophosphate is 10:1-30:1.
6. the method for preparing a primary large-particle lithium-rich manganese-based precursor according to claim 1, wherein: in the step b, the concentration of the precipitant is 5-8mol/L.
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| CN102881886A (en) * | 2012-09-24 | 2013-01-16 | 中国海洋石油总公司 | Method for preparing high-tap-density spherical lithium-rich manganese-based anode material |
| WO2015198676A1 (en) * | 2014-06-27 | 2015-12-30 | 住友金属鉱山株式会社 | Manganese composite hydroxide and method for producing same, positive electrode active material and method for producing same, and nonaqueous electrolyte secondary battery |
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| CN112694137A (en) * | 2020-12-24 | 2021-04-23 | 荆门市格林美新材料有限公司 | Small-particle-size cobalt-free lithium-rich manganese-based solid solution and lithium vanadate composite material and preparation method thereof |
| CN114735762A (en) * | 2022-04-24 | 2022-07-12 | 广东邦普循环科技有限公司 | A kind of high tap density ternary precursor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2025065786A1 (en) * | 2023-09-27 | 2025-04-03 | 格林美股份有限公司 | Modified lithium-rich manganese-based precursor, and preparation method therefor and use thereof |
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