CN115304103B - Aluminum-doped manganese carbonate and preparation method and application thereof - Google Patents

Aluminum-doped manganese carbonate and preparation method and application thereof Download PDF

Info

Publication number
CN115304103B
CN115304103B CN202211012763.9A CN202211012763A CN115304103B CN 115304103 B CN115304103 B CN 115304103B CN 202211012763 A CN202211012763 A CN 202211012763A CN 115304103 B CN115304103 B CN 115304103B
Authority
CN
China
Prior art keywords
aluminum
solution
reaction
particle size
manganese carbonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211012763.9A
Other languages
Chinese (zh)
Other versions
CN115304103A (en
Inventor
刘文泽
段小波
许开华
张坤
于杨
胡美林
陈颖
赵亚强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jingmen GEM New Material Co Ltd
Original Assignee
Jingmen GEM New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jingmen GEM New Material Co Ltd filed Critical Jingmen GEM New Material Co Ltd
Priority to CN202211012763.9A priority Critical patent/CN115304103B/en
Publication of CN115304103A publication Critical patent/CN115304103A/en
Application granted granted Critical
Publication of CN115304103B publication Critical patent/CN115304103B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/50—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to aluminum-doped manganese carbonate and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding mixed salt solution, organic acid solution and precipitant solution in parallel flow into reaction base solution to react, controlling the particle size of the product in the reaction process until the reaction is complete, and sequentially washing and drying to obtain the aluminum-doped manganese carbonate; the mixed salt solution comprises manganese salt and aluminum salt; the reaction base solution comprises a complexing agent and a dispersing agent. According to the invention, the complexing agent and the dispersing agent are added into the reaction base solution, so that aluminum element is uniformly distributed in manganese carbonate and is not easy to aggregate, the granularity distribution uniformity and sphericity of the manganese carbonate are improved, the structural stability of the manganese-rich lithium-based electrode material is further improved, the volume expansion in the charging and discharging processes is reduced, and the service life and the safety of a battery are improved; and the preparation method can realize batch production.

Description

Aluminum-doped manganese carbonate and preparation method and application thereof
Technical Field
The invention belongs to the field of battery electrode materials, relates to manganese carbonate and a preparation method and application thereof, and in particular relates to aluminum-doped manganese carbonate and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high specific energy, long cycle life, small volume, light weight, no pollution and the like, and is widely applied to the fields of electric automobiles, information technology, energy storage power stations and the like. The rapid development of new generation electronics has placed higher demands on the performance of lithium ion batteries, while increasing high energy density, and also requiring long cycle life characteristics. With the rapid development of the battery industry, the lithium-rich manganese-based electrode material becomes a good choice for the next-generation battery material due to its high capacity. However, the lithium manganate electrode material has the problem of volume expansion in the charge and discharge process, so that the circularity of the battery is seriously affected, and simultaneously, a great potential safety hazard is brought to the practical application of the lithium ion battery.
CN107316990A discloses a preparation method of a precursor of a coated nickel-cobalt-aluminum cathode material, which comprises the steps of firstly synthesizing spherical nickel-cobalt hydroxide powder with an average particle diameter D50 of 8-25 mu m in a reactor, then coating a layer of aluminum hydroxide on the surface of the powder to form coated powder, removing residues in the powder in a reinforced washing manner after solid-liquid separation and ensuring the dispersibility of the powder, and fully drying to obtain the nickel-cobalt-aluminum cathode material with the average particle diameter D50 of 8-25 mu m and tap density of 1.8g/cm 3 The nickel cobalt aluminum positive electrode material precursor. The preparation method has simple process flow and is suitable for industrial mass production of the nickel-cobalt-aluminum positive electrode material precursor.
CN106784825a discloses a spherical nickel-containing manganese carbonate material, and a preparation method and application thereof, wherein nickel in the material mainly exists in the form of nickel carbonate, and the nickel carbonate accounts for more than 0 and less than or equal to 52wt% of the spherical nickel-containing manganese carbonate material. The spherical nickel-containing manganese carbonate material is obtained by a nickel ion and manganese ion coprecipitation method, and has the advantages of uniform particle size distribution, smooth surface, fine powder and the like; the method uses solubility difference, and has the characteristics of easy operation, short time consumption, etc. Compared with the pure spherical manganese carbonate, the prepared spherical nickel-containing manganese carbonate material is favorable for the charge and discharge performance of the lithium ion battery anode material containing nickel-containing manganese carbonate and improves the conductivity of the lithium ion battery anode material.
The above prior art makes the electrode material possess good conductivity by combining other elements with the precursor material, but does not solve the problem of volume expansion during charge and discharge. The aluminum-doped manganese carbonate prepared by the preparation method can reduce the volume expansion of the electrode material in the charge and discharge process, thereby improving the safety and the cycle performance of the battery.
Disclosure of Invention
The invention aims to provide aluminum-doped manganese carbonate, a preparation method and application thereof, and the aluminum-doped manganese carbonate prepared by the preparation method can reduce the volume expansion of an electrode material in the charge and discharge process and ensure the safety and the cycle performance of a battery.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing aluminum-doped manganese carbonate, the method comprising the steps of:
(1) Adding mixed salt solution, organic acid solution and precipitant solution in parallel flow into reaction base solution to react, and controlling the particle size of the product in the reaction process until the reaction is complete;
(2) Washing and drying the product obtained in the step (1) in sequence to obtain the aluminum-doped manganese carbonate;
the mixed salt solution in the step (1) comprises manganese salt and aluminum salt;
the reaction base solution in the step (1) comprises a complexing agent and a dispersing agent.
According to the invention, the complexing agent and the dispersing agent are added into the reaction base solution, so that aluminum elements are uniformly distributed in manganese carbonate and are not easy to aggregate, the sphericity of the manganese carbonate is improved, the structural stability of the manganese-rich lithium-based electrode material is further improved, the volume expansion in the charging and discharging processes is reduced, and the service life and the safety of a battery are improved; and the preparation method can realize batch production.
Preferably, the complexing agent in step (1) comprises aqueous ammonia or oxalic acid.
Preferably, the dispersant of step (1) comprises polyethylene glycol and/or cetyltrimethylammonium bromide (CTAB).
Preferably, the complexing agent concentration in the reaction base solution in step (1) is 1-3g/L, for example, 1g/L, 1.5g/L, 2g/L, 2.3g/L, 2.5g/L or 3g/L, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the concentration of the dispersant in the reaction base liquid in the step (1) is 0.3 to 0.8g/L, and for example, may be 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L, 0.7g/L or 0.8g/L, but not limited to the values recited, and other non-recited values within the numerical range are equally applicable.
When the concentration of the complexing agent is lower than 1g/L, the aluminum-doped manganese carbonate is not easy to form; when the concentration of the complexing agent is higher than 3g/L, large particle aggregation of the aluminum-doped manganese carbonate occurs. When the concentration of the dispersing agent is lower than 0.3g/L, the obtained manganese carbonate has serious agglomeration phenomenon, and when the concentration of the dispersing agent is higher than 0.8g/L, the aluminum-doped manganese carbonate is not easy to form. Therefore, the concentration of the complexing agent in the reaction base solution is controlled to be 1-3g/L, and the concentration of the dispersing agent is controlled to be 0.3-0.8g/L, which is beneficial to uniformly distributing aluminum element in manganese carbonate and improving sphericity and granularity distribution uniformity of aluminum-doped manganese carbonate.
Preferably, the aluminum salt of step (1) comprises any one or at least two of aluminum sulfate, aluminum chloride, or aluminum nitrate, typically but not limited to combinations comprising aluminum sulfate and aluminum chloride, aluminum chloride and aluminum nitrate, aluminum sulfate and aluminum nitrate, or aluminum sulfate, aluminum chloride and aluminum nitrate.
Preferably, the manganese salt of step (1) comprises any one or a combination of at least two of manganese sulfate, manganese nitrate or manganese acetate, typically but not limited to a combination of manganese sulfate and manganese nitrate, a combination of manganese nitrate and manganese acetate, a combination of manganese sulfate and manganese acetate, or a combination of manganese sulfate, manganese nitrate and manganese acetate.
Preferably, the mass concentration of aluminum in the mixed salt solution in step (1) is 2-5g/L, and may be, for example, 2g/L, 2.5g/L, 3g/L, 4g/L or 5g/L, but not limited to the exemplified values, and other values not exemplified in the range of values are equally applicable.
Preferably, the mass concentration of manganese in the mixed salt solution in step (1) is 60-150g/L, for example, 60g/L, 70g/L, 80g/L, 100g/L, 120g/L, 140g/L or 150g/L, but not limited to the exemplified values, and other non-exemplified values within the range of values are equally applicable.
Preferably, the organic acid in the organic acid solution of step (1) comprises oxalic acid.
Preferably, the concentration of the organic acid solution in step (1) is 70-100g/L, for example, 70g/L, 75g/L, 80g/L, 85g/L, 90g/L, 95g/L or 100g/L, but not limited to the exemplified values, and other values not exemplified in the range of values are equally applicable.
Preferably, the precipitant in the precipitant solution of step (1) comprises ammonium bicarbonate.
Preferably, the concentration of the precipitant solution in step (1) is 210-260g/L, which may be, for example, 210g/L, 220g/L, 230g/L, 240g/L, 250g/L or 260g/L, but is not limited to the values exemplified, and other values not exemplified in the range of values are equally applicable.
Preferably, the flow rate of the mixed salt solution in the step (1) is 20-50L/h, for example, 20L/h, 25L/h, 30L/h, 35L/h, 40L/h, 45L/h or 50L/h, but not limited to the exemplified values, and other values not exemplified in the range of values are equally applicable.
Preferably, the flow rate of the organic acid in the step (1) is 2-8L/h, for example, 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h or 8L/h, but not limited to the exemplified values, and other values not exemplified in the range of values are equally applicable.
Preferably, the flow ratio of the mixed salt solution to the organic acid solution in the step (1) is (4-7): 1, for example, it may be 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1 or 7:1, but not limited to the exemplified values, and other values not exemplified in the numerical range are equally applicable.
Preferably, the temperature of the reaction in step (1) is 35-45 ℃, for example 35 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃ or 45 ℃, but not limited to the values exemplified, other values not exemplified in the range of values are equally applicable.
When the temperature is lower than 35 ℃, the obtained aluminum-doped manganese carbonate is not easy to form and has poor sphericity; when the temperature is higher than 45 ℃, the particle size distribution of the aluminum-doped manganese carbonate is uneven, and the aggregation phenomenon is serious. The temperature of the reaction in the step (1) is controlled within the range of 35-45 ℃, which is favorable for the uniform distribution of aluminum element in manganese carbonate and is favorable for obtaining aluminum-doped manganese carbonate with uniform particle size distribution and good sphericity.
Preferably, the pH of the reaction in step (1) is 7-9, which may be, for example, 7, 7.5, 8, 8.5 or 9, but is not limited to the values exemplified, and other values not exemplified in the range of values are equally applicable.
The invention is not limited to the specific flow rate of the precipitant solution, as long as the pH value in the reaction process can be maintained at 7-9.
Preferably, the reaction in step (1) is carried out with stirring at a speed of 400-600r/min, for example 400r/min, 450r/min, 500r/min, 550r/min or 600r/min, but not limited to the values exemplified, other values not exemplified in the range of values being equally applicable.
Preferably, the controlling of the particle size of the product in step (1) means stopping feeding and aging when the particle size reaches the first particle size; and (5) when the particle size reaches the second particle size, feeding in parallel again.
The step (1) of controlling the particle size of the product means that the particle size of the product is controlled between a first particle size and a second particle size in the preparation process; stopping feeding and ageing when the particle size reaches the first particle size, reducing the particle size in the ageing process, and feeding in parallel again when the particle size is reduced to the second particle size; the above process is repeated until the reaction is complete.
Preferably, the aging temperature is 35-45 ℃, such as 35 ℃, 38 ℃, 40 ℃, 43 ℃, or 45 ℃, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the first particle diameter D50 is 4.5-5.5 μm, and may be, for example, 4.5 μm, 4.6 μm, 4.8 μm, 4.9 μm, 5 μm, 5.1 μm, 5.2 μm, 5.4 μm or 5.5 μm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the aging time is 1-2 hours, and may be, for example, 1 hour, 1.2 hours, 1.5 hours, 1.6 hours, 1.8 hours, or 2 hours, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the washing in the step (2) is performed using hot water at 50-80 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the drying in the step (2) is 50-120 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, but the method is not limited to the listed values, and other non-listed values in the range of values are equally applicable.
As a preferred technical scheme of the preparation method according to the first aspect of the present invention, the preparation method comprises the following steps:
(1) Adding mixed salt solution, oxalic acid solution with the concentration of 70-100g/L and ammonium bicarbonate solution with the concentration of 210-260g/L into reaction base solution in parallel flow under the conditions that the reaction temperature is 35-45 ℃ and the stirring rotation speed is 400-600r/min for reaction, and controlling the particle size of a product until the reaction is complete in the reaction process;
the flow rate of the mixed salt solution is 20-50L/h, the flow rate of the organic acid solution is 2-8L/h, and the flow rate ratio of the mixed salt solution to the oxalic acid solution is (4-7): 1; the flow rate of the ammonium bicarbonate solution is that the pH value in the reaction process is maintained to be 7-9;
the control of the particle size of the product means that when the particle size reaches the first particle size, the feeding is stopped and the aging is carried out at 35-45 ℃; aging for 1-2h until the particle size reaches a second particle size, and feeding in parallel again; the first particle diameter D50 is 4.5-5.5 mu m;
(2) Washing the product obtained in the step (1) by hot water at 50-80 ℃ and drying at 50-120 ℃ to obtain the aluminum-doped manganese carbonate;
the mixed salt solution in the step (1) comprises manganese salt and aluminum salt; the mass concentration of aluminum in the mixed salt solution is 2-5g/L, and the mass concentration of manganese is 60-150g/L;
the reaction base solution in the step (1) comprises a complexing agent and a dispersing agent; the concentration of the complexing agent in the reaction base solution is 1-3g/L, and the concentration of the dispersing agent is 0.3-0.8g/L; the complexing agent comprises ammonia water or oxalic acid; the dispersant comprises polyethylene glycol and/or cetyl trimethylammonium bromide.
In a second aspect, the present invention provides an aluminium-doped manganese carbonate obtainable by the process of the first aspect.
In a third aspect, the present invention provides a lithium ion battery comprising the aluminium-doped manganese carbonate of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the complexing agent and the dispersing agent are added into the reaction base solution, so that aluminum elements are uniformly distributed in manganese carbonate and are not easy to aggregate, the obtained aluminum-doped manganese carbonate has uniform particle size distribution and good sphericity, the structural stability of the manganese-rich lithium-based electrode material is further improved, the volume expansion in the charging and discharging processes is reduced, and the service life and the safety of a battery are improved; and the preparation method can realize batch production.
Drawings
FIG. 1a is an X-ray diffraction pattern of the aluminum-doped manganese carbonate obtained in example 1;
FIGS. 1b and 1c are SEM images of aluminum-doped manganese carbonate obtained in example 1;
FIG. 1d is a graph showing the distribution of aluminum elements in the aluminum-doped manganese carbonate obtained in example 1;
FIG. 2 is an SEM image of the aluminum-doped manganese carbonate obtained in example 4;
FIG. 3 is an SEM image of the aluminum-doped manganese carbonate obtained in example 10;
FIG. 4 is an SEM image of the aluminum-doped manganese carbonate obtained in example 11;
FIGS. 5a and 5b are SEM images of the aluminum-doped manganese carbonate obtained in comparative example 3;
fig. 6a and 6b are SEM images of the aluminum-doped manganese carbonate obtained in comparative example 4.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of aluminum-doped manganese carbonate, which comprises the following steps:
(1) Under the conditions that the reaction temperature is 40 ℃ and the stirring rotation speed is 550r/min, mixed salt solution, oxalic acid solution with the concentration of 90g/L and ammonium bicarbonate solution with the concentration of 220g/L are added into the reaction base solution in parallel flow for reaction, and the particle size of the product is controlled until the reaction is complete in the reaction process;
the flow rate of the mixed salt solution is 28L/h, and the flow rate of the organic acid solution is 5L/h; the flow rate of the ammonium bicarbonate solution is such that the pH value in the reaction process is maintained at 7.3;
the control of the product particle size means that when the particle size reaches 5 μm, the feeding is stopped and the aging is carried out at 40 ℃; aging for 1.5h, and feeding in parallel flow again;
(2) Washing the product obtained in the step (1) by hot water at 75 ℃ and drying at 80 ℃ to obtain the aluminum-doped manganese carbonate;
the mixed salt solution in the step (1) comprises manganese chloride and aluminum chloride; the mass concentration of aluminum in the mixed salt solution is 3g/L, and the mass concentration of manganese is 80g/L;
the reaction base solution in the step (1) comprises a complexing agent and a dispersing agent; the complexing agent is oxalic acid, and the concentration is 2.3g/L; the dispersing agent is cetyl trimethyl ammonium bromide, and the concentration is 0.5g/L.
As shown in FIG. 1a, the XRD pattern of the aluminum-doped manganese carbonate obtained in this example is shown in FIG. 1a, and the final product obtained in this example is aluminum-doped manganese carbonate;
as shown in fig. 1b and 1c, SEM images of the aluminum-doped manganese carbonate obtained in the present example are shown in fig. 1b and 1c, and the sphericity of the aluminum-doped manganese carbonate obtained in the present example is good;
as can be seen from FIG. 1d, the distribution diagram of the aluminum element in the aluminum-doped manganese carbonate obtained in this example is shown in FIG. 1 d.
Example 2
The embodiment provides a preparation method of aluminum-doped manganese carbonate, which comprises the following steps:
(1) Adding mixed salt solution, oxalic acid solution with the concentration of 70g/L and ammonium bicarbonate solution with the concentration of 210g/L into the reaction base solution in parallel flow under the conditions that the reaction temperature is 35 ℃ and the stirring rotation speed is 600r/min, and reacting, wherein the particle size of a product is controlled until the reaction is complete in the reaction process;
the flow rate of the mixed salt solution is 21L/h, and the flow rate of the organic acid solution is 3L/h; the flow rate of the ammonium bicarbonate solution is 9 for maintaining the pH value in the reaction process;
the control of the product particle size means that when the particle size reaches 5.5 μm, the feeding is stopped and the aging is carried out at 35 ℃; aging for 2 hours, and feeding in parallel flow again;
(2) Washing the product obtained in the step (1) by hot water at 80 ℃ and drying at 120 ℃ to obtain the aluminum-doped manganese carbonate;
the mixed salt solution in the step (1) comprises manganese sulfate and aluminum sulfate; the mass concentration of aluminum in the mixed salt solution is 2g/L, and the mass concentration of manganese is 60g/L;
the reaction base solution in the step (1) comprises a complexing agent and a dispersing agent; the complexing agent is oxalic acid, and the concentration is 1g/L; the dispersing agent is cetyl trimethyl ammonium bromide, and the concentration is 0.3g/L.
Example 3
The embodiment provides a preparation method of aluminum-doped manganese carbonate, which comprises the following steps:
(1) Adding mixed salt solution, oxalic acid solution with the concentration of 100g/L and ammonium bicarbonate solution with the concentration of 260g/L into the reaction base solution in parallel flow under the conditions that the reaction temperature is 45 ℃ and the stirring rotation speed is 400r/min, and controlling the particle size of the product until the reaction is complete in the reaction process;
the flow rate of the mixed salt solution is 32L/h, and the flow rate of the organic acid solution is 8L/h; the flow rate of the ammonium bicarbonate solution is maintained to be 7 pH value in the reaction process;
the control of the product particle size means that when the particle size reaches 4.5 μm, the feeding is stopped and the aging is carried out at 45 ℃; aging for 1h, and feeding in parallel again;
(2) Washing the product obtained in the step (1) by hot water at 50 ℃ and drying at 50 ℃ to obtain the aluminum-doped manganese carbonate;
the mixed salt solution in the step (1) comprises manganese nitrate and aluminum nitrate; the mass concentration of aluminum in the mixed salt solution is 5g/L, and the mass concentration of manganese is 150g/L;
the reaction base solution in the step (1) comprises a complexing agent and a dispersing agent; the complexing agent is oxalic acid, and the concentration is 3g/L; the dispersing agent is cetyl trimethyl ammonium bromide, and the concentration is 0.8g/L.
Example 4
The embodiment provides a preparation method of aluminum-doped manganese carbonate, which is the same as that of embodiment 1 except that complexing agent oxalic acid is replaced by complexing agent ammonia water with the same mass in the reaction base solution in the step (1).
The microscope picture of the aluminum-doped manganese carbonate obtained in the embodiment is shown in fig. 2, and as can be seen from fig. 2, after the complexing agent oxalic acid is replaced by ammonia water, the manganese carbonate is seriously agglomerated, and the effect of the complexing agent is poorer than that of the oxalic acid by adopting ammonia water.
Example 5
This example provides a method for preparing aluminum-doped manganese carbonate, which is the same as example 1 except that in the reaction base solution in step (1), cetyl trimethyl ammonium bromide serving as a dispersant is replaced by polyethylene glycol serving as a dispersant with the same mass.
Example 6
The embodiment provides a preparation method of aluminum-doped manganese carbonate, which is the same as that of the embodiment 1 except that the concentration of oxalic acid as a complexing agent in the reaction base solution in the step (1) is 0.7 g/L.
Example 7
The embodiment provides a preparation method of aluminum-doped manganese carbonate, which is the same as that of the embodiment 1 except that the concentration of the complexing agent oxalic acid in the reaction base solution in the step (1) is 3.3 g/L.
Example 8
This example provides a method for preparing aluminum-doped manganese carbonate, which is the same as in example 1 except that the concentration of cetyl trimethylammonium bromide as a dispersant in the reaction base solution in step (1) is 0.2 g/L.
Example 9
This example provides a method for preparing aluminum-doped manganese carbonate, which is the same as in example 1 except that the concentration of cetyl trimethylammonium bromide as a dispersant in the reaction base solution in step (1) is 1 g/L.
Example 10
This example provides a process for preparing aluminum-doped manganese carbonate, which is the same as in example 1 except that the reaction temperature in step (1) is 30 ℃.
The SEM image of the aluminum-doped manganese carbonate obtained in this example is shown in FIG. 3, and it is understood from FIG. 3 that the reaction temperature was lowered to 30℃and the resulting manganese carbonate particles were mostly in the form of cubes and had poor sphericity.
Example 11
This example provides a process for preparing aluminum-doped manganese carbonate, which is the same as in example 1 except that the reaction temperature in step (1) is 50 ℃.
The SEM image of the aluminum-doped manganese carbonate obtained in this example is shown in fig. 4, and it can be seen from fig. 4 that the manganese carbonate is seriously agglomerated by increasing the reaction temperature to 50 ℃.
Comparative example 1
The comparative example provides a preparation method of aluminum-doped manganese carbonate, and the rest is the same as in example 1 except that the complexing agent in the reaction base solution in step (1) is replaced by a dispersing agent.
That is, the reaction base liquid in the step (1) of the present comparative example contained only the dispersant, and the concentration of the dispersant was 2.8g/L.
Comparative example 2
The comparative example provides a preparation method of aluminum-doped manganese carbonate, and the rest is the same as in example 1 except that the dispersant in the reaction base solution in step (1) is replaced by complexing agent.
Namely, the reaction base solution in the step (1) of the comparative example only comprises a complexing agent, and the concentration of the complexing agent is 2.8g/L.
Comparative example 3
This comparative example provides a method for preparing aluminum-doped manganese carbonate, which is the same as example 1 except that the reaction base solution in step (1) is pure water.
As shown in fig. 5a and 5b, the SEM images of the aluminum-doped manganese carbonate obtained in the comparative example show that the synthesized aluminum-doped manganese carbonate has poor sphericity, coarse primary crystal form and Al segregation on the surface when the complexing agent and the dispersing agent are not added to the reaction base solution in fig. 5a and 5 b.
Comparative example 4
This comparative example provides a method for preparing aluminum-doped manganese carbonate, which is the same as example 1 except that 15g/L of manganese sulfate solution is added to the reaction base solution in step (1).
As shown in fig. 6a and 6b, SEM images of the aluminum-doped manganese carbonate obtained in this comparative example show that when the base solution is changed to a manganese sulfate solution, a large amount of aluminum-doped manganese carbonate is agglomerated from fig. 6a and 6 b.
Comparative example 5
This comparative example provides a method for preparing aluminum-doped manganese carbonate, which is the same as example 1 except that the organic acid solution is not added in step (1).
Performance testing
The particle size distribution and sphericity of the aluminum-doped aluminum carbonates provided in examples 1-11 and comparative examples 1-5 were tested by: counting the D50 particle size and the D90 particle size of the obtained aluminum-doped manganese carbonate by using an European and American laser particle sizer, and calculating a D50/D90 value; sphericity was tested using SEM. The results obtained are shown in Table 1.
TABLE 1
As shown in Table 1, the particle diameter D50 of the aluminum-doped manganese carbonate obtained in the examples 1-3 is 4.9-5.1 μm, the particle diameter D90 is 7.8-8.6 μm, and the D50/D90 is more than or equal to 58.76%, and the particle diameter distribution is uniform; and the sphericity of the obtained aluminum-doped manganese carbonate is good.
As can be seen from a comparison of example 4 and example 1, when the complexing agent is ammonia water, the D50/D90 of the obtained aluminum-doped manganese carbonate is only 18.43, which indicates that the aluminum-doped manganese carbonate is seriously agglomerated, and the sphericity cannot be measured. Therefore, oxalic acid is used as a complexing agent, which is favorable for obtaining aluminum-doped manganese carbonate with uniform particle size distribution.
As is clear from a comparison of example 5 and example 1, when the dispersant cetyltrimethylammonium bromide was replaced with polyethylene glycol, the particle size of the obtained aluminum-doped manganese carbonate increased, and the sphericity was good. Therefore, cetyl trimethyl ammonium bromide is selected as a dispersing agent, which is favorable for obtaining aluminum-doped manganese carbonate with uniform particle size distribution and smaller particle size.
As can be seen from the comparison of examples 6 and 7 with example 1, when the concentration of the complexing agent is lower than 1g/L, the aluminum-doped manganese carbonate is not easy to form and has poor sphericity; when the concentration of the complexing agent is higher than 3g/L, large particle aggregation of aluminum-doped manganese carbonate occurs, and the particle sizes D50 and D90 are increased.
As is clear from comparison of examples 8 and 9 with example 1, when the concentration of the dispersant is lower than 0.3g/L, the D50/D90 of the obtained aluminum-doped manganese carbonate is reduced, and agglomeration phenomenon occurs; when the concentration of the dispersing agent in the reaction base solution is higher than 0.8g/L, the particle sizes D50 and D90 of the aluminum-doped manganese carbonate are reduced.
Therefore, the concentration of the complexing agent in the reaction base solution is controlled to be 1-3g/L, and the concentration of the dispersing agent is controlled to be 0.3-0.8g/L, which is beneficial to uniformly distributing aluminum element in manganese carbonate and improving sphericity and granularity distribution uniformity of aluminum-doped manganese carbonate.
As can be seen from comparison of examples 10 and 11 with example 1, when the reaction temperature is lower than 35 ℃, the obtained aluminum-doped manganese carbonate has uniform particle size distribution, D50/D90 can reach 63.25%, but the generated aluminum-doped manganese carbonate particles are mostly square and have poor sphericity; when the reaction temperature is higher than 45 ℃, D90 can reach 58.796 mu m, and the aluminum-doped manganese carbonate is seriously agglomerated and cannot be measured. Therefore, the reaction temperature is controlled to be 35-45 ℃, which is favorable for obtaining aluminum-doped manganese carbonate with uniform particle size distribution and good sphericity.
As is clear from a comparison of comparative example 1 and example 1, however, when only the dispersant is added to the reaction base solution, an effective amount of manganese carbonate pellets cannot be formed; as is clear from comparison of comparative example 2 and example 1, when only the complexing agent was added to the reaction base solution, the obtained aluminum-doped manganese carbonate large particles were aggregated, the particle size distribution was uneven and the sphericity was poor; as is clear from comparison of comparative examples 3 and 4 with example 1, when the composition of the reaction base liquid is changed, it is disadvantageous to obtain aluminum-doped manganese carbonate having a uniform particle size distribution and good sphericity. Therefore, the reaction base solution simultaneously comprises the complexing agent and the dispersing agent, which is favorable for forming aluminum-doped manganese carbonate with uniform particle size distribution and good sphericity.
As is clear from the comparison of comparative example 5 and example 1, the sphericity of the obtained aluminum-doped manganese carbonate was poor if no organic acid was added; oxalic acid is used as organic acid to prepare aluminum-doped manganese carbonate, which is favorable for obtaining aluminum-doped manganese carbonate with uniform particle size distribution and good sphericity.
In summary, in the preparation method of the aluminum-doped manganese carbonate provided by the invention, the complexing agent and the dispersing agent are added into the reaction base solution, so that aluminum elements are uniformly distributed in the manganese carbonate and are not easy to aggregate, the obtained manganese carbonate has uniform particle size distribution and good sphericity, the structural stability of the manganese-rich lithium-based electrode material is further improved, the volume expansion in the charging and discharging processes is reduced, and the service life and the safety of a battery are improved; and the preparation method can realize batch production.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.

Claims (21)

1. The preparation method of the aluminum-doped manganese carbonate is characterized by comprising the following steps of:
(1) Adding mixed salt solution, organic acid solution and precipitant solution in parallel flow into reaction base solution to react, and controlling the particle size of the product in the reaction process until the reaction is complete;
the temperature of the reaction is 35-45 ℃;
(2) Washing and drying the product obtained in the step (1) in sequence to obtain the aluminum-doped manganese carbonate;
the mixed salt solution in the step (1) comprises manganese salt and aluminum salt;
the reaction base solution in the step (1) is a complexing agent and a dispersing agent; the complexing agent is oxalic acid;
the concentration of the complexing agent in the reaction base solution is 1-3g/L; the concentration of the dispersing agent in the reaction base solution is 0.3-0.8g/L.
2. The method of claim 1, wherein the dispersant comprises polyethylene glycol and/or cetyltrimethylammonium bromide.
3. The method of claim 1, wherein the aluminum salt comprises any one or a combination of at least two of aluminum sulfate, aluminum chloride, or aluminum nitrate.
4. The method of claim 1, wherein the manganese salt comprises any one or a combination of at least two of manganese sulfate, manganese nitrate, or manganese acetate.
5. The method according to claim 1, wherein the mass concentration of aluminum in the mixed salt solution in the step (1) is 2 to 5g/L.
6. The method according to claim 1, wherein the mass concentration of manganese in the mixed salt solution of step (1) is 60 to 150g/L.
7. The method of claim 1, wherein the organic acid in the organic acid solution of step (1) comprises oxalic acid.
8. The method according to claim 1, wherein the concentration of the organic acid solution in the step (1) is 70 to 100g/L.
9. The method of claim 1, wherein the precipitant in the precipitant solution of step (1) comprises ammonium bicarbonate.
10. The method of claim 1, wherein the precipitant solution in step (1) has a concentration of 210-260g/L.
11. The method according to claim 1, wherein the flow rate of the mixed salt solution in the step (1) is 20 to 50L/h.
12. The method according to claim 1, wherein the flow rate of the organic acid solution in the step (1) is 2 to 8L/h.
13. The process according to claim 1, wherein the pH of the reaction in step (1) is 7-9.
14. The process according to claim 1, wherein the reaction in step (1) is accompanied by stirring at a rotation speed of 400 to 600r/min.
15. The process of claim 1, wherein controlling the product particle size in step (1) means stopping the feed and aging when the particle size reaches the first particle size; aging until the particle size reaches a second particle size, and feeding in parallel again.
16. The method of claim 15, wherein the aging temperature is 35-45 ℃.
17. The method of claim 15, wherein the first particle size D50 is 4.5-5.5 μm.
18. The method of claim 15, wherein the aging time is 1-2 hours.
19. The method according to claim 1, wherein the washing in the step (2) is washing with hot water of 50 to 80 ℃.
20. The method according to claim 1, wherein the temperature of the drying in step (2) is 50 to 120 ℃.
21. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Adding mixed salt solution, oxalic acid solution with the concentration of 70-100g/L and ammonium bicarbonate solution with the concentration of 210-260g/L into reaction base solution in parallel flow under the conditions that the reaction temperature is 35-45 ℃ and the stirring rotation speed is 400-600r/min for reaction, and controlling the particle size of a product until the reaction is complete in the reaction process;
the flow rate of the mixed salt solution is 20-50L/h, and the flow rate of the organic acid solution is 2-8L/h; the flow rate of the ammonium bicarbonate solution is that the pH value in the reaction process is maintained to be 7-9;
the control of the particle size of the product means that when the particle size reaches the first particle size, the feeding is stopped and the aging is carried out at 35-45 ℃; aging for 1-2h until the particle size reaches a second particle size, and feeding in parallel again; the first particle diameter D50 is 4.5-5.5 μm;
(2) Washing the product obtained in the step (1) by hot water at 50-80 ℃ and drying at 50-120 ℃ to obtain the aluminum-doped manganese carbonate;
the mixed salt solution in the step (1) comprises manganese salt and aluminum salt; the mass concentration of aluminum in the mixed salt solution is 2-5g/L, and the mass concentration of manganese is 60-150g/L;
the reaction base solution in the step (1) is a complexing agent and a dispersing agent; the concentration of the complexing agent in the reaction base solution is 1-3g/L, and the concentration of the dispersing agent is 0.3-0.8g/L; the complexing agent is oxalic acid; the dispersant comprises polyethylene glycol and/or cetyl trimethylammonium bromide.
CN202211012763.9A 2022-08-23 2022-08-23 Aluminum-doped manganese carbonate and preparation method and application thereof Active CN115304103B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211012763.9A CN115304103B (en) 2022-08-23 2022-08-23 Aluminum-doped manganese carbonate and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211012763.9A CN115304103B (en) 2022-08-23 2022-08-23 Aluminum-doped manganese carbonate and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115304103A CN115304103A (en) 2022-11-08
CN115304103B true CN115304103B (en) 2023-11-03

Family

ID=83865021

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211012763.9A Active CN115304103B (en) 2022-08-23 2022-08-23 Aluminum-doped manganese carbonate and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115304103B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116462242A (en) * 2023-06-07 2023-07-21 荆门市格林美新材料有限公司 Nickel-iron-manganese-copper sodium ion precursor and preparation method and application thereof

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006219323A (en) * 2005-02-09 2006-08-24 Sumitomo Metal Mining Co Ltd Lithium-manganese-nickel-aluminum complex oxide and its production method
CN101269840A (en) * 2008-03-05 2008-09-24 广州融捷材料科技有限公司 Spherical manganese carbonate and preparing method thereof
CN103035902A (en) * 2012-12-07 2013-04-10 上海空间电源研究所 Preparation method of modified manganese oxide material for lithium ion batteries
CN105244501A (en) * 2015-09-25 2016-01-13 湖北工程学院 Active substance precursor nickel manganese carbonate of lithium ion battery electrode
CN110112411A (en) * 2019-04-23 2019-08-09 上海应用技术大学 A kind of MnCO3Microballoon and preparation method thereof
CN110540250A (en) * 2018-05-28 2019-12-06 荆门市格林美新材料有限公司 preparation method of aluminum-doped cobalt carbonate
CN110817966A (en) * 2019-11-19 2020-02-21 中国科学院青海盐湖研究所 Preparation method of spherical manganese carbonate
CN111056575A (en) * 2020-01-13 2020-04-24 衢州华友钴新材料有限公司 Preparation method of compact crystal form small-particle-size spherical cobalt carbonate
CN112357971A (en) * 2020-11-11 2021-02-12 金川集团股份有限公司 Preparation method of aluminum-doped large-particle-size cobalt carbonate for battery
CN113582234A (en) * 2021-08-11 2021-11-02 南方锰业集团有限责任公司 Preparation method of battery-grade spheroidal manganese carbonate
CN113816430A (en) * 2021-07-30 2021-12-21 高点(深圳)科技有限公司 Preparation method of modified mangano-manganic oxide, product and application
CN113830839A (en) * 2021-08-18 2021-12-24 广东邦普循环科技有限公司 Preparation method and application of flaky aluminum-doped cobalt carbonate
CN114644367A (en) * 2022-03-03 2022-06-21 江西江钨钴业有限公司 Preparation method of high-dispersion nano spheroidal cobalt carbonate
CN114702081A (en) * 2022-04-25 2022-07-05 广东邦普循环科技有限公司 Preparation method and application of magnesium-titanium co-doped cobalt carbonate
WO2022142327A1 (en) * 2020-12-30 2022-07-07 巴斯夫杉杉电池材料有限公司 Aluminum-doped cobaltosic oxide core-shell material and preparation method therefor

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006219323A (en) * 2005-02-09 2006-08-24 Sumitomo Metal Mining Co Ltd Lithium-manganese-nickel-aluminum complex oxide and its production method
CN101269840A (en) * 2008-03-05 2008-09-24 广州融捷材料科技有限公司 Spherical manganese carbonate and preparing method thereof
CN103035902A (en) * 2012-12-07 2013-04-10 上海空间电源研究所 Preparation method of modified manganese oxide material for lithium ion batteries
CN105244501A (en) * 2015-09-25 2016-01-13 湖北工程学院 Active substance precursor nickel manganese carbonate of lithium ion battery electrode
CN110540250A (en) * 2018-05-28 2019-12-06 荆门市格林美新材料有限公司 preparation method of aluminum-doped cobalt carbonate
CN110112411A (en) * 2019-04-23 2019-08-09 上海应用技术大学 A kind of MnCO3Microballoon and preparation method thereof
CN110817966A (en) * 2019-11-19 2020-02-21 中国科学院青海盐湖研究所 Preparation method of spherical manganese carbonate
CN111056575A (en) * 2020-01-13 2020-04-24 衢州华友钴新材料有限公司 Preparation method of compact crystal form small-particle-size spherical cobalt carbonate
CN112357971A (en) * 2020-11-11 2021-02-12 金川集团股份有限公司 Preparation method of aluminum-doped large-particle-size cobalt carbonate for battery
WO2022142327A1 (en) * 2020-12-30 2022-07-07 巴斯夫杉杉电池材料有限公司 Aluminum-doped cobaltosic oxide core-shell material and preparation method therefor
CN113816430A (en) * 2021-07-30 2021-12-21 高点(深圳)科技有限公司 Preparation method of modified mangano-manganic oxide, product and application
CN113582234A (en) * 2021-08-11 2021-11-02 南方锰业集团有限责任公司 Preparation method of battery-grade spheroidal manganese carbonate
CN113830839A (en) * 2021-08-18 2021-12-24 广东邦普循环科技有限公司 Preparation method and application of flaky aluminum-doped cobalt carbonate
CN114644367A (en) * 2022-03-03 2022-06-21 江西江钨钴业有限公司 Preparation method of high-dispersion nano spheroidal cobalt carbonate
CN114702081A (en) * 2022-04-25 2022-07-05 广东邦普循环科技有限公司 Preparation method and application of magnesium-titanium co-doped cobalt carbonate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
提高掺铝四氧化三钴均匀性研究;刘人生;王丽平;田礼平;秦鸣飞;;世界有色金属(07);全文 *
易欣.高端球形尖晶石锰酸锂正极材料的制备及其改性研究.中国优秀硕士学位论文数据库.第35-43页. *

Also Published As

Publication number Publication date
CN115304103A (en) 2022-11-08

Similar Documents

Publication Publication Date Title
CN109455772B (en) Modified precursor and anode material for lithium ion battery and preparation methods of precursor and anode material
CN108767216B (en) Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof
CN109461891B (en) High-voltage lithium cobalt oxide cathode material and preparation method thereof
WO2014061399A1 (en) Positive active material for lithium secondary battery, and positive electrode obtained using same
KR101313575B1 (en) Manufacturing method of positive active material precursor and lithium metal composite oxides for lithium secondary battery
KR20170102293A (en) Multicomponent materials having a classification structure for lithium ion batteries, a method for manufacturing the same, an anode of a lithium ion battery and a lithium ion battery
JP2005347134A (en) Manufacturing method of positive electrode active material for lithium ion secondary battery
CN109879333B (en) Method for preparing lithium battery anode material with core-shell structure by secondary molten salt method
CN111370683B (en) Preparation method of mono-like nickel cobalt lithium manganate
WO2019044734A1 (en) Positive electrode active substance for all solid-state lithium secondary battery
CN106784795B (en) Single-crystal spherical lithium manganate material, preparation method thereof and positive electrode material
WO2012020769A1 (en) Method for producing nickel-containing complex compound
CN112010358A (en) Carbon-doped ternary precursor, preparation method thereof, ternary cathode material and lithium ion battery
CN108987740B (en) Nickel-cobalt lithium aluminate anode material, preparation method thereof and battery applying nickel-cobalt lithium aluminate anode material
CN113497227A (en) Full-concentration-gradient-adjustable mono-like lithium-rich layered oxide cathode material and preparation method thereof
CN111600010B (en) Preparation method of single crystal large particles of ternary material
CN101022161A (en) Lithiumion secondary battery anode material LixCoyLazMn(z-y-z) O4 and producing process thereof
CN115304103B (en) Aluminum-doped manganese carbonate and preparation method and application thereof
CN110504447A (en) A kind of nickel cobalt manganese presoma of Fluorin doped and the preparation method and application thereof
CN112687870B (en) Positive electrode material precursor and preparation method thereof, and positive electrode material and application thereof
CN113582256B (en) High-nickel single crystal positive electrode material, precursor thereof and preparation method of precursor
JP2009242135A (en) Cobalt oxyhydroxide particulate powder and production method of the same
CN112694104A (en) Prussian blue analogue, preparation method thereof, negative electrode material and application
CN114477311B (en) Cobalt composite hydroxide, preparation method thereof, lithium ion battery anode material and lithium ion battery
CN114645314B (en) Preparation method of ternary positive electrode material with single crystal morphology

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant