CN115304103A - Aluminum-doped manganese carbonate and preparation method and application thereof - Google Patents

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

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CN115304103A
CN115304103A CN202211012763.9A CN202211012763A CN115304103A CN 115304103 A CN115304103 A CN 115304103A CN 202211012763 A CN202211012763 A CN 202211012763A CN 115304103 A CN115304103 A CN 115304103A
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aluminum
solution
reaction
particle size
manganese carbonate
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CN115304103B (en
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刘文泽
段小波
许开华
张坤
于杨
胡美林
陈颖
赵亚强
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Jingmen GEM New Material Co Ltd
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    • 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
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    • 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
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    • C01P2004/00—Particle morphology
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/32—Spheres
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    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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 precipitator solution into the reaction base solution in a parallel flow manner for reaction, controlling the particle size of the product in the reaction process until the reaction is complete, and washing and drying the product in sequence 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 the aluminum element is uniformly distributed in the manganese carbonate and is not easy to aggregate, the particle size 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 the 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 particularly 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 electronic products puts higher requirements on the performance of lithium ion batteries, and the characteristics of long cycle life are required while the high energy density is improved. With the rapid development of the battery industry, the lithium-rich manganese-based electrode material becomes a high-quality choice for the next generation of battery materials due to the high capacity of the electrode material. However, the lithium manganate electrode material has the problem of volume expansion in the charging and discharging processes, so that the cyclability of the battery is seriously influenced, and meanwhile, great potential safety hazards are brought to the practical application of the lithium ion battery.
CN107316990A discloses a preparation method of a coated nickel-cobalt-aluminum anode material precursor, which comprises the steps of firstly synthesizing spherical nickel-cobalt hydroxide powder with the average particle size 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 by adopting a reinforced washing mode after solid-liquid separation and ensuring the dispersibility of the residues, and fully drying to obtain the coated nickel-cobalt-aluminum anode material precursor with the average particle size D50 of 8-25 mu m and the tap density of 1.8g/cm 3 The nickel-cobalt-aluminum cathode material precursor is prepared by the method. The preparation method is simple in process flow and suitable for industrial large-scale production of the nickel-cobalt-aluminum cathode material precursor.
CN106784825A discloses a spherical nickel-containing manganese carbonate material, a preparation method and an application thereof, wherein nickel in the material mainly exists in the form of nickel carbonate, and the weight percentage of the nickel carbonate in the spherical nickel-containing manganese carbonate material is more than 0 and less than or equal to 52wt%. 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 utilizes the difference of solubility, and has the characteristics of easy operation, short time consumption and the like. The prepared spherical nickel-containing manganese carbonate material has higher conductivity, and is beneficial to the charge and discharge performance of the lithium ion battery cathode material containing nickel manganese carbonate and improves the conductivity compared with the performance of pure spherical manganese carbonate.
In the prior art, other elements are combined with the precursor material, so that the electrode material has good conductivity, but the problem of volume expansion in the charging and discharging process is not solved. The aluminum-doped manganese carbonate prepared by the preparation method can reduce the volume expansion of the electrode material in the charging and discharging processes, thereby improving the safety and the cycle performance of the battery.
Disclosure of Invention
The invention aims to provide aluminum-doped manganese carbonate and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for preparing aluminum-doped manganese carbonate, which comprises the following steps:
(1) Adding mixed salt solution, organic acid solution and precipitator solution into the reaction bottom solution in a parallel flow manner for reaction, 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 the aluminum element is uniformly distributed in the manganese carbonate and is 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 the battery are improved; and the preparation method can realize batch production.
Preferably, the complexing agent in step (1) comprises ammonia or oxalic acid.
Preferably, the dispersant of step (1) comprises polyethylene glycol and/or cetyltrimethylammonium bromide (CTAB).
Preferably, the concentration of the complexing agent in the reaction solution in step (1) is 1-3g/L, and may be, for example, 1g/L, 1.5g/L, 2g/L, 2.3g/L, 2.5g/L or 3g/L, but is not limited to the values recited, and other values not recited in the range of values are also applicable.
Preferably, the concentration of the dispersant in the reaction bottom liquid in step (1) is 0.3-0.8g/L, such as 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 values not recited in the range of values 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, the aluminum-doped manganese carbonate can be aggregated into large particles. When the concentration of the dispersant is lower than 0.3g/L, the agglomeration phenomenon of the obtained manganese carbonate is serious, and when the concentration of the dispersant 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, so that the aluminum element is favorably and uniformly distributed in the manganese carbonate, and the sphericity and the particle size distribution uniformity of the aluminum-doped manganese carbonate are favorably improved.
Preferably, the aluminum salt of step (1) comprises any one or a combination of at least two of aluminum sulfate, aluminum chloride or aluminum nitrate, and typical but non-limiting combinations include a combination of aluminum sulfate and aluminum chloride, a combination of aluminum chloride and aluminum nitrate, a combination of aluminum sulfate and aluminum nitrate, or a combination of aluminum sulfate, aluminum chloride and aluminum nitrate.
Preferably, the manganese salt in step (1) comprises any one of manganese sulfate, manganese nitrate or manganese acetate or a combination of at least two of them, and typical but non-limiting combinations include 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 the step (1) is 2-5g/L, such as 2g/L, 2.5g/L, 3g/L, 4g/L or 5g/L, but not limited to the illustrated values, and other non-illustrated values in the numerical range are also applicable.
Preferably, the mass concentration of manganese in the mixed salt solution in the step (1) is 60-150g/L, such as 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 in the value range are also 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, such as 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 numerical range are also 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, such as 210g/L, 220g/L, 230g/L, 240g/L, 250g/L or 260g/L, but not limited to the exemplified values, and other non-exemplified values in the range of values are also 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 illustrated values, and other non-illustrated values in the numerical range are also applicable.
Preferably, the flow rate of the organic acid in step (1) is 2-8L/h, such as 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h or 8L/h, but not limited to the exemplified values, and other non-exemplified values in the numerical range are also 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, 4:1, 4.5.
Preferably, the reaction temperature in step (1) is 35-45 ℃, for example 35 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃ or 45 ℃, but not limited to the exemplified values, and other non-exemplified values within 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 of the aluminum-doped manganese carbonate is not uniformly distributed, and the aggregation phenomenon is serious. Controlling the reaction temperature in the step (1) within the range of 35-45 ℃, which is favorable for the uniform distribution of aluminum element in manganese carbonate and the obtainment of aluminum-doped manganese carbonate with uniform particle size distribution and good sphericity.
Preferably, the reaction of step (1) has a pH of 7 to 9, which may be, for example, 7, 7.5, 8, 8.5 or 9, but is not limited to the exemplified values, and other values not exemplified in the range of values are equally applicable.
The present invention does not limit the specific flow rate of the precipitant solution as long as the pH during the reaction can be maintained at 7 to 9.
Preferably, the reaction of step (1) is accompanied by stirring at a speed of from 400 to 600r/min, for example 400r/min, 450r/min, 500r/min, 550r/min or 600r/min, but not limited to the exemplified values, and other values within the range of values are equally applicable.
Preferably, the particle size of the product is controlled in step (1), namely, when the particle size reaches a first particle size, the feeding is stopped and aging is carried out; and aging until the particle size reaches the second particle size, and feeding in a cocurrent manner again.
The particle size of the product in the step (1) is controlled to be between a first particle size and a second particle size in the preparation process; stopping feeding and aging when the particle size reaches a first particle size, reducing the particle size in the aging process, and feeding in a parallel flow manner again when the particle size is reduced to a second particle size; the above process is repeated until the reaction is complete.
Preferably, the temperature of the aging is from 35 to 45 ℃ and may be, for example, 35 ℃, 38 ℃, 40 ℃, 43 ℃ or 45 ℃, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the first particle diameter D50 is 4.5 to 5.5. Mu.m, for example 4.5. Mu.m, 4.6. Mu.m, 4.8. Mu.m, 4.9. Mu.m, 5. Mu.m, 5.1. Mu.m, 5.2. Mu.m, 5.4. Mu.m or 5.5. Mu.m, but is not limited to the values cited, and other values not listed in the range of values are equally suitable.
Preferably, the aging time is from 1 to 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 values not recited within the range of values are equally applicable.
Preferably, the washing in step (2) is performed by using hot water at 50-80 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the temperature of the drying in step (2) is 50-120 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferable technical solution of the preparation method of the first aspect of the present invention, the preparation method comprises the steps of:
(1) Under the conditions that the reaction temperature is 35-45 ℃ and the stirring speed is 400-600r/min, the mixed salt solution, the oxalic acid solution with the concentration of 70-100g/L and the ammonium bicarbonate solution with the concentration of 210-260g/L are added into the reaction base solution in a parallel flow manner for reaction, and the particle size of the product is controlled in the reaction process until the reaction is complete;
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 to maintain the pH value in the reaction process to be 7-9;
controlling the particle size of the product refers to stopping feeding and aging at 35-45 ℃ when the particle size reaches a first particle size; aging for 1-2h until the particle size reaches a second particle size, and feeding in a parallel flow manner again; the first particle size D50 is 4.5-5.5 μm;
(2) Washing the product obtained in the step (1) with hot water at 50-80 ℃ and drying at 50-120 ℃ in sequence 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 trimethyl ammonium bromide.
In a second aspect, the invention provides an aluminum-doped manganese carbonate obtained by the preparation method of the first aspect.
In a third aspect, the invention provides a lithium ion battery comprising the aluminum-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 the aluminum element is uniformly distributed in the manganese carbonate and is not easy to aggregate, and the obtained aluminum-doped manganese carbonate has uniform particle size distribution and good sphericity, thereby improving the structural stability of the manganese-rich lithium-based electrode material, reducing the volume expansion in the charging and discharging processes, and improving the service life and the safety of the battery; 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 the aluminum-doped manganese carbonate obtained in example 1;
FIG. 1d is the Al distribution of the Al-doped manganese carbonate obtained in example 1;
FIG. 2 is an SEM image of aluminum-doped manganese carbonate obtained in example 4;
FIG. 3 is an SEM image of aluminum-doped manganese carbonate obtained in example 10;
FIG. 4 is an SEM image of 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 solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
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 speed is 550r/min, the mixed salt solution, the oxalic acid solution with the concentration of 90g/L and the ammonium bicarbonate solution with the concentration of 220g/L are added into the reaction base solution in a parallel flow manner for reaction, and the particle size of the product is controlled in the reaction process until the reaction is complete;
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 to maintain the pH value in the reaction process to be 7.3;
the particle size of the product is controlled by stopping feeding and aging at 40 ℃ when the particle size reaches 5 mu m; aging for 1.5h, and feeding in a cocurrent manner again;
(2) Washing the product obtained in the step (1) with hot water at 75 ℃ and drying the product at 80 ℃ in sequence 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.
The XRD pattern of the obtained manganese carbonate doped with aluminum in this example is shown in fig. 1a, and it can be seen from fig. 1a that the final product obtained in this example is manganese carbonate doped with aluminum;
the SEM images of the aluminum-doped manganese carbonate obtained in this example are shown in fig. 1b and 1c, and it can be seen from fig. 1b and 1c that the sphericity of the aluminum-doped manganese carbonate obtained in this example is good;
the distribution diagram of the aluminum element in the aluminum-doped manganese carbonate obtained in this embodiment is shown in fig. 1d, and it can be seen from fig. 1d that the aluminum element in the aluminum-doped manganese carbonate obtained in this embodiment is uniformly distributed.
Example 2
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 35 ℃ and the stirring speed is 600r/min, the mixed salt solution, the oxalic acid solution with the concentration of 70g/L and the ammonium bicarbonate solution with the concentration of 210g/L are added into the reaction base solution in a parallel flow manner for reaction, and the particle size of the product is controlled in the reaction process until the reaction is complete;
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 to maintain the pH value of 9 in the reaction process;
the particle size of the product is controlled by stopping feeding and aging at 35 ℃ when the particle size reaches 5.5 mu m; aging for 2h, and feeding in a cocurrent manner again;
(2) Washing the product obtained in the step (1) with hot water at 80 ℃ and drying the product at 120 ℃ in sequence 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) Under the conditions that the reaction temperature is 45 ℃ and the stirring speed is 400r/min, the mixed salt solution, the oxalic acid solution with the concentration of 100g/L and the ammonium bicarbonate solution with the concentration of 260g/L are added into the reaction base solution in a parallel flow manner for reaction, and the particle size of the product is controlled in the reaction process until the reaction is complete;
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 to maintain the pH value in the reaction process to be 7;
the particle size of the product is controlled by stopping feeding and aging at 45 ℃ when the particle size reaches 4.5 mu m; aging for 1h, and feeding in a cocurrent manner again;
(2) Washing the product obtained in the step (1) with hot water at 50 ℃ and drying at 50 ℃ in sequence 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
This example provides a method for preparing aluminum-doped manganese carbonate, which is the same as in example 1 except that in the reaction bottom solution in step (1), oxalic acid serving as a complexing agent is replaced with ammonia water serving as an equal mass of the complexing agent.
Fig. 2 shows a microscope picture of the aluminum-doped manganese carbonate obtained in this example, and it can be seen from fig. 2 that after the complexing agent oxalic acid is replaced by ammonia water, the manganese carbonate is seriously agglomerated, and the effect of the complexing agent selected from ammonia water is inferior to that of oxalic acid.
Example 5
This example provides a method for preparing aluminum-doped manganese carbonate, which is the same as in example 1, except that cetyltrimethylammonium bromide, a dispersant, is replaced with polyethylene glycol, which is an equal mass dispersant, in the reaction base solution in step (1).
Example 6
This example provides a method for preparing aluminum-doped manganese carbonate, which is the same as in example 1 except that the concentration of oxalic acid as a complexing agent in the reaction bottom solution in step (1) is 0.7 g/L.
Example 7
This example provides a method for preparing aluminum-doped manganese carbonate, which is the same as in example 1 except that the concentration of oxalic acid as a complexing agent in the reaction bottom solution in 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 cetyltrimethylammonium bromide as a dispersant in the reaction bottom liquid 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 reaction bottom solution in step (1) contains cetyltrimethylammonium bromide as a dispersant in a concentration of 1 g/L.
Example 10
This example provides a method 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 can be seen from fig. 3 that the reaction temperature is lowered to 30 ℃, most of the generated manganese carbonate particles are square blocks, and the sphericity is poor.
Example 11
This example provides a method 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 reaction temperature is raised to 50 ℃ and the manganese carbonate is seriously agglomerated.
Comparative example 1
The comparative example provides a preparation method of aluminum-doped manganese carbonate, and the method is the same as the method in the example 1 except that the complexing agent in the reaction bottom liquid in the step (1) is replaced by the dispersing agent in quality.
Namely, the reaction base solution in step (1) of this comparative example contained only a 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 method is the same as the method in the example 1 except that the dispersant in the reaction base solution in the step (1) is replaced by the complexing agent in terms of mass.
Namely, the reaction base solution in the step (1) of the comparative example only comprises the complexing agent, and the concentration of the complexing agent is 2.8g/L.
Comparative example 3
The comparative example provides a preparation method of aluminum-doped manganese carbonate, which is the same as the example 1 except that the reaction base solution in the step (1) is pure water.
The SEM images of the aluminum-doped manganese carbonate obtained in this comparative example are shown in fig. 5a and 5b, and it is understood from fig. 5a and 5b that the sphericity of the synthesized aluminum-doped manganese carbonate is poor, the primary crystal form is coarse, and Al segregation is present on the surface when the complexing agent and the dispersing agent are not added to the reaction bottom liquid.
Comparative example 4
This comparative example provides a process for the preparation of aluminium-doped manganese carbonate, which is the same as that of example 1, except that 15g/L of manganese sulphate solution is added to the reaction base solution in step (1).
The SEM images of the aluminum-doped manganese carbonate obtained in this comparative example are shown in fig. 6a and 6b, and it can be seen from fig. 6a and 6b that the aluminum-doped manganese carbonate is agglomerated in a large amount when the base solution is changed to a manganese sulfate solution.
Comparative example 5
This comparative example provides a process for the preparation of aluminum-doped manganese carbonate, which is the same as example 1 except that no organic acid solution is added in step (1).
Performance testing
The particle size distribution and sphericity of the aluminum-doped aluminum carbonate 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 Euramerican k laser particle sizer and calculating a D50/D90 value; sphericity was tested using SEM. The results obtained are shown in table 1.
TABLE 1
Figure BDA0003811230660000121
Figure BDA0003811230660000131
As can be seen from Table 1, the aluminum-doped manganese carbonate obtained in examples 1 to 3 of the present invention has a particle size D50 of 4.9 to 5.1. Mu.m, a particle size D90 of 7.8 to 8.6. Mu.m, and a D50/D90 ratio of 58.76% or more, and has a uniform particle size distribution; and the sphericity of the obtained aluminum-doped manganese carbonate is good.
As can be seen from the comparison of example 4 with example 1, when the complexing agent is ammonia, 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, the oxalic acid is selected as the complexing agent, which is favorable for obtaining the aluminum-doped manganese carbonate with uniform particle size distribution.
From the comparison between example 5 and example 1, it is understood that when the dispersant cetyltrimethylammonium bromide is replaced with polyethylene glycol, the particle size of the obtained aluminum-doped manganese carbonate is increased and the sphericity is good. Therefore, cetyl trimethyl ammonium bromide is selected as the dispersing agent, which is beneficial to obtaining the aluminum-doped manganese carbonate with uniform particle size distribution and smaller particle size.
As can be seen from the comparison between examples 6 and 7 and 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, the aluminum-doped manganese carbonate can generate large particle aggregation, and the particle sizes D50 and D90 are increased.
As can be seen from the comparison of examples 8 and 9 with example 1, when the concentration of the dispersant is less 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 dispersant in the reaction base solution is higher than 0.8g/L, the particle sizes D50 and D90 of the aluminum-doped manganese carbonate are both 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, so that the aluminum element is favorably and uniformly distributed in the manganese carbonate, and the sphericity and the particle size distribution uniformity of the aluminum-doped manganese carbonate are favorably improved.
From the comparison of examples 10 and 11 with example 1, it can be seen that when the reaction temperature is lower than 35 ℃, the particle size distribution of the obtained aluminum-doped manganese carbonate is uniform, and the D50/D90 can reach 63.25%, but most of the generated aluminum-doped manganese carbonate particles are in a square block shape 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, so that the sphericity cannot be measured. Therefore, the reaction temperature is controlled to be 35-45 ℃, which is beneficial to obtaining the aluminum-doped manganese carbonate with uniform particle size distribution and good sphericity.
As can be seen from comparison of comparative example 1 with example 1, when only the dispersant was added to the reaction bottoms, an effective amount of manganese carbonate pellets could not be formed; as can be seen from comparison of comparative example 2 with example 1, when only the complexing agent is added to the reaction base solution, the obtained aluminum-doped manganese carbonate large particles aggregate, the particle size distribution is uneven and the sphericity is poor; as is clear from comparison of comparative examples 3 and 4 with example 1, when the reaction bottom liquid composition was changed, it was not favorable to obtain the aluminum-doped manganese carbonate having a uniform particle size distribution and a good sphericity. Therefore, the reaction base solution simultaneously comprises the complexing agent and the dispersing agent, which is favorable for forming the aluminum-doped manganese carbonate with uniform particle size distribution and good sphericity.
As can be seen from comparison between comparative example 5 and example 1, the sphericity of the obtained aluminum-doped manganese carbonate is poor if no organic acid is added; the oxalic acid is used as organic acid to prepare the aluminum-doped manganese carbonate, which is beneficial to obtaining the aluminum-doped manganese carbonate with uniform particle size distribution and good sphericity.
In conclusion, in the preparation method of the aluminum-doped manganese carbonate, the complexing agent and the dispersing agent are added into the reaction base solution, so that the aluminum element is uniformly distributed in the manganese carbonate and is not easy to aggregate, the particle size of the obtained manganese carbonate is uniformly distributed, the sphericity is good, the structural stability of the manganese-rich lithium-based electrode material is 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 above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.

Claims (10)

1. The preparation method of the aluminum-doped manganese carbonate is characterized by comprising the following steps:
(1) Adding mixed salt solution, organic acid solution and precipitator solution into the reaction bottom solution in a parallel flow manner for reaction, 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.
2. The production method according to claim 1, wherein the complexing agent comprises ammonia water or oxalic acid;
preferably, the dispersant comprises polyethylene glycol and/or cetyltrimethylammonium bromide.
3. The production method according to claim 1 or 2, characterized in that the concentration of the complexing agent in the reaction base solution in the step (1) is 1 to 3g/L;
preferably, the concentration of the dispersant in the reaction bottom liquid in the step (1) is 0.3-0.8g/L.
4. The production method according to any one of claims 1 to 3, wherein the aluminum salt comprises any one of aluminum sulfate, aluminum chloride, or aluminum nitrate, or a combination of at least two thereof;
preferably, the manganese salt comprises any one of manganese sulfate, manganese nitrate or manganese acetate or a combination of at least two of the same;
preferably, the mass concentration of aluminum in the mixed salt solution in the step (1) is 2-5g/L;
preferably, the mass concentration of manganese in the mixed salt solution in the step (1) is 60-150g/L.
5. The production method according to any one of claims 1 to 4, wherein the organic acid in the organic acid solution of step (1) comprises oxalic acid;
preferably, the concentration of the organic acid solution in the step (1) is 70-100g/L;
preferably, the precipitant in the precipitant solution of step (1) comprises ammonium bicarbonate;
preferably, the concentration of the precipitant solution of step (1) is 210-260g/L.
6. The method according to any one of claims 1 to 5, wherein the flow rate of the mixed salt solution of step (1) is 20 to 50L/h;
preferably, the flow rate of the organic acid solution in the step (1) is 2-8L/h;
preferably, the flow ratio of the mixed salt solution to the organic acid solution in the step (1) is (4-7): 1;
preferably, the temperature of the reaction of step (1) is 35-45 ℃;
preferably, the reaction of step (1) has a pH of 7 to 9;
preferably, the reaction in the step (1) is accompanied by stirring, and the stirring speed is 400-600r/min.
7. The method according to any one of claims 1 to 6, wherein the controlling of the particle size of the product in the step (1) means that the feeding is stopped and aged when the particle size reaches the first particle size; aging until the particle size reaches a second particle size, and feeding in a parallel flow mode again;
preferably, the temperature of aging is 35-45 ℃;
preferably, the first particle diameter D50 is 4.5 to 5.5 μm;
preferably, the aging time is 1-2h;
preferably, the washing in the step (2) is washing by using hot water at 50-80 ℃;
preferably, the temperature for drying in the step (2) is 50-120 ℃.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) Under the conditions that the reaction temperature is 35-45 ℃ and the stirring speed is 400-600r/min, the mixed salt solution, the oxalic acid solution with the concentration of 70-100g/L and the ammonium bicarbonate solution with the concentration of 210-260g/L are added into the reaction base solution in a parallel flow manner for reaction, and the particle size of the product is controlled in the reaction process until the reaction is complete;
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 to maintain the pH value in the reaction process to be 7-9;
controlling the particle size of the product refers to stopping feeding and aging at 35-45 ℃ when the particle size reaches a first particle size; aging for 1-2h until the particle size reaches a second particle size, and feeding in a parallel flow manner again; the first particle diameter D50 is 4.5-5.5 μm;
(2) Washing the product obtained in the step (1) with hot water at 50-80 ℃ and drying at 50-120 ℃ in sequence 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 trimethyl ammonium bromide.
9. An aluminum-doped manganese carbonate, characterized in that it is obtained by the process according to any one of claims 1 to 8.
10. A lithium ion battery comprising the aluminum-doped manganese carbonate of claim 9.
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