CN115676893A - Composite manganese source for lithium manganate, preparation method of composite manganese source, lithium manganate and application of composite manganese source - Google Patents
Composite manganese source for lithium manganate, preparation method of composite manganese source, lithium manganate and application of composite manganese source Download PDFInfo
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Abstract
The invention provides a composite manganese source for lithium manganate, a preparation method thereof, lithium manganate and application. The preparation method comprises the following steps: crushing and grading metal manganese powder, adding the graded metal manganese powder into an ammonium salt solution, adding manganese dioxide, introducing air, stirring, reacting for a period of time, and filtering to obtain a reaction product; and step two, washing, drying, roasting and sieving the reaction product obtained in the step one to obtain the composite manganese source for the lithium manganate. When the composite manganese source for lithium manganate prepared by the preparation method is applied to the synthesis of lithium manganate by a high-temperature solid phase method, the degree of lattice oxygen defects of lithium manganate can be effectively reduced, and the product performance and consistency are improved; meanwhile, the amount of air blown into a kiln when the lithium manganate is synthesized by the composite manganese source high-temperature solid-phase method for the lithium manganate can be reduced, and the pot loading amount of a single pot is increased.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a composite manganese source for lithium manganate, a preparation method of the composite manganese source, lithium manganate and application of the composite manganese source.
Background
Lithium manganate (LiMn) 2 O 4 ) The lithium battery cathode material has gradually occupied the use situation of a low-cost general battery in the lithium battery cathode material by using a cheap process, a simple manganese source, good use cost performance, good environmental protection and safety performance.
Although lithium manganate (LiMn) is industrially produced at present in China 2 O 4 ) Electrolytic Manganese Dioxide (EMD) has been the primary technique, however, studies have shown that manganomanganic oxide (Mn) is used 3 O 4 ) Compared with the method for synthesizing the lithium manganate by taking EMD as a manganese source, the method for preparing the lithium manganate by replacing EMD has obvious advantages. The electrical property of the lithium manganate synthesized by adopting the manganous-manganic oxide as the manganese source is obviously improved in the aspects of capacity, multiplying power, cycle life and other electrical properties compared with the lithium manganate synthesized by adopting EMD as the manganese source.
However, the synthesis of lithium manganate by using trimanganese tetroxide as manganese source is an aerobic reaction, and the reaction equation is as follows: 8Mn 3 O 4 +5O 2 +6Li 2 CO 3 ＝12LiMn 2 O 4 +6CO 2 The process of sintering manganous manganic oxide into lithium manganate must be oxygen-rich atmosphere, and if the process still refers to manganese dioxide sintering lithium manganate (oxygen release reaction), the manganese dioxide sintering lithium manganate is supplied afterwardsThe continuous sieving causes great difficulty and the oxygen defect is serious. Therefore, in the process of synthesizing lithium manganate by industrial trimanganese tetroxide at present, a large amount of air needs to be blown in during sintering, the charging amount of a single box pot is much less than that of synthesizing lithium manganate by manganese dioxide, the total sintering amount of a sintering section in unit time is reduced, the heat dissipation of a kiln during sintering is increased, even if oxygen cannot smoothly permeate to the bottom material to participate in reaction under the condition of introducing a large amount of air, thus the oxidation of the bottom material is incomplete, the defect of lithium manganate lattice oxygen is shown in microcosmic, the hardness of a product after sintering is shown in macroscopic view, a powerful crushing process needs to be added for sieving, the difference of the upper layer and the lower layer of the single pot is obviously poor in consistency, and the electrical property is also influenced.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a composite manganese source for lithium manganate, a preparation method thereof, lithium manganate and application, and aims to solve the problem of incomplete oxidation in the process of synthesizing lithium manganate by using industrial trimanganese tetroxide at present.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a composite manganese source for lithium manganate comprises the following steps:
crushing and grading metal manganese powder, adding the graded metal manganese powder into an ammonium salt solution, adding manganese dioxide, introducing air, stirring, reacting for a period of time, and filtering to obtain a reaction product;
and step two, washing, drying, roasting and sieving the reaction product obtained in the step one to obtain the composite manganese source for the lithium manganate.
Optionally, in the first step, the addition amount of the manganese dioxide is 5-30% of the mass of the manganese metal powder.
Optionally, in the first step, the manganese dioxide is one or more of electrolytic manganese dioxide, unsintered dust collection materials in the lithium manganate production process, manganese dioxide obtained after lithium is extracted from lithium manganate waste, and airflow classification fine powder of electrolytic manganese dioxide;
the volume median particle diameter D50 of the manganese dioxide is 3-15 mu m.
Optionally, in the first step, the manganese content in the manganese metal powder is greater than 99.5%, and the particle size range of the crushed and classified manganese metal powder is 5-200 μm.
Optionally, in the first step, the concentration of the ammonium salt solution is 4-20g/L;
the ammonium salt in the ammonium salt solution is one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
Optionally, in the step one, the air is introduced at a rate of 40-120m 3 /h；
In the first step, the stirring speed is 100-500r/min, the reaction temperature is room temperature, and the reaction time is 16-30h.
Optionally, in the second step, the roasting specifically is: the reaction product is roasted in air atmosphere at 500-580 deg.c for 2-5 hr.
The invention also provides a composite manganese source for lithium manganate prepared by the preparation method of the composite manganese source for lithium manganate, wherein the composite manganese source for lithium manganate is manganese dioxide-manganic oxide composite particles, the surface layer is manganous-manganic oxide, and the inner layer is manganese dioxide;
the particle size range of the composite manganese source for lithium manganate is 1.5-40 mu m, and the volume median particle size D50 is 5-15 mu m.
The invention also provides lithium manganate which is synthesized by the composite manganese source for the lithium manganate and a lithium compound.
The invention also provides an application of the lithium manganate, and the lithium manganate is applied to preparation of a lithium ion battery anode material.
Has the advantages that:
the preparation method of the composite manganese source for the lithium manganate comprises the steps of taking metal manganese powder as a raw material to synthesize manganese tetraoxide as a main reaction, enabling the metal manganese powder to generate a new substance of manganese hydroxide in an aqueous solution of ammonium salt under the catalysis of the ammonium salt, enabling a large amount of manganese hydroxide to wrap the surface of manganese dioxide and react with oxygen in air to generate manganous manganic oxide to obtain composite particles with a surface layer of the manganous manganic oxide and an inner layer of the manganese dioxide, namely the composite manganese source for the lithium manganate, pre-sintering the composite manganese source for the lithium manganate through a roasting process to improve oxygen defects of the manganese dioxide and the manganous manganic oxide, and shortening the heat-preservation sintering time of the synthesized lithium manganate.
The inner layer of the composite manganese source for lithium manganate prepared by the method is manganese dioxide, and oxygen is discharged in the process of generating the lithium manganate through the high-temperature sintering reaction of the manganese dioxide and a lithium compound (such as lithium carbonate), so that the composite manganese source can discharge part of oxygen from the inside to the outside of particles in the sintering process. Meanwhile, the amount of air blown into the kiln when the lithium manganate is synthesized by the composite manganese source high-temperature solid phase method can be reduced, and the pot loading amount of a single pot is increased.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Wherein:
fig. 1 is a schematic diagram of charging and discharging curves of a buckle 1C of the composite manganese source products obtained in examples 1-6 and comparative examples 1-3 of the present invention, applied to the manufacture of a button cell.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
Aiming at the problem of incomplete oxidation in the process of synthesizing lithium manganate by industrial trimanganese tetroxide at present, the invention provides a preparation method of a composite manganese source for lithium manganate, which comprises the following steps:
step one, crushing and grading metal manganese powder, adding the graded metal manganese powder into an ammonium salt solution, simultaneously adding manganese dioxide, introducing air, stirring, reacting for a period of time, and filtering to obtain a reaction product.
In the specific embodiment of the invention, the metal manganese powder is crushed by adopting dry crushing equipment, wherein the dry crushing equipment is one or more of a double-roller mill, a ball mill, a mechanical crusher and a jet mill.
In the specific embodiment of the invention, the crushed manganese metal powder particles are classified and sieved by using classification equipment, and the manganese metal powder with the particle diameter larger than 200um is separated, wherein the classification equipment is one or more of a vibrating screen, a swing screen and an airflow classifier.
In one embodiment of the present invention, the amount of manganese dioxide added is 5-30% by mass (e.g., 5%, 10%, 15%, 20%, 25%, 30% and any interval therebetween) of the manganese metal powder. The manganese dioxide with the dosage can improve the condition of low oxygen utilization efficiency in the sintering process, solve the problem that the lithium manganate sintered by pure manganous manganic oxide is abnormally hard and needs to be broken by strength, and enlarge the application range of sintering temperature, so that the industrial continuous sintering is easier and more stable. Electrolytic manganese dioxide with D50 less than or equal to 5um is preferably used.
Preferably, the addition amount of manganese dioxide is 10-30% of the mass of the manganese metal powder.
Optionally, the manganese dioxide is one or more of electrolytic manganese dioxide, unsintered dust collection materials in the lithium manganate production process, manganese dioxide obtained after lithium is extracted from lithium manganate waste, and airflow-graded fine powder of electrolytic manganese dioxide.
Optionally, the volume median particle diameter D50 of the manganese dioxide is 3-15 μm (e.g., 3 μm, 5 μm, 7 μm, 9 μm, 11 μm, 15 μm and the interval between any two endpoints), and the manganese dioxide particles with the volume median particle diameter in the above range are selected to match the volume median particle diameter of the target trimanganese tetroxide of 5um, 7um, 11um, so as to prevent the particle size distribution from showing double peaks and affecting the compact density of the composite manganese.
In the first step, the manganese content in the metal manganese powder is more than 99.5%, the iron content is less than 0.05%, the particle size range of the crushed and classified metal manganese powder is 5-200 μm (such as 5 μm, 30 μm, 48 μm, 60 μm, 100 μm, 150 μm, 200 μm and the interval value between any two end values), and the metal manganese powder with different particle size ranges is selected, so that the reaction speed can be well controlled; if the particle size is smaller, the reaction between the metal manganese powder and the solution is too violent, and if the particle size is larger, the specific surface area is small, the contact area between the metal manganese powder and the solution is small, and the reaction efficiency is low.
In the invention, the ammonium salt solution is a solution of ammonium salt and pure water, the concentration of the ammonium salt solution is 4-20g/L (such as 4g/L, 6g/L, 8g/L, 10g/L, 12g/L, 14g/L, 16g/L, 18g/L, 20g/L and the interval value between any two end values), and the ammonium salt solution with the concentration range is selected, so that the hydrolysis and agglomeration speed of manganese powder in water can be well controlled; if the concentration is small, the hydrolysis efficiency is low, meanwhile, the oxidation efficiency is high, the agglomeration is poor, and if the concentration is large, the hydrolysis efficiency is high, and the oxidation efficiency is too high; preferably, the concentration of the ammonium salt solution is 10g/L.
Optionally, the ammonium salt in the ammonium salt solution is one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
In the embodiment of the invention, in the step one, the air is introduced at a speed of 40-120m 3 H (e.g. 40 m) 3 /h、60m 3 /h、80m 3 /h、100m 3 /h、120m 3 The interval value between the values of/h and any two end points), the air with the above-mentioned introduction rate range is selected, the concentration of the manganese hydroxide in the water can be well controlled to be close to stable; if the air introducing rate is low, the manganese hydroxide concentration is gradually increased, the oxidation of the product is incomplete, and if the air introducing rate is high, the manganese hydroxide concentration is always in a low level and is over-oxidized.
In the first step, the stirring speed is 100-500r/min (100 r/min, 200r/min, 300r/min, 400r/min, 500r/min and any interval value between two end values), the reaction temperature is room temperature, and the reaction time is 16-30h (such as 16h, 18h, 20h, 24h, 28h, 30h and any interval value between two end values).
The preparation method of the composite manganese source for lithium manganate can be understood as that the metal manganese powder is used as a raw material to synthesize manganese tetraoxide as a main reaction, the metal manganese powder is in an aqueous solution of ammonium salt and generates a new substance of manganese hydroxide under the catalysis of the ammonium salt, a large amount of manganese hydroxide can be coated on the surface of manganese dioxide and reacts with oxygen in air to generate manganous manganic oxide, so as to obtain composite particles with a surface layer of manganous manganic oxide and an inner layer of manganese dioxide, namely the composite manganese source for lithium manganate, and then the composite manganese source for lithium manganate is pre-sintered by a roasting process to improve oxygen defects of manganese dioxide and manganous manganic oxide and shorten the heat-preservation sintering time of the synthesized lithium manganate.
And step two, washing, drying, roasting and sieving the reaction product obtained in the step one to obtain the composite manganese source for lithium manganate.
In the specific embodiment of the invention, the washing operation adopts pure water with the temperature of 70 ℃ to wash the reaction product, and the washing times are three times; the drying temperature was 120 ℃ and the drying time was 4 hours.
In the second step, the roasting specifically comprises the following steps: the reaction product is calcined in an air atmosphere at 500-580 deg.C (e.g., 500 deg.C, 520 deg.C, 540 deg.C, 560 deg.C, 580 deg.C, and any interval therebetween) for 2-5 hours (e.g., 2 hours, 3 hours, 4 hours, 5 hours, and any interval therebetween). By adopting the roasting temperature range, the effect of pre-complete oxidation on the composite manganese can be achieved, and if the roasting temperature is lower than 450 ℃, the oxidation effect cannot be achieved; if the calcination temperature is higher than 580 deg.C, the product will be over oxidized.
The invention also provides the composite manganese source for lithium manganate prepared by the preparation method.
The composite manganese source for the lithium manganate prepared by the method is manganese dioxide-manganese tetraoxide composite particles, the surface layer is manganous-manganic oxide, and the inner layer is manganese dioxide; the composite manganese source for lithium manganate has a particle diameter in the range of 1.5 to 40 μm (e.g., 1.5 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm and any interval therebetween), and a volume median particle diameter D50 in the range of 5 to 15 μm (e.g., 5 μm, 7 μm, 9 μm, 12 μm, 15 μm and any interval therebetween). The composite manganese source for lithium manganate prepared by the method has the advantages that the inner layer is manganese dioxide, and oxygen is discharged in the process of generating lithium manganate through the high-temperature sintering reaction of manganese dioxide and a lithium compound (such as lithium carbonate), so that the composite manganese source can have a part of oxygen discharged from particles to the inside and the outside of the particles in the sintering process. Meanwhile, the amount of air blown into a kiln when the lithium manganate is synthesized by the composite manganese source high-temperature solid-phase method for the lithium manganate can be reduced, and the pot loading amount of a single pot is increased.
The invention also provides lithium manganate which is synthesized by the composite manganese source for the lithium manganate and a lithium compound.
Alternatively, the lithium compound may be a lithium salt of lithium manganate synthesized with manganous manganic oxide, and is preferably one or more of lithium carbonate and lithium hydroxide.
The invention also provides an application of the lithium manganate, wherein the lithium manganate is applied to preparing the lithium ion battery anode material.
The composite manganese source for lithium manganate, the preparation method thereof, lithium manganate and the application thereof of the present invention are described in detail by the following specific examples.
Example 1
The embodiment provides a preparation method of a composite manganese source for lithium manganate, which comprises the following steps:
(1) Crushing the manganese metal sheet by a roller mill and a ball mill until the median particle size is 120 mu m, removing manganese metal powder with the particle size of more than 200 mu m after screening by a vibrating screen, and gradually adding 1500kg of the manganese metal powder into the manganese metal sheet until the manganese metal powder contains 7.5m 3 Adding manganese powder and manganese dioxide (D50 is less than or equal to 11 mu m) accounting for 10 percent of the mass of the metal manganese powder into a reactor of pure water and 75kg of ammonium chloride, introducing air for oxidation, and controlling the air flow to be 48m 3 H, stirring speed controlAfter reacting at room temperature for 24h at 500r/min, positive pressure filtration and washing (Cl) - Content (c) of<300 ppm) and drying to obtain the manganese dioxide/manganomanganic oxide composite manganese source particles.
(2) And (2) roasting the manganese dioxide/manganic manganous oxide composite manganese source obtained in the step (1) at 550 ℃ in an air atmosphere for 2h until the reaction is finished, and obtaining a manganese dioxide/manganic manganous oxide composite manganese source product with a pretreated inner core of manganese dioxide and a surface layer of manganic manganous oxide.
The composite trimanganese tetroxide product prepared in the example was tested for median particle size and found to be 10.65 μm.
The manganese dioxide/manganomanganic oxide composite manganese source product prepared in the example and lithium carbonate are fully mixed according to the molar ratio of Li/Mn =0.53 and then are filled into a pot, the thickness of the pot is 2.5cm/3.5cm/4.5cm, the temperature is 700 ℃, and the air flow is 4.8m 3 Calcining for 12 hours under the condition of/h to obtain the lithium manganate product.
Table 1 shows the sensory hardness of the lithium manganate product obtained by sintering the composite manganese source mixed lithium source in this example under different container thicknesses, and the charging and discharging conditions of button batteries made of the lithium manganate product.
TABLE 1 Properties of lithium manganate product obtained in example 1 at different pot thicknesses
As can be seen from the performance data in table 1 and fig. 1, when the composite manganese source mixed lithium source is sintered at 700 ℃, the larger the thickness of the container is, the higher the apparent hardness of the sintered lithium manganate is, only when the lithium manganate is loaded into a pot by 2.5cm, easily smash and detain electric 1C charge-discharge curve and change gently.
Example 2
The embodiment provides a preparation method of a composite manganese source for lithium manganate, which comprises the following steps:
(1) Crushing the manganese metal sheet by a double-roller machine until the median particle size is 75 mu m, removing the manganese metal powder with the particle size of more than 120 mu m after screening by a vibrating screen, and gradually adding 1500kg of the manganese metal powder until the manganese metal powder contains 7.5m 3 Pure water and 75kg of chlorineAdding manganese powder into an ammonium reactor, simultaneously adding manganese dioxide (D50 is less than or equal to 11 mu m) accounting for 10 percent of the mass of the metal manganese powder, introducing air for oxidation, and controlling the air flow to be 60m 3 Stirring at 300r/min for 20 hr, filtering under positive pressure, and washing (Cl) - Content (c) of<300 ppm) and drying to obtain the manganese dioxide/manganomanganic oxide composite manganese source particles.
(2) And (2) roasting the manganese dioxide/manganic manganous oxide composite manganese source obtained in the step (1) at 500 ℃ in an air atmosphere for 4 hours until the reaction is finished, and obtaining a manganese dioxide/manganic manganous oxide composite manganese source product with a pretreated inner core of manganese dioxide and a surface layer of manganic manganous oxide.
The composite trimanganese tetroxide product prepared in the example is tested for median particle size, and the test result is 7.38 μm.
The manganese dioxide/manganomanganic oxide composite manganese source product prepared in the example and lithium carbonate are fully mixed according to the molar ratio of Li/Mn =0.53 and then are loaded into a pot, the thickness of the pot is 2.5cm/3.5cm/4.5cm, and the air flow is 4m at 700 DEG C 3 Calcining for 12 hours under the condition of/h to obtain the lithium manganate product.
Table 2 shows the sensory hardness of the lithium manganate product obtained by sintering the composite manganese source mixed lithium source in this example under different container thicknesses, and the charging and discharging conditions of the button cell made of the lithium manganate product.
TABLE 2 Properties of lithium manganate product obtained in example 2 at different pot thicknesses
Example 3
The embodiment provides a preparation method of a composite manganese source for lithium manganate, which comprises the following steps:
(1) Crushing the manganese metal sheet by using a double-roller machine until the median particle size is 48 mu m, removing manganese metal powder with the particle size of more than 100 mu m after screening by using a vibrating screen, and gradually adding 1500kg of the manganese metal powder into the powder until the manganese metal powder contains 7.5m 3 Adding manganese powder and manganese dioxide (D50 is less than or equal to 6 mu m) accounting for 20 percent of the mass of the metal manganese powder into a reactor of pure water and 45kg of ammonium chloride, and introducing airGas oxidation with a gas flow rate of 45m 3 Stirring at 300r/min, reacting at room temperature for 20h, filtering under positive pressure, and washing (Cl) - Content (wt.)<300 ppm) and drying to obtain the manganese dioxide/manganomanganic oxide composite manganese source particles.
(2) And (2) roasting the manganese dioxide/manganomanganic oxide composite manganese source obtained in the step (1) at 550 ℃ in an air atmosphere for 6 hours until the reaction is finished, thus obtaining a manganese dioxide/manganomanganic oxide composite manganese source product with manganese dioxide as an inner core and manganomanganic oxide as a surface layer.
The composite trimanganese tetroxide product prepared in the example is tested for median particle size, and the test result is 7.38 μm.
The manganese dioxide/manganomanganic oxide composite manganese source product prepared in the example and lithium carbonate are fully mixed according to the molar ratio of Li/Mn =0.53 and then are loaded into a pot, the thickness of the pot is 2.5cm/3.5cm/4.5cm, and the air flow is 4m at 700 DEG C 3 Calcining for 12 hours under the condition of/h to obtain the lithium manganate product.
Table 3 shows the sensory hardness of the lithium manganate product obtained by sintering the composite manganese source mixed lithium source in this example under different container thicknesses, and the charging and discharging conditions of the button cell made of the lithium manganate product.
TABLE 3 Properties of lithium manganate product obtained in example 3 at various pot thicknesses
Example 4
The embodiment provides a preparation method of a composite manganese source for lithium manganate, which comprises the following steps:
(1) Crushing the manganese metal sheet by using a double-roller machine until the median particle size is 48 mu m, removing manganese metal powder with the particle size of more than 100 mu m after screening by using a vibrating screen, and gradually adding 1500kg of the manganese metal powder into the powder until the manganese metal powder contains 7.5m 3 Adding manganese powder and manganese dioxide (D50 is less than or equal to 6 mu m) accounting for 20 percent of the mass of the metal manganese powder into a reactor of pure water and 75kg of ammonium chloride, introducing air for oxidation, and controlling the air flow to be 60m 3 Stirring at 300r/min, reacting at room temperature for 20 hr, and passing under positive pressureFiltration and washing (Cl) - Content (wt.)<300 ppm) and drying to obtain the manganese dioxide/manganomanganic oxide composite manganese source particles.
(2) And (2) roasting the manganese dioxide/manganomanganic oxide composite manganese source obtained in the step (1) at 550 ℃ in an air atmosphere for 6 hours until the reaction is finished, thus obtaining a manganese dioxide/manganomanganic oxide composite manganese source product with manganese dioxide as an inner core and manganomanganic oxide as a surface layer.
The composite trimanganese tetroxide product prepared in the example is tested for median particle size, and the test result is 7.38 μm.
The manganese dioxide/manganous manganic oxide composite manganese source product prepared in the embodiment and lithium carbonate are fully mixed according to the molar ratio of Li/Mn =0.53, and then are filled into a pot, the thickness of the pot is 2.5cm/3.5cm/4.5cm, and the mixture is calcined for 12 hours at 700 ℃ to obtain a lithium manganate product.
Table 4 shows the sensory hardness of the lithium manganate product obtained by sintering the composite manganese source mixed lithium source in this example under different container thicknesses, and the charging and discharging conditions of the button cell made of the lithium manganate product.
TABLE 4 Properties of lithium manganate product obtained in example 4 at various pot thicknesses
Example 5
The embodiment provides a preparation method of a composite manganese source for lithium manganate, which comprises the following steps:
(1) Crushing the manganese metal sheet by a double-roller machine until the median particle size is 48 mu m, removing manganese metal powder with the particle size of more than 100 mu m after screening by a vibrating screen, and gradually adding 1500kg of the manganese metal powder until the manganese metal powder contains 7.5m 3 Adding manganese powder and manganese dioxide (D50 is less than or equal to 6 mu m) accounting for 30 percent of the mass of the metal manganese powder into a reactor of pure water and 75kg of ammonium chloride, introducing air for oxidation, and controlling the air flow to be 40m 3 H, the stirring speed is controlled at 300r/min,after 20h reaction at room temperature, positive pressure filtration and washing (Cl) - Content (c) of<300 ppm) and drying to obtain the manganese dioxide/manganomanganic oxide composite manganese source particles.
(2) And (2) roasting the manganese dioxide/manganomanganic oxide composite manganese source obtained in the step (1) at 550 ℃ in an air atmosphere for 6 hours until the reaction is finished, thus obtaining a manganese dioxide/manganomanganic oxide composite manganese source product with manganese dioxide as an inner core and manganomanganic oxide as a surface layer.
The composite trimanganese tetroxide product prepared in the example is tested for median particle size, and the test result is 7.38 μm.
And (3) fully mixing the manganese dioxide/mangano-manganic oxide composite manganese source product prepared in the embodiment with lithium carbonate according to the molar ratio of Li/Mn =0.53, then loading into a pot, wherein the pot thickness is 3.5cm/4.5cm/5.5cm, and calcining for 12 hours at 700 ℃ to obtain the lithium manganate product.
Table 5 shows the sensory hardness of the lithium manganate product obtained by sintering the composite manganese source mixed lithium source in this example under different container thicknesses, and the charging and discharging conditions of the button cell made of the lithium manganate product.
TABLE 5 Properties of lithium manganate product obtained in example 5 at various pot thicknesses
Example 6
The embodiment provides a preparation method of a composite manganese source for lithium manganate, which comprises the following steps:
(1) Crushing the manganese metal sheet by a double-roller machine until the median particle size is 60 mu m, removing manganese metal powder with the particle size of more than 100 mu m after screening by a vibrating screen, and gradually adding 1500kg of the manganese metal powder until the manganese metal powder contains 7.5m 3 Adding manganese powder and manganese dioxide (D50 is less than or equal to 6 mu m) accounting for 15 percent of the mass of the manganese metal powder into a reactor of pure water and 45kg of ammonium chloride, introducing air for oxidation, and controlling the air flow to be 40m 3 Stirring at 300r/min, reacting at room temperature for 20h, filtering under positive pressure, and washing (Cl) - Content (c) of<300 ppm) and drying to obtain the manganese dioxide/manganomanganic oxide composite manganese source particles.
(2) And (2) roasting the manganese dioxide/manganomanganic oxide composite manganese source obtained in the step (1) in an air atmosphere at 500 ℃ for 4 hours until the reaction is finished, thus obtaining a manganese dioxide/manganomanganic oxide composite manganese source product with manganese dioxide as an inner core and manganomanganic oxide as a surface layer.
The composite trimanganese tetroxide product prepared in the example was tested for median particle size and found to be 7.38 μm.
The manganese dioxide/manganomanganic oxide composite manganese source product prepared in the example and lithium carbonate are fully mixed according to the molar ratio of Li/Mn =0.53 and then are filled into a pot, the thickness of the pot is 3.5cm/4.5cm/5.5cm, and the air flow is 4m at 700 DEG C 3 Calcining for 12 hours under the condition of/h to obtain the lithium manganate product.
Table 6 shows the sensory hardness of the lithium manganate product obtained by sintering the composite manganese source mixed lithium source in this example under different container thicknesses, and the charging and discharging conditions of the button cell made of the lithium manganate product.
TABLE 6 Properties of lithium manganate product obtained in example 6 at different pot thicknesses
Comparative example 1
The comparative example provides a preparation method of manganous-manganic oxide for lithium manganate, and the preparation method comprises the following steps:
(1) Crushing the manganese metal sheet by using a double-roller machine until the median particle size is 60 mu m, removing manganese metal powder with the particle size of more than 100 mu m after screening by using a vibrating screen, and gradually adding 1500kg of manganese metal powder into the powder until the manganese metal powder contains 7.5m 3 Pure water and 75kg ammonium chloride in a reactor, and introducing air for oxidation, wherein the air flow is controlled to be 50m 3 Stirring at 300r/min, reacting at room temperature for 20h, filtering under positive pressure, and washing (Cl) - Content (wt.)<300 ppm) to obtain manganous manganic oxide particles after drying.
(2) And (2) roasting the manganous-manganic oxide obtained in the step (1) in an air atmosphere at the baking temperature of 500 ℃ for 4 hours until the reaction is finished.
The medium particle size of the trimanganese tetroxide product prepared in step (1) of the comparative example was tested, and the test result was 7.38 μm.
The manganomanganic oxide product prepared in the comparative example and lithium carbonate are fully mixed according to the mol ratio of Li/Mn =0.53 and then are filled into a pot, the thickness of the pot is 2.5cm/3.5cm/4.5cm, the air flow is 6m at 670 DEG C 3 Calcining for 12 hours under the condition of/h to obtain the lithium manganate product.
Table 7 shows the sensory hardness of the lithium manganate product obtained by sintering the composite manganese source mixed lithium source of the comparative example under different pot thicknesses and the charge-discharge conditions of the button cell prepared from the lithium manganate product.
TABLE 7 Properties of lithium manganate product obtained in comparative example 1 under different pot thicknesses
As can be seen from the performance data of comparative example 1 and Table 7, the air flow rate was increased by 25% to 6m without the addition of manganese dioxide even though the sintering temperature was 30 ℃ lower than that of each example 3 And in the/h period, the sintered lithium manganate still has high apparent hardness, can not be simply mixed and then is immediately screened into small-particle lithium manganate finished products, and the test electrification 1C prepared by sintering in various thicknesses has abnormal charge-discharge performance.
Comparative example 2
The comparative example provides a preparation method of manganous-manganic oxide for lithium manganate, and the preparation method comprises the following steps:
(1) Crushing the manganese metal sheet by using a double-roller machine until the median particle size is 60 mu m, removing manganese metal powder with the particle size of more than 100 mu m after screening by using a vibrating screen, and gradually adding 1500kg of manganese metal powder into the powder until the manganese metal powder contains 7.5m 3 Pure water and 75kg ammonium chloride in a reactor, and introducing air for oxidation, wherein the air flow is controlled to be 50m 3 Stirring at 300r/min for 20 hr, filtering under positive pressure, and washing (Cl) - Content (c) of<300 ppm) to obtain manganomanganic oxide particles after drying.
(2) And (2) roasting the manganous-manganic oxide obtained in the step (1) in an air atmosphere at 500 ℃ for 4h until the reaction is finished.
The manganous-manganic oxide product prepared in the step (1) of the comparative example is tested for the median particle size, and the test result is 7.38 mu m.
The manganomanganic oxide product prepared in the comparative example and lithium carbonate are fully mixed according to the mol ratio of Li/Mn =0.53 and are filled into a pot, the thickness of the pot is 2.5cm/3.5cm/4.5cm, the air flow is 8m at 670 DEG C 3 Calcining for 12 hours under the condition of/h to obtain the lithium manganate product.
Table 8 shows the sensory hardness of the lithium manganate product obtained by sintering the composite manganese source mixed lithium source of the comparative example under different pot thicknesses and the charge-discharge conditions of the button cell prepared from the lithium manganate product.
TABLE 8 Properties of lithium manganate product obtained in comparative example 2 under different pot thicknesses
As can be seen from the performance data of comparative example 2 and Table 8, comparative example 2 has a 30 ℃ reduction in sintering temperature and an increase in sintering air flow to 8m 3 During the sintering process, the lithium manganate is still hard after sintering, can be crushed only when the finger exerts great force, is still not convenient to screen into small-particle lithium manganate, and the test buckle electricity 1C prepared by sintering in various thicknesses has abnormal charge and discharge performance.
Comparative example 3
The comparative example provides a preparation method of manganous-manganic oxide for lithium manganate, and the preparation method comprises the following steps:
(1) Crushing the manganese metal sheet by a double-roller machine until the median particle size is 48 mu m, removing manganese metal powder with the particle size of more than 100 mu m after screening by a vibrating screen, and gradually adding 1500kg of the manganese metal powder until the manganese metal powder contains 7.5m 3 In a reactor of pure water and 45kg ammonium chloride, air is introduced for oxidation, and the air flow is controlled to be 55m 3 Stirring at 300r/min, reacting at room temperature for 20h, filtering under positive pressure, and washing (Cl) - Content (wt.)<300 ppm) to obtain manganomanganic oxide particles after drying.
(2) And (2) roasting the manganous-manganic oxide obtained in the step (1) in an air atmosphere at 500 ℃ for 4h until the reaction is finished.
The medium particle size of the trimanganese tetroxide product prepared in step (1) of the comparative example was tested, and the test result was 7.38 μm.
The manganomanganic oxide product prepared in the comparative example and lithium carbonate are fully mixed according to the mol ratio of Li/Mn =0.53 and are filled into a pot, the thickness of the pot is 2.5cm/3.5cm/4.5cm, the air flow is 10m at 660 DEG C 3 Calcining for 12 hours under the condition of/h to obtain the lithium manganate product.
Table 9 shows the sensory hardness of the lithium manganate product obtained by sintering the composite manganese source mixed lithium source in the comparative example under different pot thicknesses and the charge-discharge condition of the button cell prepared from the lithium manganate product.
TABLE 9 Properties of lithium manganate product obtained in comparative example 3 under different pot thicknesses
As can be seen from the performance data of comparative example 3 and Table 9, comparative example 3 has a 40 ℃ reduction in sintering temperature over the examples and an increase in sintering air flow to 10m 3 During the sintering process, the powder is still hard after sintering, the powder can be crushed only when the finger exerts great force, the powder is still not convenient to screen into small-particle lithium manganate, and the charging and discharging are normal only when the test button electricity 1C manufactured during the sintering process with the thickness of 2.5cm is used.
The properties of the composite manganese source products obtained in examples 1-6 and comparative examples 1-3 and the charge and discharge conditions (i.e., discharge capacity at 1C) applied to the manufacture of button cells are shown in Table 10 and FIG. 1.
TABLE 10 Properties of composite manganese source products obtained in examples and comparative examples and applications in manufacturing of button cell charging and discharging conditions
As can be seen from the performance data in table 10 and fig. 1, when the composite manganese source products obtained in comparative examples 1 to 3 are applied to the manufacture of button cells, the charging and discharging capacity of the button cell 1C is relatively low, the charging and discharging curve of the button cell 1C changes dramatically, and the charging and discharging performance of the button cell 1C is not good.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the composite manganese source for lithium manganate is characterized by comprising the following steps:
crushing and grading metal manganese powder, adding the graded metal manganese powder into an ammonium salt solution, adding manganese dioxide, introducing air, stirring, reacting for a period of time, and filtering to obtain a reaction product;
and step two, washing, drying, roasting and sieving the reaction product obtained in the step one to obtain the composite manganese source for the lithium manganate.
2. The method for preparing the composite manganese source for lithium manganate according to claim 1, wherein in the first step, the amount of manganese dioxide added is 5-30% by mass of said manganese metal powder.
3. The method for preparing the composite manganese source for lithium manganate according to claim 1, wherein in the first step, the manganese dioxide is one or more of electrolytic manganese dioxide, unsintered dust collection material in the lithium manganate production process, manganese dioxide obtained after lithium extraction from lithium manganate waste, and airflow classification fine powder of electrolytic manganese dioxide;
the volume median particle diameter D50 of the manganese dioxide is 3-15 mu m.
4. The method of preparing the composite manganese source for lithium manganate according to claim 1, wherein in the first step, the manganese content in the manganese metal powder is more than 99.5%, and the particle size of the crushed and classified manganese metal powder is in the range of 5 to 200 μm.
5. The method of producing the composite manganese source for lithium manganate according to claim 1, wherein in said first step, said ammonium salt solution has a concentration of 4 to 20g/L;
the ammonium salt in the ammonium salt solution is one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
6. The method of producing the composite manganese source for lithium manganate according to claim 1, wherein in said first step, said air is introduced at a rate of 40 to 120m 3 /h；
In the first step, the stirring speed is 100-500r/min, the reaction temperature is room temperature, and the reaction time is 16-30h.
7. The method for preparing the composite manganese source for lithium manganate according to any one of claims 1 to 6, wherein in the second step, said calcination is specifically: the reaction product is roasted for 2 to 5 hours in the air atmosphere of 500 to 580 ℃.
8. A composite manganese source for lithium manganate produced by the method for producing a composite manganese source for lithium manganate according to any of claims 1 to 7, wherein said composite manganese source for lithium manganate is a manganese dioxide-manganese tetraoxide composite particle, the surface layer is trimanganese tetraoxide, and the inner layer is manganese dioxide;
the particle size range of the composite manganese source for lithium manganate is 1.5-40 mu m, and the volume median particle size D50 is 5-15 mu m.
9. A lithium manganate produced by synthesizing the composite manganese source for lithium manganate according to claim 8, and a lithium compound.
10. The use of the lithium manganate according to claim 9 for preparing a positive electrode material of a lithium ion battery.
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| CN111477865A (en) * | 2020-04-02 | 2020-07-31 | 广西锰华新能源科技发展有限公司 | Method for producing lithium manganate in internal oxygen mode |
| CN111620379A (en) * | 2020-05-19 | 2020-09-04 | 广西锰华新能源科技发展有限公司 | Preparation method of high-end lithium manganate raw material |
| CN114044539A (en) * | 2021-10-30 | 2022-02-15 | 湖南海利锂电科技股份有限公司 | Preparation method of high-cycle power type lithium manganate |
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| CN102842708A (en) * | 2012-08-14 | 2012-12-26 | 中钢集团安徽天源科技股份有限公司 | Manganous-manganic oxide preparation method for battery positive pole material lithium manganate and product thereof |
| CN108059190A (en) * | 2017-12-14 | 2018-05-22 | 中钢集团安徽天源科技股份有限公司 | A kind of LiMn2O4 compound mangano-manganic oxide and its industrial production process |
| CN111477865A (en) * | 2020-04-02 | 2020-07-31 | 广西锰华新能源科技发展有限公司 | Method for producing lithium manganate in internal oxygen mode |
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