CN109650457B - Preparation method of spheroidal manganous-manganic oxide - Google Patents
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- CN109650457B CN109650457B CN201910137284.1A CN201910137284A CN109650457B CN 109650457 B CN109650457 B CN 109650457B CN 201910137284 A CN201910137284 A CN 201910137284A CN 109650457 B CN109650457 B CN 109650457B
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- C—CHEMISTRY; METALLURGY
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- 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
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention belongs to the field of raw materials for lithium manganate of a battery anode, and particularly relates to a preparation method of spheroidal manganous-manganic oxide, which comprises the steps of preparing manganese powder with the granularity of less than or equal to 100 mu m from metal manganese sheets with the purity of more than 99wt.% by using crushing equipment, adding deionized water to prepare suspension with a certain liquid-solid ratio, adding ammonium salt with the weight of 1-3% of the manganese powder and 0.2-1 per mill of surfactant, controlling the reaction temperature, adding an oxidant, adding ammonia water to control the pH in the reaction process, reacting for several hours at a certain stirring speed, and washing, flash evaporating and drying slurry after the reaction is finished to prepare the spheroidal manganous-manganic oxide.
Description
Technical Field
The invention belongs to the field of raw materials for lithium manganate of a battery anode, and particularly relates to a preparation method of spheroidal manganous-manganic oxide.
Background
The manganous-manganic oxide is an important raw material for producing manganese-zinc ferrite soft magnetic materials in the electronic industry, and is also applied to the fields of thermistors, pigments, catalysts and the like in a small amount. In recent years, manganous manganic oxide is applied to the field of batteries, and is mainly used for preparing lithium manganate cathode materials of lithium ion batteries. Because the production process of the lithium manganate material usually adopts dry mixing, the manganous-manganic oxide product is required to have regular particle morphology, uniform distribution, no abnormal agglomerated particles and good powder dispersibility so as to ensure the uniformity of mixing the manganese source and the lithium source.
At present, domestic manufacturers mainly adopt an electrolytic manganese metal suspension oxidation method to produce the mangano-manganic oxide, the method crushes manganese metal sheets to prepare suspension, then carries out air oxidation to obtain mangano-manganic oxide slurry, and the slurry is washed and dried to obtain the mangano-manganic oxide. The manganous-manganic oxide prepared by the traditional process has small median diameter, irregular particle appearance and poor uniformity, and is difficult to be directly used in the battery industry; in addition, a spray drying method is generally adopted in the drying process, and the principle is as follows: the air passes through the filter and the heater and enters an air distributor at the top of the centrifugal spray dryer, and the hot air uniformly enters the dryer in a spiral shape. The manganous-manganic oxide feed liquid is conveyed to a centrifugal atomizer at the top of the dryer from a feed liquid tank through a filter by a pump, so that the feed liquid is sprayed into extremely small fog-like liquid drops, the feed liquid is in parallel flow contact with hot air, moisture is rapidly evaporated, the feed liquid is dried into a finished product in an extremely short time, the finished product is discharged from the bottom of the drying tower and a cyclone separator, and waste gas is discharged by a fan. The manganous-manganic oxide is prepared by a spray drying method, in order to ensure that slurry is sufficiently atomized, the mass percentage concentration of feed liquid is not more than 55%, the gas consumption per ton of product is more than 80 cubic meters, the energy consumption is high, in addition, the prepared manganous-manganic oxide powder particles are easy to agglomerate, the water content of the product is not easy to control, and the mass content of the water is more than 0.3%.
The invention provides a preparation method of spherical-like manganous-manganic oxide, aiming at solving the problems that the traditional soft magnetic manganous-manganic oxide is difficult to apply in the battery industry and the like, and simultaneously solving the problems that the median diameter is smaller, particles are easy to agglomerate, the appearance is irregular, the energy consumption is higher, the moisture quality content is higher and the like in the preparation process. The method prepares the sphere-like manganous-manganic oxide powder by controlling the corrosion rate of the metal manganese in the solution and the agglomeration mode of the manganous-manganic oxide particles, and in addition, a flash evaporation drying method is adopted in the drying process of the method. The flash drying principle is as follows: hot air enters the stirring, crushing and drying chamber from the bottom of the dryer at a proper spouting speed through the human mouth pipe, strong shearing, floating and rotating effects are generated on materials, and the materials are micronized through centrifugation, shearing, collision and friction, so that mass and heat transfer are enhanced. At the lower part of the dryer, larger and wetter particle groups are mechanically crushed under the action of the stirrer, particles with lower moisture content and smaller particle size are entrained by the rotating airflow and rise, and are further dried in the rising process, the top of the drying chamber is provided with a grading cyclone which can grade the materials, and agglomerated powder returns to the cavity for further crushing, so that the uniformity and the dispersibility of the particles are ensured.
The manganous-manganic oxide prepared by the method is suitable for being used for preparing a lithium manganate cathode material in the field of lithium ion batteries, on one hand, the dried product maintains the spheroidal morphology in the reaction process, the product has good dispersibility, abnormal agglomerated particles do not exist, the water content of the product is easy to control, in addition, the concentration of the feed liquid can be improved to more than 80%, and the gas consumption per ton of the product can be reduced by more than half.
Disclosure of Invention
D50The index is the particle size corresponding to a cumulative percentage of particle size distribution in a sample of up to 50%, also known as the "median particle size" or "median particle size", and is commonly used to refer to the particle size of the population. Lithium ionD of lithium manganate cathode material generally required by battery industry50About 10 μm to achieve both electrochemical performance and processability. The manganous manganic oxide prepared by the traditional process has smaller grain diameter and median diameter D50Generally less than 3 mu m, irregular particle appearance, poor uniformity and difficult application in the lithium manganate industry. In addition, the traditional method adopts spray drying to prepare the manganous-manganic oxide, the mass percentage concentration of the feed liquid is generally not more than 55 percent, the energy consumption is higher, and the prepared manganous-manganic oxide powder particles are easy to agglomerate. In addition, the problem that the product moisture in the traditional preparation process of the trimanganese tetroxide is difficult to control is solved, and the moisture content is generally more than 0.3 percent by mass. The invention provides a novel preparation method for solving the problems of irregular particle appearance, easy agglomeration, high energy consumption, high water content, high mass content and the like.
The invention relates to a preparation method of spheroidal manganous-manganic oxide, which is obviously characterized in that the synthesis conditions and the reaction process are regulated and controlled by controlling the granularity of initial manganese powder, the types of a catalyst and a surfactant so as to effectively control and improve the microscopic morphology and the structure of a product. In addition, a flash evaporation drying method is introduced, so that on the basis of keeping the appearance of the trimanganese tetroxide particles in the reaction process, drying energy consumption is saved, and the water content of the trimanganese tetroxide industrial product is reduced.
Specifically, the invention relates to a preparation method of spheroidal manganous-manganic oxide, which comprises the following steps:
(1) preparing manganese powder with the granularity of less than or equal to 100 mu m from metal manganese sheets with the purity of more than 99wt.% by using crushing equipment;
(2) adding the manganese powder prepared in the step (1) into a reaction kettle, and adding deionized water to prepare suspension; adding ammonium salt accounting for 1-3% of the weight of the manganese powder and surfactant accounting for 0.2-1 per mill of the weight of the manganese powder; controlling the reaction temperature; adding an oxidant; adding ammonia water to control the reaction pH; stirring and reacting for 10-20 hours, filtering and washing;
(3) and (4) adding the washed material cake into flash evaporation drying equipment for drying to obtain the spheroidal manganous-manganic oxide.
Wherein, step (2), preferably:
the liquid-solid ratio of the suspension is (2-5) to 1, preferably (2-4) to 1;
the ammonium salt is one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium formate, ammonium acetate and ammonium citrate.
The surfactant is one or more of polyacrylic acid, ammonium polyacrylate, polyethylene glycol, polyvinyl alcohol and polyacrylamide.
The oxidant is one or more of oxygen, compressed air and hydrogen peroxide.
The reaction temperature is 50-80 ℃, and preferably 60-80 ℃.
The pH value is 6.5-7.5, preferably 6.9-7.1.
The stirring speed is 200-500 r/min, preferably 350-500 r/min.
And impurities such as chloride, ammonium salt, calcium, magnesium and the like are removed by washing.
Preferably, the flash evaporation process parameters in the step (3) are as follows: the inlet temperature is 200-300 ℃, and preferably 250-300 ℃; the outlet temperature is 100-120 ℃, and preferably 110-120 ℃; negative pressure is 500-1000 Pa, preferably 800-1000 Pa; the crushing and stirring speed is 50-150 rpm, preferably 100-150 rpm.
The invention also relates to spheroidal mangano-manganic oxide prepared by any one of the methods, which is characterized in that: the manganous manganic oxide prepared by the method has a spherical or sphere-like particle shape and a median diameter D503 to 15 μm, preferably 5 to 15 μm, and more preferably 10 to 12 μm.
Preferably, the water content of the mangano-manganic oxide product is less than 0.3 percent by mass.
Preferably, the natural gas used in the preparation method of the trimanganese tetroxide is less than 40 cubic meters per ton of the product.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a flow diagram of flash drying used in the examples, wherein: 1. a blower; 2. heating furnace; 3. a flash evaporation host; 4. a feeder; 5. a cyclone separator; 6. a bag-type dust collector; 7. draught fan
FIG. 2 is a scanning electron micrograph of a trimanganese tetroxide product prepared in example 1
FIG. 3 is a scanning electron micrograph of a trimanganese tetroxide product prepared in example 2
FIG. 4 is a scanning electron micrograph of a trimanganese tetroxide product prepared in example 3
FIG. 5 is a scanning electron micrograph of a trimanganese tetroxide product obtained in example 4
FIG. 6 is a scanning electron micrograph of a trimanganese tetroxide product obtained in example 5
Detailed Description
The present invention will be further described with reference to the following examples. The described embodiments and their results are only intended to illustrate the invention and should not be taken as limiting the invention described in detail in the claims.
Example 1
Crushing 1000Kg of high-purity metal manganese sheet by a double-roller machine to within 100 mu m, mixing for 2 hours by a double-cone mixer, and putting the high-purity metal manganese sheet into the mixer after 4m of the high-purity metal manganese sheet is added3Preparing suspension in a pure water reaction kettle, adding 25kg of ammonium sulfate and 0.8kg of ammonium polyacrylate, controlling the temperature in the reaction kettle at 60 ℃, introducing air for oxidation under the condition of stirring, wherein the air amount is controlled at 300m3H, controlling the stirring speed at 350r/min, adding ammonia water to control the pH value of the reaction to be 7 +/-0.1, finishing the reaction after 15 hours, filtering and washing slurry to obtain a cake with the water content of 16 percent by mass, adding the cake into flash evaporation drying equipment, controlling the air quantity of a blower and an induced draft fan to ensure that the negative pressure in a tower is 800Pa, controlling the temperature of a burner to ensure that the inlet temperature is maintained at 250 ℃, the outlet temperature is maintained at 110 ℃, crushing and stirring speed is 100 r/min, and drying to obtain the spheroidal manganous manganic oxide powder.
The manganous-manganic oxide product prepared in the example has good particle dispersibility, is spherical or quasi-spherical in shape, has a median particle size of 10.8 mu m, uses 33 cubic natural gas per ton of product, and has a water content of 0.2%.
Example 2
The process was the same as in example 1, except that the high-purity manganese metal sheet was crushed to within 50 μm using a twin-roll mill.
The manganous-manganic oxide product prepared in the example has good particle dispersibility, is spherical or quasi-spherical in shape, has the median particle diameter of 5.8 mu m, uses 37 cubic volumes of natural gas per ton of the product, and has the water content of 0.22 percent.
Example 3
The process was the same as in example 1, except that 0.8kg of polyvinyl alcohol was used as the surfactant.
The mangano-manganic oxide product prepared in the example has a median particle size of 12.5 mu m, 33 cubic meters of natural gas is used per ton of product, and the water content of the product is 0.19 percent.
Example 4
The process was the same as in example 1, except that 0.8kg of polyacrylamide was used as the surfactant.
The medium particle size of the mangano-manganic oxide product prepared in the example is 4.7 mu m, the natural gas used per ton of the product is 36 cubic meters, and the water content of the product is 0.25 percent.
Example 5
The process was the same as in example 1, except that the washed trimanganese tetroxide cake was mixed with deionized water to make a slurry with 50% solid content, and dried using a spray drying apparatus, the rotational speed of the atomizing disk was set at 15000 rpm, the inlet temperature was controlled at 250 ℃ and the outlet temperature was maintained at 110 ℃ to obtain trimanganese tetroxide powder.
The medium particle size of the mangano-manganic oxide product prepared in the example is 10.2 mu m, the natural gas used in one ton of the product is 88 cubic meters, and the water content of the product is 0.35 percent.
Example 6
The process is the same as that of example 1, except that the cake is added into a flash drying device, the temperature of a burner is controlled, the inlet temperature is maintained at 200 ℃, the outlet temperature is maintained at 110 ℃, the crushing and stirring speed is 100 r/min, and the sphere-like manganous manganic oxide powder is prepared after drying.
The medium particle size of the mangano-manganic oxide product prepared in the example is 10.1 mu m, the natural gas used per ton of the product is 34 cubic meters, and the water content of the product is 0.25 percent.
Example 7
The process is the same as that of example 1, except that the cake is added into a flash drying device, the temperature of the burner is controlled, the inlet temperature is maintained at 300 ℃, the outlet temperature is maintained at 110 ℃, the crushing and stirring speed is 100 r/min, and the sphere-like manganous manganic oxide powder is prepared after drying.
The medium particle size of the mangano-manganic oxide product prepared in the example is 10.5 mu m, the volume of natural gas used per ton of the product is 38 cubic meters, and the water content of the product is 0.15 percent.
Claims (9)
1. A preparation method of spheroidal manganous-manganic oxide comprises the following steps:
(1) preparing manganese metal sheets with the purity of more than 99wt.% into manganese powder with the particle size of less than or equal to 100 mu m by using crushing equipment;
(2) adding the manganese powder prepared in the step (1) into a reaction kettle, and adding deionized water to prepare suspension; adding ammonium salt accounting for 1-3% of the weight of the manganese powder and surfactant accounting for 0.2-1 per mill of the weight of the manganese powder; controlling the reaction temperature; adding an oxidant; adding ammonia water to control the reaction pH; stirring and reacting for 10-20 hours, filtering and washing;
(3) adding the washed material cake into flash evaporation drying equipment for drying to prepare spheroidal manganous manganic oxide;
wherein the liquid-solid ratio of the suspension liquid in the step (2) is (2-5) to 1;
the ammonium salt in the step (2) is one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium formate, ammonium acetate and ammonium citrate;
the surfactant in the step (2) is one or more of polyacrylic acid, ammonium polyacrylate, polyethylene glycol and polyacrylamide;
the oxidant in the step (2) is one or more of oxygen, compressed air and hydrogen peroxide;
the reaction temperature in the step (2) is 50-80 ℃;
the pH value in the step (2) is 6.9-7.1;
the flash evaporation process parameters in the step (3) are as follows: the inlet temperature is 200-300 ℃; the outlet temperature is 100-120 ℃; negative pressure is 500-1000 Pa; the crushing and stirring speed is 50-150 r/min.
2. The preparation method according to claim 1, wherein the liquid-solid ratio of the suspension in the step (2) is (2-4): 1.
3. The method according to claim 1, wherein the reaction temperature in the step (2) is 60 to 80 ℃.
4. The preparation method of claim 1, wherein the flash evaporation process parameters in the step (3) are as follows: the inlet temperature is 250-300 ℃.
5. The preparation method of claim 1, wherein the flash evaporation process parameters in the step (3) are as follows: the outlet temperature is 110-120 ℃.
6. The preparation method of claim 1, wherein the flash evaporation process parameters in the step (3) are as follows: the negative pressure is 800-1000 Pa.
7. The preparation method of claim 1, wherein the flash evaporation process parameters in the step (3) are as follows: the crushing and stirring speed is 100-150 r/min.
8. The method according to claim 1, wherein the stirring speed in step (2) is 200 to 500 r/min.
9. The method according to claim 1, wherein the stirring speed in step (2) is 350 to 500 r/min.
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| CN110776015A (en) * | 2019-11-05 | 2020-02-11 | 江西智锂科技有限公司 | Synthesis method of battery-grade trimanganese tetroxide |
| CN110759384A (en) * | 2019-11-08 | 2020-02-07 | 中信大锰矿业有限责任公司 | Method for preparing spheroidal manganous manganic oxide by manganese sulfate solution |
| CN111892091B (en) * | 2020-08-27 | 2023-04-07 | 湖南特种金属材料有限责任公司 | Preparation method of mangano-manganic oxide for drilling mud |
| CN113690011A (en) * | 2021-07-13 | 2021-11-23 | 贵州金瑞新材料有限责任公司 | Demagnetisation process for preparing battery-grade trimanganese tetroxide by manganese sheet method |
| CN113735175B (en) * | 2021-08-17 | 2022-09-06 | 华中农业大学 | Nano-mimetic enzyme, preparation method and seed soaking agent containing nano-mimetic enzyme |
| CN115959716A (en) * | 2022-12-06 | 2023-04-14 | 中钢天源股份有限公司 | Nickel-manganese binary precursor and preparation method thereof |
| CN115959710A (en) * | 2022-12-06 | 2023-04-14 | 中钢天源股份有限公司 | Preparation method of battery-grade manganese sesquioxide and product thereof |
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| CN106335929B (en) * | 2016-08-15 | 2018-05-25 | 中南大学 | A kind of preparation method of the mangano-manganic oxide of micro nano structure |
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