A high tap density battery grade trimanganese tetraoxide preparation system

Abstract

The utility model discloses a high vibration density battery grade four manganese dioxide preparation system, including first synthetic device, second synthetic device, filter equipment and drying device, first synthetic device and second synthetic device all are connected first storage tank, second storage tank, third storage tank, fourth storage tank and fifth storage tank, the discharge port of first synthetic device is connected with the feed port of second synthetic device, and the first stirring structure is arranged in first synthetic device, and the second stirring mechanism is arranged in second synthetic device, and the stirring power of first stirring mechanism is greater than the stirring power of second stirring mechanism, the discharge port of second synthetic device is connected filter equipment, and the slag outlet of filter equipment is connected drying device, the utility model discloses can realize the low consumption control of ammonia water, the efficient utilization of mother liquor to can obtain the battery grade four manganese dioxide product of even granularity, high sphericity, higher vibration.

Description

Technical Field

[0001] This utility model relates to the field of manganese tetroxide production technology, specifically a high tap density battery-grade manganese tetroxide preparation system. Background Technology

[0002] Lithium manganese oxide is an important cathode material for lithium-ion batteries, and manganese tetroxide (Mn3O4) can serve as a high-quality manganese source for its preparation. Mn3O4 has a spinel structure, resulting in minimal phase structure changes and internal stress during lithium manganese oxide preparation. This leads to significantly improved capacity and cycle performance compared to lithium manganese oxide prepared via traditional electrolytic manganese dioxide. Tap density is one of the key indicators of Mn3O4; a high tap density not only effectively improves the battery's energy density and volumetric specific capacity but also enhances cycle stability and rate performance.

[0003] Currently, the main methods for preparing manganese tetroxide include solid-phase and liquid-phase methods. The solid-phase method requires high-temperature calcination, resulting in coarse particles and making subsequent processing difficult. The liquid-phase method has a more complex process flow, higher costs, and poor tap density stability, making it difficult to meet the requirements of high-performance battery materials. Patent CN120463243A proposes a method for preparing manganese tetroxide with controllable tap density. This method is based on in-depth research on the growth characteristics of manganese tetroxide crystal particles. By optimizing process parameters and controlling the behavior of particles at different growth stages, it successfully achieves accurate prediction and precise control of the product's tap density. However, this method is cumbersome in pH adjustment and easily causes a large amount of ammonia to volatilize at high temperatures, resulting in high costs.

[0004] Therefore, the present invention aims to provide a method for preparing high-tap-density battery-grade manganese tetroxide, in order to solve the problems of low tap density of manganese tetroxide prepared by existing manganese tetroxide production systems and low production efficiency and high cost caused by the ineffective utilization of mother liquor. Utility Model Content

[0005] The technical problem solved by this invention is to provide a high tap density battery-grade manganese tetroxide preparation system to overcome the shortcomings in the above-mentioned background technology.

[0006] The technical problem solved by this utility model is achieved by the following technical solution:

[0007] A high-taper-density battery-grade manganese tetroxide preparation system includes a first synthesis unit, a second synthesis unit, a filtration unit, and a drying unit. Both the first and second synthesis units are connected to a first storage tank, a second storage tank, a third storage tank, a fourth storage tank, and a fifth storage tank. The first storage tank provides manganese chloride solution to both synthesis units; the second storage tank provides liquid alkali; the third storage tank provides ammonia; the fourth storage tank provides a slow-release agent solution; and the fifth storage tank provides the mother liquor to the first synthesis unit. The outlet of the first synthesis unit is connected to the inlet of the second synthesis unit. The first synthesis unit contains a first stirring structure, and the second synthesis unit contains a second stirring mechanism. The stirring power of the first stirring mechanism is greater than that of the second stirring mechanism. The outlet of the second synthesis unit is connected to the filtration unit, and the slag outlet of the filtration unit is connected to the drying unit.

[0008] In this invention, both the first synthesis device and the second synthesis device are connected to a vent pipe at their bottoms.

[0009] In this invention, both the first synthesis apparatus and the second synthesis apparatus include a reaction vessel, and a heating jacket is provided on the reaction vessel.

[0010] In this invention, a temperature sensor and a pH sensor are installed inside the reaction vessel.

[0011] In this invention, a flow valve is installed at the discharge port of the third storage tank.

[0012] In this invention, the filtration device includes a plate and frame filter press.

[0013] In this invention, the outlet of the filtration device is connected to a fifth storage tank.

[0014] In this invention, a concentration sensor is installed in the fifth storage tank.

[0015] In this invention, the drying device includes a disc dryer.

[0016] Beneficial effects: The high tap density battery-grade manganese tetroxide preparation system of this utility model can realize the preparation of initial microcrystals and dense seed crystals from mother liquor, and the growth of large-particle-size manganese tetroxide. During the synthesis process, a low-flow-rate co-current ammonia water can be provided through a third storage tank, thereby producing a manganese tetroxide product with high density.

[0017] In this invention, the ammonia-containing mother liquor can be recycled for use as the base liquid, saving ammonia water while further reducing the difficulty and cost of wastewater treatment, thereby reducing production costs and improving overall efficiency. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of a preferred embodiment of the present invention.

[0019] The components are: 1. First storage tank; 2. Second storage tank; 3. Third storage tank; 4. Fourth storage tank; 5. Fifth storage tank; 6. First synthesis device; 7. Second synthesis device; 8. Filtering device; 9. Drying device; 10. Ventilation pipe; 11. First stirring mechanism; 12. Second stirring mechanism. Detailed Implementation

[0020] To make the technical means, creative features, objectives and effects of this utility model easier to understand, the following description, in conjunction with specific illustrations, further elaborates on this utility model.

[0021] See Figure 1 As shown, the high tap density battery-grade manganese tetroxide preparation system of this utility model includes a first synthesis device 6, a second synthesis device 7, a filtration device 8, and a drying device 9. The first synthesis device 6 and the second synthesis device 7 are both connected to a first storage tank 1, a second storage tank 2, a third storage tank 3, a fourth storage tank 4, and a fifth storage tank 5. The first storage tank 1 provides manganese chloride solution to the first synthesis device 6 and the second synthesis device 7; the second storage tank 2 provides liquid alkali to the first synthesis device 6 and the second synthesis device 7; the third storage tank 3 provides ammonia water to the first synthesis device 6 and the second synthesis device 7; the fourth storage tank 4 provides a slow-release agent solution to the first synthesis device 6 and the second synthesis device 7, the slow-release agent solution being one or more of EDTA, sodium acetate, and sodium oxalate; and the fifth storage tank 5 provides the reaction mother liquor to the first synthesis device 6. The discharge port of the first synthesis device 6 is connected to the inlet of the second synthesis device 7, the discharge port of the second synthesis device 7 is connected to the filter device 8, the slag outlet of the filter device 8 is connected to the drying device 9, and the product from the drying device 9 is manganese tetroxide with high tap density.

[0022] In this invention, the first synthesis device 6 is a reaction vessel with a heating jacket. The first synthesis device 6 receives the mother liquor from the fifth storage tank 5, as well as the manganese chloride solution from the first storage tank 1, the liquid alkali from the second storage tank 2, the ammonia from the third storage tank 3, and the slow-release agent from the fourth storage tank 4. The first synthesis device 6 is equipped with a first stirring structure with a high-speed stirring paddle. The volumetric power of the first stirring mechanism 11 is ≥5.0kW / m3 to ensure that the manganese tetroxide particles are fully dispersed and reformed into dense particles during the seed crystal preparation process.

[0023] The second synthesis unit 7, connected to the first synthesis unit 6, is also a reactor. The reactor is equipped with a heating jacket. The second synthesis unit 7 receives manganese tetroxide seed slurry from the first synthesis unit 6 as the reaction base liquid, as well as manganese chloride solution from the first storage tank 1, liquid alkali from the second storage tank 2, ammonia from the third storage tank 3, and a slow-release agent from the fourth storage tank 4, to further react and prepare high-tap-density manganese tetroxide. The second synthesis unit 7 is equipped with a second stirring mechanism 12. The stirring power of the second stirring mechanism 12 is lower than that of the first stirring mechanism 11. The low-speed stirring mechanism 12 has a low-speed stirring paddle, and its volumetric power is 2–5 kW / m³. 3 This can reduce power consumption and is beneficial for the growth of large-particle-size manganese tetroxide.

[0024] Both the first synthesis device 6 and the second synthesis device 7 are connected to a vent pipe 10 at the bottom, which is used to provide oxygen for the reaction.

[0025] Both the first synthesis device 6 and the second synthesis device 7 are equipped with temperature and pH sensors to monitor the reaction temperature and pH value in real time. During the reaction, the pH of the system is maintained at a slightly alkaline level, with pH fluctuations within 0.5, and the reaction temperature is maintained at 70±10℃. The reaction time in the first synthesis device 6 is 3–6 hours, and the reaction time in the second synthesis device 7 is approximately 12 hours. As an improvement, an alarm device can be further added to this invention.

[0026] In this invention, a flow valve is installed on the third storage tank 3. This flow valve controls the amount of ammonia entering the first synthesis unit 6 and the second synthesis unit 7, maintaining a low flow rate and keeping the ammonia nitrogen concentration in both units between 0.5 and 1.5 g / L. Because the outlet of the filter device 8 is connected to the fifth storage tank 5, the filtered ammonia-containing mother liquor can be recycled to replenish ammonium ions. This further reduces the feed flow rate of the co-current ammonia in subsequent reactions, thus avoiding the problems of large ammonia consumption and high-temperature volatilization associated with the one-time addition of ammonia in traditional manganese tetroxide production processes.

[0027] The filtration device 8 is preferably a plate and frame filter press, used to filter the liquid coming out of the second synthesis device 7. The filtered liquid enters the fifth storage tank 5, which can be used as the reaction mother liquor for the first synthesis device 6. A concentration sensor is installed in the fifth storage tank 5. When the filtered liquid continues to enter the fifth storage tank 5 and the Na concentration in the reaction mother liquor in the fifth storage tank 5 is >100g / L, the filtered liquid enters the wastewater treatment process. This method can recycle the filtered liquid, prevent crystallization caused by excessive NaCl concentration in the mother liquor, and improve the final treatment efficiency of wastewater.

[0028] The filter residue outlet of the filter device 8 is connected to the drying device 9. The drying device 9 is preferably a disc dryer. After the disc dryer dries the wet material, a battery-grade manganese tetroxide product with high tap density can be obtained.

[0029] In actual production, the manganese tetroxide preparation system described in this invention can produce battery-grade manganese tetroxide products with uniform particle size, high sphericity, and higher tap density, wherein the Mn content is >71%, the D50 is 7-15 μm, and the tap density is >2.55 g / cm³. 3 The product exhibits excellent performance. Therefore, this invention can achieve low-consumption control of ammonia water, efficient utilization of mother liquor, and yield battery-grade manganese tetroxide products with uniform particle size, high sphericity, and higher tapping strength.

[0030] In the description of this utility model, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc., indicating the orientation or positional relationship are based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this utility model and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this utility model.

[0031] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this utility model, "multiple" means two or more, unless otherwise explicitly specified.

[0032] In this utility model, unless otherwise explicitly specified and limited, the terms "installation", "connection", "linking", "fixing", etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components.

[0033] In the description of this utility model, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc., indicating the orientation or positional relationship are based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this utility model and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this utility model.

[0034] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this utility model, "multiple" means two or more, unless otherwise explicitly specified.

[0035] In this utility model, unless otherwise explicitly specified and limited, the terms "installation", "connection", "linking", "fixing", etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components.

[0036] The above description, in conjunction with specific embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, several simple deductions or substitutions can be made without departing from the concept of the present invention.

Claims

1. A high-tap-density battery-grade manganese tetroxide preparation system, characterized in that, The apparatus includes a first synthesis unit, a second synthesis unit, a filtration unit, and a drying unit. Both the first and second synthesis units are connected to a first storage tank, a second storage tank, a third storage tank, a fourth storage tank, and a fifth storage tank. The first storage tank provides manganese chloride solution to both synthesis units; the second storage tank provides liquid alkali; the third storage tank provides ammonia; the fourth storage tank provides a slow-release agent solution; and the fifth storage tank provides the mother liquor to the first synthesis unit. The outlet of the first synthesis unit is connected to the inlet of the second synthesis unit. The first synthesis unit contains a first stirring structure, and the second synthesis unit contains a second stirring mechanism. The stirring power of the first stirring mechanism is greater than that of the second stirring mechanism. The outlet of the second synthesis unit is connected to the filtration unit, and the slag outlet of the filtration unit is connected to the drying unit.

2. The high tap density battery-grade manganese tetroxide preparation system according to claim 1, characterized in that, Both the first and second synthesis devices are connected to a vent pipe at their bottoms.

3. The high tap density battery-grade manganese tetroxide preparation system according to claim 1, characterized in that, Both the first and second synthesis apparatuses include a reaction vessel, and a heating jacket is provided on the reaction vessel.

4. The high tap density battery-grade manganese tetroxide preparation system according to claim 3, characterized in that, Temperature and pH sensors are installed inside the reactor.

5. The high tap density battery-grade manganese tetroxide preparation system according to claim 1, characterized in that, A flow valve is installed at the discharge port of the third storage tank.

6. The high tap density battery-grade manganese tetroxide preparation system according to claim 1, characterized in that, The filtration device includes a plate and frame filter press.

7. The high tap density battery-grade manganese tetroxide preparation system according to claim 5, characterized in that, The outlet of the filtration device is connected to the fifth storage tank.

8. The high tap density battery-grade manganese tetroxide preparation system according to claim 7, characterized in that, A concentration sensor is installed in the fifth storage tank.

9. The high tap density battery-grade manganese tetroxide preparation system according to claim 1, characterized in that, The drying device includes a disc dryer.

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