CN112897583B - Battery grade monocrystal manganous manganic oxide preparation device and method - Google Patents

Battery grade monocrystal manganous manganic oxide preparation device and method Download PDF

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CN112897583B
CN112897583B CN202110459602.3A CN202110459602A CN112897583B CN 112897583 B CN112897583 B CN 112897583B CN 202110459602 A CN202110459602 A CN 202110459602A CN 112897583 B CN112897583 B CN 112897583B
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manganous
battery
rotary kiln
kiln
grinding roller
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CN112897583A (en
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胡义华
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Hu Li
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The application discloses a battery-level monocrystal manganous-manganic oxide preparation device, which comprises a rotary kiln, wherein at least one damage and wrapping mechanism is arranged in the rotary kiln, the damage and wrapping mechanism comprises a plurality of blocking teeth and a grinding roller, the blocking teeth are arranged on the inner wall of the rotary kiln in a spacing ring manner, and the grinding roller is arranged between the kiln tail and the blocking teeth. The application also provides a preparation method of the battery-grade monocrystalline manganous-manganic oxide. The application can prepare the battery-grade monocrystal manganous-manganic oxide, and better meets the requirements of the lithium manganate battery anode material precursor.

Description

Battery grade monocrystal manganous manganic oxide preparation device and method
Technical Field
The application relates to the technical field related to new energy battery electrode materials. More particularly, the application relates to a method for preparing monocrystalline manganous-manganic oxide.
Background
The dry method production technology of manganous manganic oxide is two, firstly, the direct roasting method of manganese carbonate or manganese hydroxide is mature in process route, the method is a means for mainly producing the manganous oxide at present, usually manganese carbonate is produced and prepared by carbonization of manganese sulfate, manganese hydroxide is produced and prepared by neutralization of the manganese sulfate by alkali, and both are required to co-produce the manganese sulfate, so that the production cost is increased. Secondly, a two-stage roasting method (application number is 201811286919.6) of manganese sulfate, which is a production method invented by technicians of our company in the last two years, well solves the problems of manganese sulfate calcination and tail gas treatment generated in the calcination process, but does not carry out more deep discussion and research on specific monocrystal trimanganese tetraoxide required by a precursor of a new energy lithium battery material, and particularly does not relate to equipment and conditions required by monocrystal trimanganese tetraoxide preparation. In the prior art, aiming at the preparation method of the monocrystal manganous manganic oxide, only a technology for producing the monocrystal manganous oxide by a wet method is invented by Biedi Co., ltd Chen Xiaofang in 2012, namely, alkali is added into an aqueous solution of a manganese compound to obtain manganese hydroxide, and then oxidant is added to oxidize and the like to obtain the monocrystal manganous oxide under a series of chemical means. Therefore, it is needed to provide a method for directly preparing monocrystal manganous manganic oxide by dry calcination of solid manganese sulfate, so that the physicochemical properties of the product completely meet the properties of the precursor of the new energy lithium battery anode material.
Disclosure of Invention
The application aims to provide a device and a method for preparing battery-grade monocrystalline manganous-manganic oxide, which can prepare battery-grade monocrystalline manganous-manganic oxide and better meet the requirements of a precursor of a lithium manganate battery anode material.
To achieve these objects and other advantages and in accordance with the purpose of the application, as embodied and broadly described herein, a battery grade single crystal manganous oxide production apparatus is provided, comprising a rotary kiln having at least one damage-wrap mechanism disposed therein, the damage-wrap mechanism comprising a plurality of blocking teeth spaced apart from one another and a plurality of grinding rollers disposed between a kiln tail and the plurality of blocking teeth.
Further, the number of the package destroying mechanisms is at least two, and the package destroying mechanisms are arranged at intervals.
Further, the height of the blocking teeth is consistent with the diameter of the grinding roller, and the interval of the blocking teeth is 2/3 of the diameter of the grinding roller.
Further, the grinding roller is cylindrical and is arranged approximately coaxially with the rotary kiln.
Further, the number of the grinding rollers is at least three.
The application also provides a preparation method of the battery-grade monocrystalline manganous-manganic oxide, which comprises the following steps: the manganese sulfate raw material or the manganese sulfate raw material containing impurities is put into the battery grade monocrystal manganous-manganic oxide preparation device and calcined for 8 to 16 hours at 900 to 1300 ℃.
Further, the battery-level monocrystal manganous-manganic oxide preparation device comprises two damage wrapping mechanisms, wherein the temperature of the damage wrapping mechanism close to the kiln tail is at least 1100 ℃, and the temperature of the damage wrapping mechanism close to the kiln head is at least 1150 ℃.
Further, the method further comprises the following steps: and cooling the calcined material to normal temperature at a cooling rate of 5-20 ℃/min.
Further, the method further comprises the following steps: pulverizing the cooled material to D 50 Is 5-10 micrometers, D 90 15-20 microns.
Further, the content of impurity elements in the manganese sulfate raw material containing impurities is detected before calcination, and if the content is lower than a predetermined value, the corresponding impurity element compound is added.
The application at least comprises the following beneficial effects:
according to the application, on the basis of the existing rotary kiln, the damage wrapping mechanism is added, so that wrapping balls formed at the junction of the preheating zone and the high-temperature zone in the rotary kiln can be better damaged, fine particles are formed, the material is thoroughly decomposed through high-temperature calcination, the temperature is uniform, the good manganous manganic oxide with a single crystal structure is formed, and the requirements of a precursor of a lithium manganate battery anode material can be better met.
Additional advantages, objects, and features of the application will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the application.
Drawings
FIGS. 1-2 are schematic structural views of a preparation device according to the present application;
fig. 3 is an SEM image of example 1 of the present application.
Fig. 4 is an SEM image of example 2 of the present application.
Fig. 5 is an SEM image of example 3 of the present application.
Fig. 6 is an SEM image of comparative example 1 of the present application.
FIG. 7 is an SEM image of comparative example 2 of the present application;
FIG. 8 is a diagram of the product of comparative example 3 of the present application.
Detailed Description
The present application is described in further detail below with reference to the drawings to enable those skilled in the art to practice the application by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
As shown in fig. 1-2, the embodiment of the application provides a battery level monocrystal manganous manganic oxide preparation device, which comprises a rotary kiln 1, wherein at least one damage and wrapping mechanism is arranged in the rotary kiln 1, the damage and wrapping mechanism comprises a plurality of blocking teeth 2 and a grinding roller 3, the blocking teeth 2 are arranged on the inner wall of the rotary kiln 1 in a spacing ring manner, and the grinding roller 3 is arranged between the kiln tail and the blocking teeth 2.
The solid powder is calcined in the common rotary kiln, namely the materials are melted and decomposed together at the junction of the preheating zone and the high-temperature zone, so that the solid powder is easy to wrap and form balls with innumerable sizes. The manganese sulfate powder is calcined so as well, and the generated manganous manganic oxide has larger thermal resistance, once the ball is formed, the material at the center of the ball is not thoroughly decomposed, and the product is unqualified. In the above embodiment, the rotary kiln body may be provided inside the rotary kiln using the prior art, with a breaking wrap mechanism downstream (from the kiln tail to the kiln head) of forming the wrapped pellets to break the wrapped pellets. Specifically, a plurality of teeth that block set up at rotary kiln inside circumference interval, block the interval of tooth can block wrap up the ball through can, the roller is accepted by blocking the tooth, avoids the roller to kiln head slip, the roller follows the rotary kiln rotation, utilizes with rotary kiln between relative motion roll and broken to being blocked the wrap up ball that the tooth blockked. It should be noted that the weight and size of the grinding roller can be set according to practical requirements, such as being determined through multiple tests. When the monocrystal manganous-manganic oxide is prepared, the monocrystal manganous-manganic oxide is fed from the kiln tail, the raw materials gradually move from the kiln tail to the kiln head, the wrapping mechanism is destroyed to break wrapping balls generated between a preheating zone and a high-temperature zone of the raw materials, and after further calcination, the monocrystal manganous-manganic oxide is discharged from the kiln head and subjected to further treatment. Therefore, the embodiment adds the damage wrapping mechanism on the basis of the existing rotary kiln, can better damage wrapping balls formed at the junction of the preheating zone and the high-temperature zone in the rotary kiln, forms fine particles, thoroughly decomposes materials through high-temperature calcination and has uniform temperature, thereby forming the good manganous manganic oxide with a single crystal structure, and can better meet the requirements of the precursor of the anode material of the lithium manganate battery.
In other embodiments, the number of the breaking wrap mechanisms is at least two and is spaced apart. The calcination of the raw material mainly comprising manganese sulfate in a rotary kiln requires four stages, namely a first stage, a preheating and dehydration (external water and crystallization water) stage; a second, pre-reaction stage; thirdly, a reaction stage; fourth, single crystal formation and cooling stage. Through experiments and production observation, the second and third stages are the easiest to form a package in the four stages, the second stage package material is manganese sulfate and other materials for packaging manganous oxide, molten manganese sulfate and other materials are decomposed and then packaged by manganese sulfate and other materials; the third-stage wrapping material is a material such as manganese sulfate which is wrapped by manganous oxide and is not decomposed, and the manganous oxide has high thermal resistance, so that the material such as manganese sulfate which is wrapped in the innermost layer cannot be decomposed. Therefore, it is preferable to provide two breaking and wrapping mechanisms, which are respectively designed at the positions of the second stage and the third stage, wherein the temperature of the breaking and wrapping mechanism near the kiln tail is at least 1100 ℃, and the temperature of the breaking and wrapping mechanism near the kiln head is at least 1150 ℃.
In other embodiments, the height of the plurality of blocking teeth 2 is consistent with the diameter of the roller, and the spacing of the plurality of blocking teeth is 2/3 of the diameter of the roller 3, as shown in FIG. 2.
In other embodiments, the grinding roller 3 is cylindrical and is disposed substantially coaxially with the rotary kiln 1, so as to facilitate movement in the rotary kiln under the driving of the rotary kiln 1, and roll the wrapped balls.
In other embodiments, the number of the grinding rollers 3 is at least three, so that the extrusion effect of the grinding rollers 3 on the wrapped balls can be improved.
The embodiment of the application also provides a preparation method of the battery-grade monocrystalline manganous-manganic oxide, which comprises the following steps: the manganese sulfate raw material or the manganese sulfate raw material containing impurities is put into the battery grade monocrystal manganous-manganic oxide preparation device and calcined at 900-1300 ℃ for 8-16 hours, preferably at 1050-1300 ℃.
The manganese sulfate raw material is manganese sulfate monohydrate, and specific indexes are shown in the following table:
numbering device Chemical composition Index (I)
1 The main content of manganese (Mn) is more than or equal to (%) (Wt) 31.50
2 Magnesium (Mg) is less than or equal to (%) (Wt) 1.00
3 Nickel (Ni) is less than or equal to (PPM) 1500
4 Cobalt (Co) is less than or equal to (PPM) 500
5 Aluminum (Al) is less than or equal to (PPM) 500
Chemical element control index of single crystal manganous oxide:
numbering device Chemical composition Index (I)
1 The main content of manganese (Mn) is more than or equal to (%) (Wt) 71.50
2 Sulfur (S) is less than or equal to (%) (Wt) 0.05
3 Magnesium (Mg) (%) (Wt) 1.00—1.50
4 Nickel (Ni) (PPM) 100—5000
5 Cobalt (Co) (PPM) 100—1000
6 Aluminum (Al) (PPM) 100-1000
The reaction principle is as follows:
(1)x 1 MnSO 4 +x 2 MgO→{x 3 Mn 3 O 4 +x 4 Mn 2 O 3 ·x 5 MgO}+x 6 SO 2 ↑+x 7 O 2 ↑
(2)y 1 MnSO 4 +y 2 Al 2 O 3 →{y 3 Mn 3 O 4 +y 4 Al 2 O 3 ·y 5 MnO}+y 6 SO 2 ↑+y 7 O 2 ↑
(3)z 1 MnSO 4 +z 2 Co 2 O 3 →{z 3 Mn 3 O 4 +z 4 Co 2 O 3 ·z 5 MnO}+z 6 SO 2 ↑+z 7 O 2 ↑
(4)w 1 MnSO 4 +w 2 NiO→{w 3 Mn 3 O 4 +w 4 Mn 2 O 3 ·w 5 NiO}+w 6 SO 2 ↑+w 7 O 2 ↑
wherein: x is x 2 、y 2 、z 2 、w 2 X is a group 5 、y 5 、z 5 、w 5 0 to 0.2.
In other embodiments, the battery level single crystal manganous oxide production apparatus comprises two said disruption wrap mechanisms, wherein the temperature of the disruption wrap mechanism near the kiln end is at least 1100 ℃, and the temperature of the disruption wrap mechanism near the kiln head is at least 1150 ℃.
In other embodiments, further comprising: and cooling the calcined material to normal temperature at a cooling rate of 5-20 ℃/min, wherein the cold source can be air or industrial tap water.
In other embodiments, further comprising: pulverizing the cooled material to D 50 Is 5-10 micrometers, D 90 15-20 microns, an air mill may be used.
In other embodiments, the content of impurity elements in the impurity-containing manganese sulfate feedstock is detected prior to calcination, and if it is below a predetermined value, the corresponding impurity element compound is added. The additives may be: a battery grade aluminum hydroxide or battery grade aluminum oxide; b battery grade nickel sulfate or nickel carbonate; c battery grade magnesium carbonate or magnesium oxide; and D, battery grade cobalt sulfate or cobalt carbonate. When the impurity content in the raw materials is detected, wherein the contents of magnesium, aluminum, cobalt and nickel are not in accordance with the requirements, the raw materials are required to be added with either A, B, C or D, so that the calcined raw materials are ensured to contain a specified amount of impurity elements, and the requirements of the lithium manganate battery anode material precursor are met.
The following is a detailed description of several embodiments:
example 1:
taking 2000kg of manganese sulfate raw material, directly conveying the raw material into the preparation device by using a feeder after detecting that the impurity content in the raw material meets the index requirement, burning natural gas, controlling the burning atmosphere, controlling the temperature of a part close to a kiln tail damage and wrapping mechanism to be 1130 ℃, and controlling the temperature of a part close to a kiln head damage and wrapping mechanism to be 1200 ℃ and calcining for 15hr; tail gas generated by calcination, namely sulfur dioxide gas, is absorbed by manganese ore pulp of a cooperation unit, and is discharged after being treated to be qualified according to the environmental protection requirement; the calcined material is conveyed to a rotary cooler by a high-temperature screw, the material is cooled in a rotary kiln by external normal-temperature industrial tap water, the material is cooled to normal temperature at a cooling speed of 20 ℃/min, and then the material is finished by a 400-type air mill.
Product detection results:
1. single crystal manganous oxide chemical element detection index:
numbering device Chemical composition Index (I)
1 Manganese (Mn) (%) as a main content (Wt) 71.65
2 Sulfur (S) (%) (Wt) 0.01
3 Magnesium (Mg) (%) (Wt) 1.350
4 Nickel (Ni) (PPM) 3500
5 Cobalt (Co) (PPM) 550
6 Aluminum (Al) (PPM) 350
2. Physical detection index:
(1) Particle size: d (D) 50 7.0 micrometers, D 90 18 microns;
(2) Tap density: d, d Vibration device ＝2.10g/cm 3 ；
(3) The electron microscope observation of the crystal phase structure (SEM image) is shown in FIG. 3, the particle size is uniform, and the surface is smooth.
Example 2:
taking 1000kg of manganese sulfate raw material, and detecting that the impurity content of the raw material is only that the magnesium element does not meet the requirement, namely that the magnesium (Mg) content is 0.1%, the index value is more than or equal to 0.45%, and 12.25kg of battery grade magnesium carbonate or 8.46kg of magnesium hydroxide is required to be supplemented; weighing the raw materials according to the calculated value, uniformly mixing the raw materials with 1000kg of manganese sulfate by using a high-speed mixer, conveying the mixed materials to a preparation device of the application by using a feeder, burning natural gas, controlling the burning atmosphere, controlling the temperature close to a kiln tail damage and wrapping mechanism to 1150 ℃, controlling the temperature close to a kiln head damage and wrapping mechanism to 1250 ℃, and calcining for 15 hours; tail gas generated by calcination, namely sulfur dioxide gas, is absorbed by manganese ore pulp of a cooperation unit, and is discharged after being treated to be qualified according to the environmental protection requirement; the calcined material is conveyed to a rotary cooler by a high-temperature screw, the material is cooled in a rotary kiln by external normal-temperature industrial tap water, the material is cooled to normal temperature at a cooling speed of 10 ℃/min, and then the material is finished by a 400-type air mill.
Product detection results:
1. single crystal manganous oxide chemical element detection index:
numbering device Chemical composition Index (I)
1 Manganese (Mn) (%) as a main content (Wt) 71.88
2 Sulfur (S) (%) (Wt) 0.02
3 Magnesium (Mg) (%) (Wt) 1.250
4 Nickel (Ni) (PPM) 1500
5 Cobalt (Co) (PPM) 350
6 Aluminum (Al) (PPM) 260
2. Physical detection index:
(1) Particle size: d (D) 50 6.5 micrometers, D 90 17 micrometers;
(2) Tap density: d, d Vibration device ＝2.15g/cm 3 ；
(3) The electron microscope observation of the crystal phase structure (SEM image) is shown in FIG. 4, the particle size is uniform, and the surface is smooth. .
Example 3:
taking 1500kg of manganese sulfate raw material, and detecting the impurity content in the raw material: magnesium (Mg) 0.53%; nickel (Ni) 25PPM; cobalt (Co) is 15PPM; aluminum (Al) was 30PPM. Only magnesium element meets the requirement, and other elements need to be supplemented. Supplementing according to the index requirements: (1) 8.839kg of battery grade nickel sulfate (containing 6 crystal water) or 4.00kg of nickel carbonate; (2) Battery grade cobalt sulfate (containing 7 crystal water) 2.762kg or cobalt carbonate 1.17kg; (3) 0.64kg of battery grade alumina or 0.976kg of aluminum hydroxide; weighing the raw materials according to the calculated value, uniformly mixing the raw materials with 1500kg of manganese sulfate by using a high-speed mixer, conveying the mixed materials to a preparation device of the application by using a feeder, burning natural gas, controlling the burning atmosphere, controlling the temperature close to a kiln tail damage wrapping mechanism to be 1100 ℃, controlling the temperature close to a kiln head damage wrapping mechanism to be 1260 ℃, and calcining for 15 hours; tail gas generated by calcination, namely sulfur dioxide gas, is absorbed by manganese ore pulp of a cooperation unit, and is discharged after being treated to be qualified according to the environmental protection requirement; the calcined material is conveyed to a rotary cooler by a high-temperature screw, the material is cooled in a rotary kiln by external normal-temperature industrial tap water, the material is cooled to normal temperature at a cooling speed of 15 ℃/min, and then the material is finished by a 400-type air mill.
Product detection results:
1. single crystal manganous oxide chemical element detection index:
numbering device Chemical composition Index (I)
1 Manganese (Mn) (%) as a main content (Wt) 71.77
2 Sulfur (S) (%) (Wt) 0.015
3 Magnesium (Mg) (%) (Wt) 1.180
4 Nickel (Ni) (PPM) 3100
5 Cobalt (Co) (PPM) 850
6 Aluminum (Al) (PPM) 500
2. Physical detection index:
(1) Particle size: d (D) 50 7.5 micrometers, D 90 18 microns;
(2) Tap density: d, d Vibration device ＝2.05g/cm 3 ；
(3) The electron microscope observation of the crystal phase structure (SEM image) is shown in fig. 5, and it can be seen that the particles are uniformly and tightly distributed, and nickel and cobalt participate in the structure.
Comparative example 1:
taking 2000kg of manganese sulfate raw material, directly conveying the raw material into the preparation device by using a feeder after detecting that the impurity content in the raw material meets the index requirement, burning natural gas, controlling the burning atmosphere, controlling the temperature of the part close to a kiln tail damage and wrapping mechanism to be 750 ℃, controlling the temperature of the part close to a kiln head damage and wrapping mechanism to be 850 ℃, and calcining for 15hr; tail gas generated by calcination, namely sulfur dioxide gas, is absorbed by manganese ore pulp of a cooperation unit, and is discharged after being treated to be qualified according to the environmental protection requirement; the calcined material is conveyed to a rotary cooler by a high-temperature screw, the material is cooled in a rotary kiln by external normal-temperature industrial tap water, the material is cooled to normal temperature at a cooling speed of 20 ℃/min, and then the material is finished by a 400-type air mill.
Product detection results:
1. single crystal manganous oxide chemical element detection index:
numbering device Chemical composition Index (I)
1 Manganese (Mn) (%) as a main content (Wt) 65.65
2 Sulfur (S) (%) (Wt) 3.51
3 Magnesium (Mg) (%) (Wt) 0.980
4 Nickel (Ni) (PPM) 2400
5 Cobalt (Co) (PPM) 320
6 Aluminum (Al) (PPM) 185
2. Physical detection index:
(1) Particle size: d (D) 50 7.0 micrometers, D 90 18 microns;
(2) Tap density: d, d Vibration device ＝1.40g/cm 3 ；
(3) The electron microscope observation of the crystal phase structure (SEM image) is shown in FIG. 6, and it can be seen that the particle surface is not smooth, is in a wool shape and has uneven size; the unreacted starting materials were also detected.
Comparative example 2:
taking 2000kg of manganese sulfate raw material, directly conveying the raw material into the preparation device by using a feeder after detecting that the impurity content in the raw material meets the index requirement, burning natural gas, controlling the burning atmosphere, controlling the temperature of the part close to a kiln tail damage and wrapping mechanism to be 1250 ℃, controlling the temperature of the part close to a kiln head damage and wrapping mechanism to be 1400 ℃ and calcining for 15hr; tail gas generated by calcination, namely sulfur dioxide gas, is absorbed by manganese ore pulp of a cooperation unit, and is discharged after being treated to be qualified according to the environmental protection requirement; the calcined material is conveyed to a rotary cooler by a high-temperature screw, the material is cooled in a rotary kiln by external normal-temperature industrial tap water, the material is cooled to normal temperature at a cooling speed of 20 ℃/min, and then the material is finished by a 400-type air mill.
Product detection results:
1. single crystal manganous oxide chemical element detection index:
numbering device Chemical composition Index (I)
1 Manganese (Mn) (%) as a main content (Wt) 72.02
2 Sulfur (S) (%) (Wt) 0.005
3 Magnesium (Mg) (%) (Wt) 1.330
4 Nickel (Ni) (PPM) 3450
5 Cobalt (Co) (PPM) 530
6 Aluminum (Al) (PPM) 340
2. Physical detection index:
(1) Particle size: d (D) 50 7.0 micrometers, D 90 18 microns;
(2) Tap density: d, d Vibration device ＝2.45g/cm 3 ；
(3) When the crystal phase structure (SEM image) is observed by an electron microscope, the surface of the particles is smooth, but the particles are uneven in size, some particles are bonded into clusters, and the temperature is high, so that single crystals are bonded together.
Comparative example 3:
taking 2000kg of manganese sulfate raw material, and directly conveying the raw material to an original general rotary kiln, namely a rotary kiln without saw teeth and grinding rollers, wherein the diameter of the rotary kiln is 2.2 meters and the length of the rotary kiln is 12 meters through detecting that the impurity content in the raw material meets the index requirement; the use of natural gas combustion, calcination temperature, calcination time, tail gas treatment mode, post-calcination material shaping, etc. were the same as in example 1.
Product detection results:
1. chemical element detection indexes of the product:
numbering device Chemical composition Index (I)
1 Manganese (Mn) (%) as a main content (Wt) 65.00
2 Sulfur (S) (%) (Wt) 4.59
3 Magnesium (Mg) (%) (Wt) 1.270
4 Nickel (Ni) (PPM) 500
5 Cobalt (Co) (PPM) 150
6 Aluminum (Al) (PPM) 150
2. The photo of the product is shown in figure 8, the calcined product is wrapped to form ball groups with different sizes, and the maximum size is that
10cm, the unreacted manganese sulfate is wrapped in the center, and the white point in the picture is manganese sulfate.
The number of equipment and the scale of processing described herein are intended to simplify the description of the present application. The application, modification and variation of the preparation method of the single crystal trimanganese tetroxide of the present application will be apparent to those skilled in the art.
Although embodiments of the present application have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the application would be readily apparent to those skilled in the art, and accordingly, the application is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.

Claims (4)

1. The preparation method of the battery-grade monocrystalline manganous-manganic oxide is characterized by comprising the following steps: putting a manganese sulfate raw material or a manganese sulfate raw material containing impurities into a battery grade monocrystal manganous-manganic oxide preparation device, and calcining at 900-1300 ℃ for 8-16 hours;
the battery-level monocrystal manganous-manganic oxide preparation device comprises a rotary kiln, wherein two damage and wrapping mechanisms are arranged in the rotary kiln at intervals, each damage and wrapping mechanism comprises a plurality of blocking teeth and a grinding roller, the blocking teeth are arranged on the inner wall of the rotary kiln in a spacing ring manner, and the grinding roller is arranged between the kiln tail and the blocking teeth; the heights of the blocking teeth are consistent with the diameter of the grinding roller, and the intervals of the blocking teeth are 2/3 of the diameter of the grinding roller; the grinding roller is cylindrical, and the axis of the grinding roller is parallel to the axis of the rotary kiln; the number of the grinding rollers is at least three;
the calcination of the manganese sulfate raw material in the rotary kiln is required to pass through four stages, namely a preheating and dehydration stage, a pre-reaction stage, a reaction stage and a monocrystal forming and cooling stage, and two damage wrapping mechanisms are respectively arranged at the positions of the pre-reaction stage and the reaction stage; wherein the temperature of the part of the broken wrapping mechanism close to the kiln tail is at least 1100 ℃, and the temperature of the part of the broken wrapping mechanism close to the kiln head is at least 1150 ℃.
2. The method for preparing single crystal manganous oxide of battery grade according to claim 1, further comprising:
and cooling the calcined material to normal temperature at a cooling speed of 5-20 ℃/min.
3. The method for preparing single crystal manganous oxide of battery grade according to claim 2, further comprising:
pulverizing the cooled material to D 50 Is 5-10 micrometers, D 90 15-20 microns.
4. The method for producing a battery-grade single crystal manganous oxide according to claim 2, wherein the content of impurity elements in the impurity-containing manganese sulfate raw material is detected before calcination, and if it is lower than a predetermined value, a corresponding impurity element compound is added.
CN202110459602.3A 2021-04-27 2021-04-27 Battery grade monocrystal manganous manganic oxide preparation device and method Active CN112897583B (en)

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