CN112968166A - Preparation method of lithium manganate positive electrode material - Google Patents

Preparation method of lithium manganate positive electrode material Download PDF

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CN112968166A
CN112968166A CN202110299387.5A CN202110299387A CN112968166A CN 112968166 A CN112968166 A CN 112968166A CN 202110299387 A CN202110299387 A CN 202110299387A CN 112968166 A CN112968166 A CN 112968166A
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lithium manganate
preparation
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electrode material
water
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陈鹏鹛
陈静波
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Anhui Boshi Hi Hi Tech New Material Co ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to the field of chemical power supplies, in particular to a preparation method of a lithium manganate positive electrode material, which comprises the following steps: s1, weighing raw and auxiliary materials: weighing raw and auxiliary materials according to the molar weight ratio of a manganese compound, sodium sulfate, a lithium source, a doping element M, a 60% hydrogen peroxide solution and ammonia water =1.8:0.7:0.9:0.1:20:50, and storing the raw and auxiliary materials for later use after weighing; s2, mixing raw and auxiliary materials: firstly, adding a proper amount of deionized water into a stirring type reaction kettle, then adding a weighed amount of manganese compound and a weighed amount of sodium sulfate in S1 into the stirring type reaction kettle, and opening the stirring type reaction kettle until the manganese compound and the sodium sulfate are dissolved in the deionized water. The method has the beneficial effects that Mn2O3 generated by a chemical precipitation method and a roasting method is used as a precursor, and the method has the advantages of manganese dioxide and manganous-manganic oxide, can meet the requirements of high-end lithium manganate, can produce a lithium manganate product with excellent performance, and saves cost.

Description

Preparation method of lithium manganate positive electrode material
Technical Field
The invention relates to the field of chemical power sources, in particular to a preparation method of a lithium manganate positive electrode material.
Background
The lithium ion battery has the characteristics of high energy density, high working voltage, good cycle performance, small self-discharge, small volume and the like, is widely applied to the fields of mobile communication equipment, small electronic products, aerospace and the like, and the lithium manganate material serving as one of the lithium ion battery anode materials has the advantages of rich resource reserves, no pollution, good safety performance, long cycle life and the like, and meets the requirements of the current market on the safety, service life and production cost of the battery.
Chinese patent No. CN111640937A provides a preparation method of a single-crystal lithium manganate material, weighing raw materials of a manganese compound and sodium sulfate according to a required proportion, adding the raw materials into deionized water, stirring for 1-10h, reacting for 10-15h at the temperature of 100 ℃ and 150 ℃, cooling, filtering, collecting precipitate, washing for 1-5 times by using the deionized water, and drying to obtain a precursor of beta-MnO 2; mixing the obtained beta-MnO 2 precursor with a lithium source and a compound doped with an element M according to a certain proportion, and sintering to obtain a finished product, wherein the molecular formula of the finished product is Li1+ aMn2-a-bMbO4, and a is more than or equal to 0 and less than or equal to 0.2.
At present, manganese raw materials of lithium manganate produced in batch are mainly manganese dioxide and trimanganese tetroxide, manganese dioxide is high in raw material impurities and different in particle morphology due to the reason of a preparation process, the requirement of high-end lithium manganate cannot be met, trimanganese tetroxide is low in impurities and can be made into microscopic spherical particles, oxygen absorption is required due to the reaction of lithium manganate produced by the manganese dioxide, a plate body effect occurs, oxygen cannot permeate into materials, the performance of lithium manganate can only be improved by reducing the charging amount, the cost is high, and therefore the preparation method of the lithium manganate anode material needs to be researched and developed urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium manganate cathode material, which aims to solve the problems that the raw material impurities of manganese dioxide proposed in the background technology are high, the particle morphology is different, the requirement of high-end lithium manganate cannot be met, oxygen absorption is required in the reaction of producing lithium manganate by using trimanganese tetroxide, a plate body effect occurs, and the cost is high due to the preparation process.
The technical scheme of the invention is as follows: a preparation method of a lithium manganate positive electrode material comprises the following steps:
s1, weighing raw and auxiliary materials: weighing raw and auxiliary materials according to the molar ratio of manganese compound, sodium sulfate, lithium source, doping element M, 60% hydrogen peroxide solution and ammonia water =0.7-2:0.7-0.8:0.9-1.1:0-0.2:20-30:50-70, and storing the raw and auxiliary materials for later use after weighing;
s2, mixing raw and auxiliary materials: firstly, adding a proper amount of deionized water into a stirring type reaction kettle, then adding a weighed amount of manganese compound and a weighed amount of sodium sulfate into the stirring type reaction kettle in S1, starting the stirring type reaction kettle until the manganese compound and the sodium sulfate are dissolved in the deionized water to form a suspension, then adding 60% hydrogen peroxide solution and ammonia water into the ionized water, after the addition of the 60% hydrogen oxide solution and the ammonia water is finished, finally, heating the suspension in a constant-temperature water bath kettle to ensure that the suspension is rapidly boiled, then cooling the suspension, filtering, and collecting precipitates;
s3, preparing Mn2O3Precursor: firstly drying the precipitate obtained in S2 below 100 ℃, then placing the dried precipitate into an argon atmosphere furnace, and roasting at the temperature of 200-300 ℃ for 24-36h to obtain Mn2O3A precursor;
s4, sintering a finished product: the Mn obtained in S3 was added2O3And adding a proper amount of pure water into the precursor, the lithium source weighed in S1 and the compound doped with the element M to mix and pelletize to form a granular mixture, then putting the granular mixture into a sintering machine, sintering at the temperature of 1000-1100 ℃ for 20-24h, and naturally crystallizing to obtain a finished product.
Further, the manganese compound in S1 is MnO or MnO2、Mn203、Mn3O4、Mn2O5、Mn03One or more of them.
Furthermore, the doping element M in S1 is one or more of Al, Ti, Zr, Si, Zn, Mg, Ga, B, Cr, Co and Y.
Further, in S2, when the hydrogen oxide solution and the ammonia water are added to the ionized water, the hydrogen oxide solution and the ammonia water are added slowly while controlling the adding speed of the hydrogen peroxide solution and the ammonia water.
Further, in the step S2, when the hydrogen oxide solution and the ammonia water are added to the ionized water, the reaction system should be kept weakly acidic, and the pH value of the reaction system should be kept at 6.9-7.3.
Further, the rotation speed of the stirring type reaction kettle in the S2 is 200-500r/min, and the stirring time is 10-15 min.
Further, the heating temperature of the constant-temperature water bath kettle in the S2 is 100-150 ℃, and the heating time is 4-20min after the suspension is boiled.
Further, after the precipitate is collected in S2, the precipitate should be rinsed 3-5 times with pure water until the precipitate forms particles with uniform color and no impurities on the surface.
Further, the mixing time in the S4 is 2.5-3min, and the diameter of the sphere after pelletizing is 20-25 mm.
Further, the molecular formula of the finished product obtained in the S4 is LiaMn2-bMbO4A is more than or equal to 1 and less than or equal to 1.2, and b is more than 0 and less than or equal to 0.2.
Compared with the prior art, the preparation method of the lithium manganate cathode material provided by the invention has the following improvements and advantages:
(1) the invention generates Mn by a chemical precipitation method and a roasting method2O3As a precursor, the lithium manganate has the advantages of manganese dioxide and manganous-manganic oxide, can meet the requirement of high-end lithium manganate, can produce a lithium manganate product with excellent performance, and simultaneously saves cost.
(2) The lithium manganate material produced by the invention is prepared by mixing Mn2O3As a precursor, Mn is then added2O3The precursor is mixed with a lithium source and a doping element compound and sintered to obtain a finished product, and the finished product has the advantages of small gap, high compaction density, good rate capability, high initial release and cycle performance and the like.
(3) According to the invention, the doping element M is adopted, and the material is doped and modified, so that the safety performance and the high-temperature cycle performance of the lithium ion battery prepared from the lithium manganate material can be obviously improved.
(4) The invention not only has excellent high-temperature storage and high-temperature cycle performance, but also has very high energy density, and completely meets the requirements of the field of electric automobiles and electric bicycles for the anode material of the lithium ion battery.
Drawings
The invention is further explained below with reference to the figures and examples.
FIG. 1 is a flow chart of the present invention.
Detailed Description
The present invention will be described in detail with reference to fig. 1, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A preparation method of a lithium manganate positive electrode material comprises the following steps:
s1, weighing raw and auxiliary materials: weighing raw and auxiliary materials according to the molar weight ratio of a manganese compound, sodium sulfate, a lithium source, a doping element M, a 60% hydrogen peroxide solution and ammonia water =1.8:0.7:0.9:0.1:20:50, and storing the raw and auxiliary materials for later use after weighing;
s2, mixing raw and auxiliary materials: firstly, adding a proper amount of deionized water into a stirring type reaction kettle, then adding a weighed amount of manganese compound and a weighed amount of sodium sulfate into the stirring type reaction kettle in S1, starting the stirring type reaction kettle until the manganese compound and the sodium sulfate are dissolved in the deionized water to form a suspension, then adding 60% hydrogen peroxide solution and ammonia water into the ionized water, after the addition of the 60% hydrogen oxide solution and the ammonia water is finished, finally, heating the suspension in a constant-temperature water bath kettle to ensure that the suspension is rapidly boiled, then cooling the suspension, filtering, and collecting precipitates;
s3, preparing Mn2O3Precursor: the precipitate obtained in S2 was first dried at 100 ℃ and then the dried precipitate was put into an argon atmosphere furnace and calcined at 200 ℃ for 24 hours to obtain Mn2O3A precursor;
s4, sintering a finished product: the Mn obtained in S3 was added2O3Adding a proper amount of pure water into the precursor, the lithium source weighed in S1 and the compound doped with the element M to mix and pelletize to form a granular mixture, and then putting the granular mixture into the furnaceSintering in a sintering machine at 1000 deg.c for 20 hr to crystallize naturally to obtain the product.
Further, the manganese compound in S1 is MnO.
Further, the doping element M in S1 is Al.
Further, in S2, when the hydrogen oxide solution and the ammonia water are added to the ionized water, the hydrogen oxide solution and the ammonia water are added slowly while controlling the addition rate of the hydrogen peroxide solution and the ammonia water.
Further, in S2, when the hydrogen oxide solution and the aqueous ammonia are added to the ionized water, the reaction system should be kept weakly acidic, and the pH of the reaction system should be kept at 6.9.
Further, the rotation speed of the stirring type reaction kettle in the S2 is 200r/min, and the stirring time is 10 min.
Further, the heating temperature of the constant-temperature water bath kettle in S2 is 100-150 ℃, and the heating time is 40min after the suspension is boiled.
Further, after the precipitate is collected in S2, the precipitate should be rinsed 3 times with pure water until the precipitate forms particles with uniform color and no impurities on the surface.
Further, the mixing time in S4 was 2.5min, and the sphere diameter after pelletization was 20 mm.
Further, the molecular formula of the finished product obtained in S4 is LiaMn2-bMbO4A is more than or equal to 1 and less than or equal to 1.2, and b is more than 0 and less than or equal to 0.2.
Example two
A preparation method of a lithium manganate positive electrode material comprises the following steps:
s1, weighing raw and auxiliary materials: weighing raw and auxiliary materials according to the molar weight ratio of a manganese compound, sodium sulfate, a lithium source, a doping element M, a 60% hydrogen peroxide solution and ammonia water =1.6:0.7:0.9:0.2:20:50, and storing the raw and auxiliary materials for later use after weighing;
s2, mixing raw and auxiliary materials: firstly, adding a proper amount of deionized water into a stirring type reaction kettle, then adding a weighed amount of manganese compound and a weighed amount of sodium sulfate into the stirring type reaction kettle in S1, starting the stirring type reaction kettle until the manganese compound and the sodium sulfate are dissolved in the deionized water to form a suspension, then adding 60% hydrogen peroxide solution and ammonia water into the ionized water, after the addition of the 60% hydrogen oxide solution and the ammonia water is finished, finally, heating the suspension in a constant-temperature water bath kettle to ensure that the suspension is rapidly boiled, then cooling the suspension, filtering, and collecting precipitates;
s3, preparing Mn2O3Precursor: the precipitate obtained in S2 was first dried at 100 ℃ and then the dried precipitate was put into an argon atmosphere furnace and calcined at 200 ℃ for 24 hours to obtain Mn2O3A precursor;
s4, sintering a finished product: the Mn obtained in S3 was added2O3And adding a proper amount of pure water into the precursor, the lithium source weighed in S1 and the compound doped with the element M to mix and pelletize to form a granular mixture, putting the granular mixture into a sintering machine, sintering at 1000 ℃ for 20 hours, and naturally crystallizing to obtain a finished product.
Further, the manganese compound in S1 is MnO2。
Further, the doping element M in S1 is Ti.
Further, in S2, when the hydrogen oxide solution and the ammonia water are added to the ionized water, the hydrogen oxide solution and the ammonia water are added slowly while controlling the addition rate of the hydrogen peroxide solution and the ammonia water.
Further, in S2, when the hydrogen oxide solution and the aqueous ammonia are added to the ionized water, the reaction system should be kept weakly acidic, and the pH of the reaction system should be kept at 6.9.
Further, the rotation speed of the stirring type reaction kettle in the S2 is 200r/min, and the stirring time is 10 min.
Further, in S2, the temperature of the constant temperature water bath is 100 deg.C, and the heating time is 4min after the suspension is boiled.
Further, after the precipitate is collected in S2, the precipitate should be rinsed 3 times with pure water until the precipitate forms particles with uniform color and no impurities on the surface.
Further, the mixing time in S4 was 2.5min, and the sphere diameter after pelletization was 20 mm.
Further, S4 the molecular formula of the finished product is LiaMn2-bMbO4A is more than or equal to 1 and less than or equal to 1.2, and b is more than 0 and less than or equal to 0.2.
EXAMPLE III
A preparation method of a lithium manganate positive electrode material comprises the following steps:
s1, weighing raw and auxiliary materials: weighing raw and auxiliary materials according to the molar weight ratio of a manganese compound, sodium sulfate, a lithium source, a doping element M, a 60% hydrogen peroxide solution and ammonia water =1.7:0.7:0.9:0.15:20:50, and storing the raw and auxiliary materials for later use after weighing;
s2, mixing raw and auxiliary materials: firstly, adding a proper amount of deionized water into a stirring type reaction kettle, then adding a weighed amount of manganese compound and a weighed amount of sodium sulfate into the stirring type reaction kettle in S1, starting the stirring type reaction kettle until the manganese compound and the sodium sulfate are dissolved in the deionized water to form a suspension, then adding 60% hydrogen peroxide solution and ammonia water into the ionized water, after the addition of the 60% hydrogen oxide solution and the ammonia water is finished, finally, heating the suspension in a constant-temperature water bath kettle to ensure that the suspension is rapidly boiled, then cooling the suspension, filtering, and collecting precipitates;
s3, preparing Mn2O3Precursor: the precipitate obtained in S2 was first dried at 100 ℃ and then the dried precipitate was put into an argon atmosphere furnace and calcined at 200 ℃ for 24 hours to obtain Mn2O3A precursor;
s4, sintering a finished product: the Mn obtained in S3 was added2O3And adding a proper amount of pure water into the precursor, the lithium source weighed in S1 and the compound doped with the element M to mix and pelletize to form a granular mixture, putting the granular mixture into a sintering machine, sintering at 1000 ℃ for 20 hours, and naturally crystallizing to obtain a finished product.
Further, the manganese compound in S1 is Mn203。
Further, the doping element M in S1 is Zr.
Further, in S2, when the hydrogen oxide solution and the ammonia water are added to the ionized water, the hydrogen oxide solution and the ammonia water are added slowly while controlling the addition rate of the hydrogen peroxide solution and the ammonia water.
Further, in S2, when the hydrogen oxide solution and the aqueous ammonia are added to the ionized water, the reaction system should be kept weakly acidic, and the pH of the reaction system should be kept at 6.9.
Further, the rotation speed of the stirring type reaction kettle in the S2 is 200r/min, and the stirring time is 10 min.
Further, in S2, the temperature of the constant temperature water bath is 100 deg.C, and the heating time is 4min after the suspension is boiled.
Further, after the precipitate is collected in S2, the precipitate should be rinsed 3 times with pure water until the precipitate forms particles with uniform color and no impurities on the surface.
Further, the mixing time in S4 was 2.5min, and the sphere diameter after pelletization was 20 mm.
Further, the molecular formula of the finished product obtained in S4 is LiaMn2-bMbO4A is more than or equal to 1 and less than or equal to 1.2, and b is more than 0 and less than or equal to 0.2.
The manganese compounds adopted in the first embodiment, the second embodiment and the third embodiment have different types and molar weight ratios, the doping element M has different types and molar weight ratios, and other parameters are consistent, so that the effect is the best in the third embodiment by comparing the finally obtained lithium manganate through experiments.
The working principle is as follows: firstly, weighing raw and auxiliary materials according to a molar ratio of manganese compound, sodium sulfate, lithium source and doping element M:60% hydrogen peroxide solution and ammonia water =1.7:0.7:0.9:0.15:20:50, storing the raw and auxiliary materials for later use after weighing, then adding a proper amount of deionized water into a stirring type reaction kettle, weighing the manganese compound and the sodium sulfate, adding the manganese compound and the sodium sulfate into the stirring type reaction kettle, opening the stirring type reaction kettle, regulating the rotating speed to be 200r/min for 10min until the manganese compound and the sodium sulfate are dissolved in the deionized water to form a suspension, slowly adding the 60% hydrogen peroxide solution and the ammonia water into the ionized water, keeping the pH value of the reaction system to be 6.9 in the adding process, heating the suspension in a constant temperature water bath after adding the 60% hydrogen oxide solution and the ammonia water, heating to 100 ℃, the suspension is rapidly boiled untilBoiling the suspension for 4min, cooling the suspension, filtering, collecting precipitate, rinsing the precipitate with pure water for 3 times until the precipitate forms particles with uniform color and no impurities on the surface, drying the obtained precipitate at 100 deg.C, calcining the dried precipitate in an argon atmosphere furnace at 200 deg.C for 24 hr to obtain Mn2O3Precursor, then Mn2O3Adding a proper amount of pure water into the precursor, the lithium source weighed in S1 and the compound doped with the element M, mixing and pelletizing for 2.5min, wherein the diameter of the pelletized sphere is 20mm, forming a granular mixture, finally putting the granular mixture into a sintering machine, sintering at 1000 ℃ for 20h, and naturally crystallizing to obtain a finished product LiaMn2-bMbO4A is more than or equal to 1 and less than or equal to 1.2, and b is more than 0 and less than or equal to 0.2.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A preparation method of a lithium manganate positive electrode material is characterized by comprising the following steps: the method comprises the following steps:
s1, weighing raw and auxiliary materials: weighing raw and auxiliary materials according to the molar ratio of manganese compound, sodium sulfate, lithium source, doping element M, 60% hydrogen peroxide solution and ammonia water =0.7-2:0.7-0.8:0.9-1.1:0-0.2:20-30:50-70, and storing the raw and auxiliary materials for later use after weighing;
s2, mixing raw and auxiliary materials: firstly, adding a proper amount of deionized water into a stirring type reaction kettle, then adding a weighed amount of manganese compound and a weighed amount of sodium sulfate into the stirring type reaction kettle in S1, starting the stirring type reaction kettle until the manganese compound and the sodium sulfate are dissolved in the deionized water to form a suspension, then adding 60% hydrogen peroxide solution and ammonia water into the ionized water, after the addition of the 60% hydrogen oxide solution and the ammonia water is finished, finally, heating the suspension in a constant-temperature water bath kettle to ensure that the suspension is rapidly boiled, then cooling the suspension, filtering, and collecting precipitates;
s3, preparing Mn2O3Precursor: firstly drying the precipitate obtained in S2 at 100 ℃, then placing the dried precipitate into an argon atmosphere furnace, and roasting at the temperature of 200-300 ℃ for 24-36h to obtain Mn2O3A precursor;
s4, sintering a finished product: the Mn obtained in S3 was added2O3And adding a proper amount of pure water into the precursor, the lithium source weighed in S1 and the compound doped with the element M to mix and pelletize to form a granular mixture, then putting the granular mixture into a sintering machine, sintering at the temperature of 1000-1100 ℃ for 20-24h, and naturally crystallizing to obtain a finished product.
2. The preparation method of the lithium manganate positive electrode material according to claim 1, characterized in that: the manganese compound in S1 is MnO or MnO2、Mn203、Mn3O4、Mn2O5、Mn03One or more of them.
3. The preparation method of the lithium manganate positive electrode material according to claim 1, characterized in that: and the doping element M in the S1 is one or more of Al, Ti, Zr, Si, Zn, Mg, Ga, B, Cr, Co and Y.
4. The preparation method of the lithium manganate positive electrode material according to claim 1, characterized in that: in the step S2, when the hydrogen oxide solution and the ammonia water are added to the ionized water, the hydrogen oxide solution and the ammonia water are added slowly while controlling the adding speed of the hydrogen peroxide solution and the ammonia water.
5. The preparation method of the lithium manganate positive electrode material according to claim 1, characterized in that: in the step S2, when the hydrogen oxide solution and the ammonia water are added to the ionized water, the reaction system should be kept weakly acidic, and the pH value of the reaction system should be kept at 6.9-7.3.
6. The preparation method of the lithium manganate positive electrode material according to claim 1, characterized in that: the rotation speed of the stirring type reaction kettle in the S2 is 200-500r/min, and the stirring time is 10-15 min.
7. The preparation method of the lithium manganate positive electrode material according to claim 1, characterized in that: the heating temperature of the constant-temperature water bath kettle in the S2 is 100-150 ℃, and the heating time is 4-20min after the suspension is boiled.
8. The preparation method of the lithium manganate positive electrode material according to claim 1, characterized in that: after the precipitate is collected in S2, the precipitate should be rinsed 3-5 times with pure water until the precipitate forms particles with uniform color and no impurities on the surface.
9. The preparation method of the lithium manganate positive electrode material according to claim 1, characterized in that: the mixing time in the S4 is 2.5-3min, and the diameter of the pelletized sphere is 20-25 mm.
10. The preparation method of the lithium manganate positive electrode material according to claim 1, characterized in that: the molecular formula of the finished product obtained in S4 is LiaMn2-bMbO4A is more than or equal to 1 and less than or equal to 1.2, and b is more than 0 and less than or equal to 0.2.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3033899B1 (en) * 1999-01-12 2000-04-17 宇部興産株式会社 Positive electrode active material for lithium secondary battery, method for producing the same and use thereof
CN1283313A (en) * 1997-12-22 2001-02-07 石原产业株式会社 Lithium manganate, method of producing the same and lithium cell using the same
EP1116692A1 (en) * 1999-03-30 2001-07-18 Toho Titanium Co., Ltd. Method for preparing lithium manganate, lithium manganate, positive electrode for lithium secondary cell containing the same as active material and lithium secondary cell
KR20080022057A (en) * 2006-09-05 2008-03-10 니폰 가가쿠 고교 가부시키가이샤 Lithium manganate for positive electrode sub-active material of lithium secondary battery, method for preparing lithium manganate, positive electrode active material of lithium secondary battery and lithium secondary battery
CN102544473A (en) * 2012-02-29 2012-07-04 河南理工大学 Lithium ion battery anode material layered lithium manganese oxide and manufacturing method thereof
KR20150020145A (en) * 2013-08-14 2015-02-25 이화여자대학교 산학협력단 LAYERED POROUS Mn2O3 NANOSHEET AND PREPARING METHOD OF THE SAME
CN104876274A (en) * 2015-06-16 2015-09-02 安徽机电职业技术学院 Preparation method of manganous-manganic oxide
CN105152218A (en) * 2015-08-05 2015-12-16 柳州豪祥特科技有限公司 Preparation method of layered lithium manganate
CN106006747A (en) * 2016-05-13 2016-10-12 中国科学院宁波材料技术与工程研究所 Method for easily and conveniently preparing Mn3O4 nanopowder and product of method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1283313A (en) * 1997-12-22 2001-02-07 石原产业株式会社 Lithium manganate, method of producing the same and lithium cell using the same
JP3033899B1 (en) * 1999-01-12 2000-04-17 宇部興産株式会社 Positive electrode active material for lithium secondary battery, method for producing the same and use thereof
EP1116692A1 (en) * 1999-03-30 2001-07-18 Toho Titanium Co., Ltd. Method for preparing lithium manganate, lithium manganate, positive electrode for lithium secondary cell containing the same as active material and lithium secondary cell
KR20080022057A (en) * 2006-09-05 2008-03-10 니폰 가가쿠 고교 가부시키가이샤 Lithium manganate for positive electrode sub-active material of lithium secondary battery, method for preparing lithium manganate, positive electrode active material of lithium secondary battery and lithium secondary battery
CN102544473A (en) * 2012-02-29 2012-07-04 河南理工大学 Lithium ion battery anode material layered lithium manganese oxide and manufacturing method thereof
KR20150020145A (en) * 2013-08-14 2015-02-25 이화여자대학교 산학협력단 LAYERED POROUS Mn2O3 NANOSHEET AND PREPARING METHOD OF THE SAME
CN104876274A (en) * 2015-06-16 2015-09-02 安徽机电职业技术学院 Preparation method of manganous-manganic oxide
CN105152218A (en) * 2015-08-05 2015-12-16 柳州豪祥特科技有限公司 Preparation method of layered lithium manganate
CN106006747A (en) * 2016-05-13 2016-10-12 中国科学院宁波材料技术与工程研究所 Method for easily and conveniently preparing Mn3O4 nanopowder and product of method

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LINGLING ZHANG等: "Synthesis of porous Mn2O3 embedded in reduced graphene oxide as advanced anode materials for lithium storage", 《 NEW J. CHEM.》 *
ROBERTO PÉ REZ-GARIBAY等: "Synthesis of Mn2O3from Manganese Sulfated Leaching Solutions", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 *
李叶珠等: "高活性Mn2O3制备尖晶石LiMn2O4及其性能研究", 《稀有金属》 *
陈志文等: "纳米Mn2O3的制备及其分形凝聚", 《中国科学技术大学学报》 *

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