CN113120964A - Preparation method of spherical lithium manganate material - Google Patents

Preparation method of spherical lithium manganate material Download PDF

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Publication number
CN113120964A
CN113120964A CN202110304544.7A CN202110304544A CN113120964A CN 113120964 A CN113120964 A CN 113120964A CN 202110304544 A CN202110304544 A CN 202110304544A CN 113120964 A CN113120964 A CN 113120964A
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lithium manganate
raw materials
glue solution
mixing
manganate material
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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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Anhui Boshi Hi Hi Tech New Material Co ltd
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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
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • 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
    • 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
    • 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
    • C01P2004/32—Spheres
    • 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
    • C01P2006/10—Solid density
    • 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
    • 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

Abstract

The invention relates to the field of preparation of lithium manganate materials, in particular to a preparation method of a spherical lithium manganate material, which comprises the following steps: s1, mixing raw materials: weighing three raw materials of manganese oxide, lithium source compound and metal ion substance according to the required proportion, and then putting the raw materials into mixing equipment for mixing, thereby uniformly mixing the raw materials; s2, primary sintering: feeding the mixed raw materials in the previous step into a muffle furnace, and then starting the muffle furnace to pre-burn the mixed raw materials to obtain the lithium manganate material, wherein the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2; s3, glue solution preparation: weighing the raw materials required by the glue solution according to the required proportion. The method has the beneficial effects that the glue solution is added during grinding, so that the glue solution is uniformly coated on the surface of the lithium manganate material, the gram volume and the high-temperature cycle performance of the lithium manganate are improved, the service life of the lithium manganate battery is prolonged, and the electrochemical performance of the lithium manganate material can be improved by adopting the preparation of nano-electrolytic MnO ₂, Mn3O4 and LiOH during the preparation of the lithium manganate.

Description

Preparation method of spherical lithium manganate material
Technical Field
The invention relates to the field of preparation of lithium manganate materials, in particular to a preparation method of a spherical lithium manganate material.
Background
Lithium manganate is one of the more promising lithium ion anode materials, and compared with the traditional anode materials such as lithium cobaltate, the lithium manganate has the advantages of rich resources, low cost, no pollution, good safety, good rate capability and the like, and is an ideal anode material of a power battery.
Chinese patent No. CN107565122A provides a preparation method of a doped nickel cobalt lithium manganate positive electrode material. The preparation method comprises the following specific processes: and carrying out ball milling and mixing on the nickel-cobalt-manganese precursor, the niobium source and the lithium salt according to a certain proportion, and carrying out operations such as pre-sintering, secondary ball milling, calcining in a high-temperature atmosphere furnace and the like to obtain the doped nickel-cobalt lithium manganate cathode material.
Chinese patent No. CN104600281A provides a preparation method of a lithium manganate material, which is characterized in that: firstly, uniformly mixing a lithium source and a manganese source according to a molar ratio, putting the mixture into a box-type resistance furnace for high-temperature sintering, and cooling to room temperature to obtain the lithium manganate material.
At present, batteries prepared from the existing lithium manganate material have low volume specific capacity, poor cycle performance and fast high-temperature cycle attenuation, so that the service life of the lithium manganate battery is short, and meanwhile, most of the existing lithium manganate prepared from manganese salt and lithium salt has poor electrochemical performance, so that the research and development of a preparation method of a spherical lithium manganate material are urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of a spherical lithium manganate material, which aims to solve the problems that a battery prepared from lithium manganate provided in the background art has short service life and lithium manganate prepared from manganese salt and lithium salt has poor electrochemical performance.
The technical scheme of the invention is as follows: a preparation method of a spherical lithium manganate material comprises the following steps:
s1, mixing raw materials: weighing three raw materials of manganese oxide, lithium source compound and metal ion substance according to the required proportion, and then putting the raw materials into mixing equipment for mixing, thereby uniformly mixing the raw materials;
s2, primary sintering: feeding the mixed raw materials in the previous step into a muffle furnace, and then starting the muffle furnace to pre-burn the mixed raw materials to obtain the lithium manganate material, wherein the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2;
s3, glue solution preparation: weighing raw materials required by the glue solution according to the required proportion, and then putting the raw materials into a high-speed stirrer for mixing to obtain the glue solution;
s4, grinding and mixing: adding the prepared glue solution into a ball mill according to a certain proportion to perform wet ball milling, wherein the glue solution is uniformly adhered to the surface of a lithium manganate material in the ball milling process;
s5, granulating and drying: after the ball milling in the previous step is finished, putting the lithium manganate and the glue solution mixture into granulation drying equipment for drying, and meanwhile, completing granulation in the drying process, wherein the granulated particles are uniform in size and good in sphericity;
s6, secondary sintering: and (4) sending the lithium manganate particles after the last granulation step into the muffle furnace again, and then starting the muffle furnace to pre-burn the spherical raw materials after the granulation is finished, so as to obtain the finished lithium manganate material.
Further, the mass ratio of the manganese oxide to the lithium source compound in the S1 is 1-1.1:2, and the manganese oxide is nano electrolytic MnO2And Mn3O4, the lithium source compound being LiOH.
Further, the nano electrolytic MnO2The purity of the product with Mn3O4 is more than 99%, and the LiOH content is more than 95%.
Further, in the S1, the metal ion substance is one or more of rare earth elements La, Ce and Nd.
Further, the raw materials are mixed at different frequencies in the step S1, and the mixing time is 0.5-3 h.
Further, the pre-sintering time in the S2 is 5-12h, and the pre-sintering temperature is 400-800 ℃.
Further, the glue solution raw materials in the S3 are solvent, adhesive and coating material, and the solid content of the mixed glue solution is controlled to be 5-30%.
Further, the solvent is pure water, the binder is PVA, and the coating material is one of oxides of Mg, Al, Ti, W, Zr, Ga, B, Cr, Co and the like.
Further, the mass ratio of the glue solution in the S4 to the lithium manganate material is as follows: 1:1-10, and the ball milling time is 0.5-5 h.
Further, the secondary sintering temperature in the S6 is 500-800 ℃, the sintering time is 10-30h, and the density of the sintered product is more than 3.1g/cm 3.
Compared with the prior art, the invention provides a preparation method of a spherical lithium manganate material by improvement, which has the following improvements and advantages:
(1) according to the glue solution designed by the invention, when the lithium manganate material is ground, the glue solution can be added into a grinding machine, so that the glue solution is uniformly coated on the surface of the lithium manganate material, and thus the gram capacity and high-temperature cycle performance of lithium manganate are improved, and the service life of a lithium manganate battery is prolonged.
(2) Nano electrolytic MnO designed by the invention2Mn3O4 and LiOH with a tetragonal spinel structure, and nano electrolytic MnO is adopted when preparing lithium manganate2Mn3O4 and LiOH can improve the electrochemical performance of the lithium manganate material.
(3) After the metal ion substance adopted by the invention is mixed with the lithium manganate material, the high-temperature cycle performance of the lithium manganate material can be improved by doping zirconium, rare earth elements and neodymium, and the electrochemical performance of the lithium manganate material is further improved.
(4) The preparation method of the lithium manganate has the advantages of simple process during preparation, lower preparation difficulty of the lithium manganate material, easy control and operation of the preparation process, lower production cost and better industrialization prospect.
Drawings
The invention is further explained below with reference to the figures and examples:
FIG. 1 is a flow chart of the preparation 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.
The invention provides a preparation method of a spherical lithium manganate material by improvement, as shown in figure 1, comprising the following steps:
s1, mixing raw materials: weighing three raw materials of manganese oxide, lithium source compound and metal ion substance according to the required proportion, and then putting the raw materials into mixing equipment for mixing, thereby uniformly mixing the raw materials;
s2, primary sintering: feeding the mixed raw materials in the previous step into a muffle furnace, and then starting the muffle furnace to pre-burn the mixed raw materials to obtain the lithium manganate material, wherein the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2;
s3, glue solution preparation: weighing raw materials required by the glue solution according to the required proportion, and then putting the raw materials into a high-speed stirrer for mixing to obtain the glue solution;
s4, grinding and mixing: adding the prepared glue solution into a ball mill according to a certain proportion to perform wet ball milling, wherein the glue solution is uniformly adhered to the surface of a lithium manganate material in the ball milling process;
s5, granulating and drying: after the ball milling in the previous step is finished, putting the lithium manganate and the glue solution mixture into granulation drying equipment for drying, and meanwhile, completing granulation in the drying process, wherein the granulated particles are uniform in size and good in sphericity;
s6, secondary sintering: and (4) sending the lithium manganate particles after the last granulation step into the muffle furnace again, and then starting the muffle furnace to pre-burn the spherical raw materials after the granulation is finished, so as to obtain the finished lithium manganate material.
Further, the mass ratio of the manganese oxide to the lithium source compound in S1 is 1.04:2, and the manganese oxide is nano electrolytic MnO2And Mn3O4, the lithium source compound being LiOH.
Further, nano-electrolytic MnO2The purity of the product with Mn3O4 is more than 99%, and the LiOH content is more than 95%.
Further, in S1, the metal ion substance is one or more of rare earth elements La (lanthanum), Ce (cerium) and Nd (neodymium).
Further, the raw materials were mixed at different frequencies in S1 for a mixing time of 2 hours.
Further, in S2, the burn-in time was 8 hours, and the burn-in temperature was 500 ℃.
Further, the glue solution raw materials in the S3 are solvent, adhesive and coating material, and the solid content of the mixed glue solution is controlled at 20%.
Further, the solvent is pure water, the binder is PVA (polyvinyl alcohol), and the coating material is Al.
Further, the mass ratio of the glue solution in the S4 to the lithium manganate material is as follows: 1:7, and the ball milling time is 0.5-5 h.
Furthermore, the secondary sintering temperature in S6 is 600 ℃, the sintering time is 12h, and the density of the sintered product is more than 3.1g/cm 3.
Example one
A preparation method of a spherical lithium manganate material comprises the following steps:
s1, mixing raw materials: weighing Mn3O4 and nano electrolytic MnO according to the required proportion2The preparation method comprises the following steps of (1) mixing three raw materials of LiOH and metal ion substances (La, Ce and Nd) in a mixing device, wherein the raw materials are mixed at different frequencies for 2 hours, so that the raw materials are uniformly mixed;
s2, primary sintering: feeding the mixed raw materials in the last step into a muffle furnace, then starting the muffle furnace to pre-sinter the mixed raw materials, wherein the pre-sintering time is 8 hours, and the pre-sintering temperature is 500 ℃, so that the lithium manganate material is obtained, the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2;
s3, glue solution preparation: weighing raw materials required by glue solution according to a required ratio, wherein the glue solution raw materials comprise a solvent, a binder and a coating material, the solvent is pure water, the binder is PVA (polyvinyl alcohol), and the coating material is Al, and then putting the raw materials into a high-speed mixer for mixing to obtain the glue solution with the solid content of 20%;
s4, grinding and mixing: adding the prepared glue solution into a ball mill according to a ratio of 1:5 after the same sintering for wet ball milling for 2h, wherein the glue solution is uniformly adhered to the surface of a lithium manganate material in the ball milling process;
s5, granulating and drying: after the ball milling in the previous step is finished, putting the lithium manganate and the glue solution mixture into granulation drying equipment for drying, and meanwhile, completing granulation in the drying process, wherein the granulated particles are uniform in size and good in sphericity;
s6, secondary sintering: and (3) feeding the lithium manganate particles after the last granulation step into a muffle furnace again, starting the muffle furnace to pre-sinter the spherical raw materials after the granulation is finished, wherein the sintering temperature is 600 ℃, and the sintering time is 12 hours, so that the lithium manganate material with the finished product density of more than 3.1g/cm3 is obtained.
Example two
A preparation method of a spherical lithium manganate material comprises the following steps:
s1, mixing raw materials: weighing Mn3O4 and nano electrolytic MnO according to the required proportion2The preparation method comprises the following steps of (1) mixing three raw materials of LiOH and metal ion substances (La, Ce and Nd) in a mixing device, wherein the raw materials are mixed at different frequencies for 2 hours, so that the raw materials are uniformly mixed;
s2, primary sintering: feeding the mixed raw materials in the last step into a muffle furnace, then starting the muffle furnace to pre-sinter the mixed raw materials, wherein the pre-sintering time is 8 hours, and the pre-sintering temperature is 500 ℃, so that the lithium manganate material is obtained, the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2;
s3, glue solution preparation: weighing raw materials required by glue solution according to a required ratio, wherein the glue solution raw materials comprise a solvent, a binder and a coating material, the solvent is pure water, the binder is PVA (polyvinyl alcohol), and the coating material is Al, and then putting the raw materials into a high-speed mixer for mixing to obtain the glue solution with the solid content of 20%;
s4, grinding and mixing: adding the prepared glue solution into a ball mill according to a ratio of 1:1, sintering the same time, and carrying out wet ball milling for 2h, wherein the glue solution is uniformly adhered to the surface of a lithium manganate material in the ball milling process;
s5, granulating and drying: after the ball milling in the previous step is finished, putting the lithium manganate and the glue solution mixture into granulation drying equipment for drying, and meanwhile, completing granulation in the drying process, wherein the granulated particles are uniform in size and good in sphericity;
s6, secondary sintering: and (3) feeding the lithium manganate particles after the last granulation step into a muffle furnace again, starting the muffle furnace to pre-sinter the spherical raw materials after the granulation is finished, wherein the sintering temperature is 600 ℃, and the sintering time is 12 hours, so that the lithium manganate material with the finished product density of more than 3.1g/cm3 is obtained.
EXAMPLE III
A preparation method of a spherical lithium manganate material comprises the following steps:
s1, mixing raw materials: weighing Mn3O4 and nano electrolytic MnO according to the required proportion2The preparation method comprises the following steps of (1) mixing three raw materials of LiOH and metal ion substances (La, Ce and Nd) in a mixing device, wherein the raw materials are mixed at different frequencies for 2 hours, so that the raw materials are uniformly mixed;
s2, primary sintering: feeding the mixed raw materials in the last step into a muffle furnace, then starting the muffle furnace to pre-sinter the mixed raw materials, wherein the pre-sintering time is 8 hours, and the pre-sintering temperature is 500 ℃, so that the lithium manganate material is obtained, the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2;
s3, glue solution preparation: weighing raw materials required by glue solution according to a required ratio, wherein the glue solution raw materials comprise a solvent, a binder and a coating material, the solvent is pure water, the binder is PVA (polyvinyl alcohol), and the coating material is Al, and then putting the raw materials into a high-speed mixer for mixing to obtain the glue solution with the solid content of 20%;
s4, grinding and mixing: adding the prepared glue solution into a ball mill according to a ratio of 1:3 after the same sintering for wet ball milling for 2h, wherein the glue solution is uniformly adhered to the surface of a lithium manganate material in the ball milling process;
s5, granulating and drying: after the ball milling in the previous step is finished, putting the lithium manganate and the glue solution mixture into granulation drying equipment for drying, and meanwhile, completing granulation in the drying process, wherein the granulated particles are uniform in size and good in sphericity;
s6, secondary sintering: and (3) feeding the lithium manganate particles after the last granulation step into a muffle furnace again, starting the muffle furnace to pre-sinter the spherical raw materials after the granulation is finished, wherein the sintering temperature is 600 ℃, and the sintering time is 12 hours, so that the lithium manganate material with the finished product density of more than 3.1g/cm3 is obtained.
Example four
A preparation method of a spherical lithium manganate material comprises the following steps:
s1, mixing raw materials: weighing Mn3O4 and nano electrolytic MnO according to the required proportion2The preparation method comprises the following steps of (1) mixing three raw materials of LiOH and metal ion substances (La, Ce and Nd) in a mixing device, wherein the raw materials are mixed at different frequencies for 2 hours, so that the raw materials are uniformly mixed;
s2, primary sintering: feeding the mixed raw materials in the last step into a muffle furnace, then starting the muffle furnace to pre-sinter the mixed raw materials, wherein the pre-sintering time is 8 hours, and the pre-sintering temperature is 500 ℃, so that the lithium manganate material is obtained, the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2;
s3, glue solution preparation: weighing raw materials required by glue solution according to a required ratio, wherein the glue solution raw materials comprise a solvent, a binder and a coating material, the solvent is pure water, the binder is PVA (polyvinyl alcohol), and the coating material is Al, and then putting the raw materials into a high-speed mixer for mixing to obtain the glue solution with the solid content of 20%;
s4, grinding and mixing: adding the prepared glue solution into a ball mill according to a ratio of 1:7 for wet ball milling for 2h, wherein the glue solution is uniformly adhered to the surface of the lithium manganate material in the ball milling process;
s5, granulating and drying: after the ball milling in the previous step is finished, putting the lithium manganate and the glue solution mixture into granulation drying equipment for drying, and meanwhile, completing granulation in the drying process, wherein the granulated particles are uniform in size and good in sphericity;
s6, secondary sintering: and (3) feeding the lithium manganate particles after the last granulation step into a muffle furnace again, starting the muffle furnace to pre-sinter the spherical raw materials after the granulation is finished, wherein the sintering temperature is 600 ℃, and the sintering time is 12 hours, so that the lithium manganate material with the finished product density of more than 3.1g/cm3 is obtained.
EXAMPLE five
A preparation method of a spherical lithium manganate material comprises the following steps:
s1, mixing raw materials: weighing Mn3O4 and nano electrolytic MnO according to the required proportion2The preparation method comprises the following steps of (1) mixing three raw materials of LiOH and metal ion substances (La, Ce and Nd) in a mixing device, wherein the raw materials are mixed at different frequencies for 2 hours, so that the raw materials are uniformly mixed;
s2, primary sintering: feeding the mixed raw materials in the last step into a muffle furnace, then starting the muffle furnace to pre-sinter the mixed raw materials, wherein the pre-sintering time is 8 hours, and the pre-sintering temperature is 500 ℃, so that the lithium manganate material is obtained, the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2;
s3, glue solution preparation: weighing raw materials required by glue solution according to a required ratio, wherein the glue solution raw materials comprise a solvent, a binder and a coating material, the solvent is pure water, the binder is PVA (polyvinyl alcohol), and the coating material is Al, and then putting the raw materials into a high-speed mixer for mixing to obtain the glue solution with the solid content of 20%;
s4, grinding and mixing: adding the prepared glue solution into a ball mill according to a ratio of 1:9 after the same sintering for wet ball milling for 2h, wherein the glue solution is uniformly adhered to the surface of a lithium manganate material in the ball milling process;
s5, granulating and drying: after the ball milling in the previous step is finished, putting the lithium manganate and the glue solution mixture into granulation drying equipment for drying, and meanwhile, completing granulation in the drying process, wherein the granulated particles are uniform in size and good in sphericity;
s6, secondary sintering: sending the lithium manganate particles after the last granulation step into a muffle furnace again, starting the muffle furnace to pre-sinter the spherical raw materials after the granulation is finished, wherein the sintering temperature is 600 ℃, and the sintering time is 12 hours, so that the lithium manganate material with the finished product density of more than 3.1g/cm3 is obtained
The glue solutions adopted in the embodiments 1 to 5 are different in quality, and the lithium manganate obtained finally has the best effect through experimental comparison such as charging and discharging, differential thermal analysis and the like.
The working principle is as follows: s1, mixing raw materials: the working personnel weigh Mn3O4 and nano electrolytic MnO according to the required proportion2LiOH, metal ion substance (La, Ce, Nd)Adding the three raw materials into a mixing device by a worker for mixing, wherein the raw materials are mixed by adopting different frequencies during mixing for 2 hours, so that the raw materials are uniformly mixed; s2, primary sintering: feeding the mixed raw materials into a muffle furnace by a worker, then starting the muffle furnace to pre-sinter the mixed raw materials, wherein the pre-sintering time is 5-12h, and the pre-sintering temperature is 400-800 ℃, so as to obtain the lithium manganate material, the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2; s3, glue solution preparation: the method comprises the following steps that working personnel weigh raw materials required by glue solution according to a required proportion, the raw materials of the glue solution comprise a solvent, a binder and a coating material, the solvent is pure water, the binder is PVA (polyvinyl alcohol), and the coating material is Al, and then the raw materials are put into a high-speed stirrer to be mixed, so that the glue solution with the solid content of 20% is obtained; s4, grinding and mixing: adding the prepared glue solution into a ball mill according to a ratio of 1:7 by a worker for wet ball milling, wherein the sintered lithium manganate is subjected to sintering for the same time, the ball milling time is 2 hours, and the glue solution is uniformly adhered to the surface of a lithium manganate material in the ball milling process; s5, granulating and drying: after the ball milling in the previous step is finished, the worker puts the lithium manganate and the glue solution mixture into granulation drying equipment for drying, and granulation is finished in the drying process, so that the granulated particles are uniform in size and good in sphericity; s6, secondary sintering: and (3) feeding the lithium manganate particles subjected to the last granulation step into a muffle furnace again by a worker, starting the muffle furnace to pre-sinter the spherical raw materials subjected to the granulation, wherein the sintering temperature is 600 ℃, and the sintering time is 12 hours, so that the lithium manganate material with the finished product density of more than 3.1g/cm3 is obtained.
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 spherical lithium manganate material is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing raw materials: weighing three raw materials of manganese oxide, lithium source compound and metal ion substance according to the required proportion, and then putting the raw materials into mixing equipment for mixing, thereby uniformly mixing the raw materials;
s2, primary sintering: feeding the mixed raw materials in the previous step into a muffle furnace, and then starting the muffle furnace to pre-burn the mixed raw materials to obtain the lithium manganate material, wherein the molecular formula of the obtained finished product is Li1+ aMn2-aO4, and a is more than or equal to 0 and less than or equal to 0.2;
s3, glue solution preparation: weighing raw materials required by the glue solution according to the required proportion, and then putting the raw materials into a high-speed stirrer for mixing to obtain the glue solution;
s4, grinding and mixing: adding the prepared glue solution into a ball mill according to a certain proportion to perform wet ball milling, wherein the glue solution is uniformly adhered to the surface of a lithium manganate material in the ball milling process;
s5, granulating and drying: after the ball milling in the previous step is finished, putting the lithium manganate and the glue solution mixture into granulation drying equipment for drying, and meanwhile, completing granulation in the drying process, wherein the granulated particles are uniform in size and good in sphericity;
s6, secondary sintering: and (4) sending the lithium manganate particles after the last granulation step into the muffle furnace again, and then starting the muffle furnace to pre-burn the spherical raw materials after the granulation is finished, so as to obtain the finished lithium manganate material.
2. The method for preparing the spherical lithium manganate material according to claim 1, wherein the method comprises the following steps: the mass ratio of the manganese oxide to the lithium source compound in the S1 is 1-1.1:2, and the manganese oxide is nano electrolytic MnO2And Mn3O4, the lithium source compound being LiOH.
3. The method for preparing the spherical lithium manganate material according to claim 2, characterized in that: the nano electrolytic MnO2Has high purity with Mn3O499% and LiOH is greater than 95%.
4. The method for preparing the spherical lithium manganate material according to claim 1, wherein the method comprises the following steps: and the metal ion substance in S1 is one or more of rare earth elements La, Ce and Nd.
5. The method for preparing the spherical lithium manganate material according to claim 1, wherein the method comprises the following steps: and mixing the raw materials by adopting different frequencies in the S1 for 0.5-3 h.
6. The method for preparing the spherical lithium manganate material according to claim 1, wherein the method comprises the following steps: the presintering time in the S2 is 5-12h, and the presintering temperature is 400-800 ℃.
7. The method for preparing the spherical lithium manganate material according to claim 1, wherein the method comprises the following steps: the raw materials of the glue solution in the S3 are solvent, adhesive and coating material, and the solid content of the mixed glue solution is controlled to be 5-30%.
8. The method for preparing a spherical lithium manganate material according to claim 7, characterized in that: the solvent is pure water, the binder is PVA, and the coating material is one of oxides of Mg, Al, Ti, W, Zr, Ga, B, Cr, Co and other elements.
9. The method for preparing the spherical lithium manganate material according to claim 1, wherein the method comprises the following steps: the mass ratio of the glue solution in the S4 to the lithium manganate material is as follows: 1:1-10, and the ball milling time is 0.5-5 h.
10. The method for preparing the spherical lithium manganate material according to claim 1, wherein the method comprises the following steps: the secondary sintering temperature in the S6 is 500-800 ℃, the sintering time is 10-30h, and the density of the sintered product is more than 3.1g/cm3。
CN202110304544.7A 2021-03-23 2021-03-23 Preparation method of spherical lithium manganate material Withdrawn CN113120964A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335507A (en) * 2021-12-16 2022-04-12 安徽博石高科新材料股份有限公司 Surface pressing type mixing and secondary sintering method of lithium battery positive electrode material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335507A (en) * 2021-12-16 2022-04-12 安徽博石高科新材料股份有限公司 Surface pressing type mixing and secondary sintering method of lithium battery positive electrode material
CN114335507B (en) * 2021-12-16 2024-02-20 安徽博石高科新材料股份有限公司 Press-face type mixing and secondary sintering method for lithium battery anode material

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