CN113089095A - Preparation method of single-crystal lithium manganate material - Google Patents

Preparation method of single-crystal lithium manganate material Download PDF

Info

Publication number
CN113089095A
CN113089095A CN202110299376.7A CN202110299376A CN113089095A CN 113089095 A CN113089095 A CN 113089095A CN 202110299376 A CN202110299376 A CN 202110299376A CN 113089095 A CN113089095 A CN 113089095A
Authority
CN
China
Prior art keywords
lithium manganate
pyrite
additive
manganous
manganese
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202110299376.7A
Other languages
Chinese (zh)
Inventor
马岩华
赵春波
王剑锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Boshi Hi Hi Tech New Material Co ltd
Original Assignee
Anhui Boshi Hi Hi Tech New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui Boshi Hi Hi Tech New Material Co ltd filed Critical Anhui Boshi Hi Hi Tech New Material Co ltd
Priority to CN202110299376.7A priority Critical patent/CN113089095A/en
Publication of CN113089095A publication Critical patent/CN113089095A/en
Priority to JP2022031996A priority patent/JP7318037B2/en
Priority to KR1020220028815A priority patent/KR20220131830A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
    • 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
    • C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
    • C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to the technical field of preparation of single-crystal lithium manganate materials, in particular to a preparation method of a single-crystal lithium manganate material, which comprises the following steps: the manganese sulfate material adopted by the invention is naturally crystallized from a solution by a physical method, does not need to consume excessive electric energy and heat energy, and is environment-friendly and low in consumption; mixing with additive M, grinding to disperse the additive in manganese sulfate powder, and fast high temperature desulfurizing to obtain additive doped manganous-manganic oxide. Not only can the additive be distributed more uniformly and fully enter the crystal lattice of the final product, but also the cost is obviously lower than that of the electrolytic manganese dioxide material consuming a large amount of electric energy, and is usually less than half of the cost.

Description

Preparation method of single-crystal lithium manganate material
Technical Field
The invention relates to the technical field of preparation of single-crystal lithium manganate materials, in particular to a preparation method of a single-crystal lithium manganate material.
Background
As an energy storage component of clean energy, a lithium ion battery is widely applied to a plurality of fields such as electric automobiles, electric bicycles, electric tools, digital products, mobile power supplies, energy storage batteries and the like. The lithium battery anode material is a key part of a lithium battery, and lithium manganate serving as an anode active material has gradually become one of mainstream materials of a civil lithium ion power battery.
The lithium manganate cathode material has the advantages of high voltage, good rate capability, good low-temperature performance, good safety performance, low cost and the like. However, the high self-discharge rate and poor high-temperature cycle performance become main problems which restrict the development of the method to more application fields. For the improvement of lithium manganate material, there are mainly doped coating plasma phase and surface modification methods. In addition, the lithium manganate material is subjected to single crystallization, so that the surface area is reduced, excessive side reactions are prevented from occurring in the charging and discharging processes of the battery, and the high-temperature cycle performance and the self-discharge problem of the manufactured battery are improved.
Meanwhile, the single-crystal lithium manganate can use higher voltage, is convenient to mix with lithium cobaltate and a single-crystal lithium nickel cobalt manganate material, and is compounded into an application route of the anode material with higher cost performance. Therefore, the single crystallization of the lithium manganate material is a relatively commercially valuable positive electrode material process route.
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 0.20.
In the prior art, the lithium manganate material is prepared by a single-crystallization process, wherein electrolytic manganese dioxide is used as a precursor, and is mixed with lithium carbonate, and a high-temperature solid-phase reaction is performed. By increasing the sintering temperature and prolonging the heat preservation time, the lithium manganate polycrystal formed in the sintering process gradually grows up in the long-time mass transfer process to form a larger monocrystal, so that the single-crystal lithium manganate material with the primary grain size of more than 2 mu m is prepared. However, the method has high energy consumption and high requirement on the purity of raw materials, and meanwhile, the molar ratio of manganese to lithium is generally 2: 1.09-1.12, the consumption of lithium materials is large, and the low cost advantage of the lithium manganate material is limited, so that the development of a preparation method of a single-crystal lithium manganate material is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of a single-crystal lithium manganate material, which aims to solve the problems that the energy consumption is high, the requirement on the purity of raw materials is high, the consumption of lithium materials is high, and the low-cost advantage of the lithium manganate material is limited in the background technology.
The technical scheme of the invention is as follows: a preparation method of a single-crystal lithium manganate material comprises the following steps:
s1, crushing and grinding: respectively putting the pyrite and the manganese ore into a pulverizer to be pulverized, and then pouring the pulverized pyrite and manganese ore into a grinding machine to be ground to obtain pyrite and manganese ore powder;
s2, crystallization: putting the concentrated solution of manganese sulfate solution into crystallization equipment until manganese sulfate is crystallized;
s3, first addition: adding an entering additive M into the manganese sulfate solid powder;
s4, crushing: pouring the manganese sulfate solid powder and the additive M into a ball mill, starting the ball mill to crush and uniformly mix the manganese sulfate solid powder and the additive M to obtain a uniformly mixed material;
s5, desulfurization: the uniformly mixed material is placed at a high temperature for firing, so that sulfur element in the material is separated, and a manganous-manganic oxide material is formed;
s6, second addition: adding lithium carbonate into the manganous-manganic oxide material;
s7, mixing: pouring the manganous-manganic oxide material and the lithium carbonate into a stirrer to stir the manganous-manganic oxide material and the lithium carbonate, and fully mixing the manganous-manganic oxide material and the lithium carbonate;
s8, sintering: putting the fully mixed trimanganese tetroxide material and lithium carbonate into a sintering chamber for sintering, wherein the formed trimanganese tetroxide material forms a trace molten state;
s9, cooling: and cooling a trace molten state formed by the manganous manganic oxide material to obtain a part of agglomerates, thereby obtaining the monocrystalline lithium manganate material.
In S4, the additive M is a compound of Al, Mg, Nb, Cr, Ti, Co, Ni, Zr.
Furthermore, in S9, the particle size distribution D50 is 3-8 μm by crushing and dispersing treatment, and in S5, the burning temperature of the uniformly mixed materials is set at 1200-1400 ℃.
Further, in S7, the molar ratio of the manganous manganic oxide to the lithium carbonate is 2: 1.07-1.12.
Further, in S8, the sintering temperature is set to be 700-850 ℃, the sintering time is set to be 5-15h, in S7, the rotating speed of the stirrer is set to be 1000-1200r/min, the stirring and mixing time is set to be 5-6min, in S2, the temperature of the crystallization equipment is set to be 500-600 ℃, and the concentration time is set to be 1.5-2 h.
Further, in S2, the manganese sulfate solution is preferably concentrated before crystallization, and is poured into a concentration device for concentration, where the concentration ambient temperature is set at 200-.
Further, pouring pyrite and manganese ore powder into a stirrer between the steps S1 and S2, starting the stirrer, slowly adding sulfuric acid into the stirrer, and reacting to obtain a manganese sulfate solution.
Further, in the step S9, due to the action of the additive M, the material agglomerates in a trace molten state are easy to crush and disperse, so that the required particle size distribution of the lithium manganate material is achieved.
In S5, the released sulfur is filtered and purified by a desulfurization solvent filtration and purification device during desulfurization, and an amine liquid desulfurization method is used in the desulfurization solvent filtration and purification device.
Further, in S1, before the pyrite and the manganese ore are pulverized, the pyrite and the manganese ore are firstly cleaned by using deionized water, the pyrite and the manganese ore are quickly dried by using a hot air blower after the cleaning, the obtained pyrite and manganese ore powder is washed by using deionized water again, and then the obtained pyrite and manganese ore powder is dried in a drying oven.
Compared with the prior art, the invention provides a preparation method of a single-crystal lithium manganate material by improvement, which has the following improvements and advantages:
(1) the manganese sulfate material adopted by the invention is naturally crystallized from the solution by a physical method, and the method does not need to consume excessive electric energy and heat energy, is environment-friendly and has low consumption; mixing with additive M, grinding to disperse the additive in manganese sulfate powder, and fast high temperature desulfurizing to obtain additive doped manganous-manganic oxide. Not only can the additive be distributed more uniformly and fully enter the crystal lattice of the final product, but also the cost is obviously lower than that of the electrolytic manganese dioxide material consuming a large amount of electric energy, and is usually less than half of the cost.
(2) The invention adopts the manganese oxide subjected to high-temperature desulfurization as a precursor, the sulfur content of the manganese oxide is usually less than 0.2 percent and is obviously lower than 1.2 percent of electrolytic manganese dioxide, and the adverse effect of sulfur element remained in the material on the final lithium ion battery is avoided.
(3) The invention adopts single crystal and mono-like manganous-manganic oxide precursor, which can reduce 4-6% of the consumption of lithium element material compared with the traditional method.
(4) The sintering process for producing the single crystal lithium manganate by the method disclosed by the invention can be carried out by keeping the temperature below 850 ℃ for 10 hours, and the traditional method needs to keep the temperature above 900 ℃ for more than 20 hours, so that the process cost of the method disclosed by the invention is less than half of that of the conventional method.
Drawings
The invention is further explained below with reference to the figures and examples:
FIG. 1 is a generalized diagram of the present invention;
fig. 2 is a flow chart of the present invention.
Detailed Description
The present invention will be described in detail with reference to fig. 1-2, 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 single-crystal lithium manganate material comprises the following steps:
s1, crushing and grinding: respectively putting the pyrite and the manganese ore into a pulverizer to be pulverized, then pouring the pulverized pyrite and manganese ore into a grinding mill to be ground to obtain pyrite and manganese ore powder, pouring the pyrite and manganese ore powder into a stirrer, starting the stirrer, then slowly adding sulfuric acid into the stirrer, and reacting to obtain a manganese sulfate solution;
s2, crystallization: pouring the manganese sulfate solution into concentration equipment, concentrating the manganese sulfate solution, setting the concentration environment temperature at 300 ℃, putting the concentrated manganese sulfate solution into crystallization equipment, setting the temperature of the crystallization equipment at 600 ℃, setting the concentration time for 2 hours, and waiting until manganese sulfate is crystallized;
s3, first addition: adding an entering additive M into the manganese sulfate solid powder;
s4, crushing: pouring manganese sulfate solid powder and an additive M into a ball mill, starting the ball mill to crush and uniformly mix the manganese sulfate solid powder and the additive M to obtain a uniformly mixed material, wherein the additive M is Al2O3 and MgCO 3;
s5, desulfurization: the evenly mixed material is placed at a high temperature for burning, the burning temperature is set at 1250 ℃, so that sulfur element in the material is separated, and the manganous-manganic oxide material is formed;
s6, second addition: adding lithium carbonate into the manganous-manganic oxide material;
s7, mixing: and pouring the manganous-manganic oxide material and lithium carbonate into a stirrer to stir the manganous-manganic oxide material and the lithium carbonate, wherein the manganous-manganic oxide and the lithium carbonate are mixed according to the molar ratio of manganese element to lithium element of 2: 1.07, setting the rotating speed of a stirrer at 1000r/min, and setting the stirring and mixing time at 5h to fully mix the mangano-manganic oxide material and the lithium carbonate;
s8, sintering: putting the fully mixed trimanganese tetroxide material and lithium carbonate into a sintering chamber for sintering, wherein the sintering temperature is set at 800 ℃, the sintering time is set at 10 hours, and the formed trimanganese tetroxide material forms a trace molten state;
s9, cooling: and cooling a trace amount of molten state formed by the manganous manganic oxide material to obtain partial agglomerates, wherein the agglomerates of the trace amount of molten state material are easy to crush and disperse under the action of the additive M, and the particle size distribution D50 is enabled to be between 5 mu M through crushing and dispersing treatment to achieve the particle size distribution required by the lithium manganate material, so that the single-crystal state lithium manganate material is obtained.
Example two
A preparation method of a single-crystal lithium manganate material comprises the following steps:
s1, crushing and grinding: respectively putting the pyrite and the manganese ore into a pulverizer to be pulverized, then pouring the pulverized pyrite and manganese ore into a grinding mill to be ground to obtain pyrite and manganese ore powder, pouring the pyrite and manganese ore powder into a stirrer, starting the stirrer, then slowly adding sulfuric acid into the stirrer, and reacting to obtain a manganese sulfate solution;
s2, crystallization: pouring the manganese sulfate solution into concentration equipment, concentrating the manganese sulfate solution, setting the concentration environment temperature at 300 ℃, putting the concentrated manganese sulfate solution into crystallization equipment, setting the temperature of the crystallization equipment at 600 ℃, setting the concentration time for 2 hours, and waiting until manganese sulfate is crystallized;
s3, first addition: adding an entering additive M into the manganese sulfate solid powder;
s4, crushing: pouring manganese sulfate solid powder and an additive M into a ball mill, starting the ball mill to crush and uniformly mix the manganese sulfate solid powder and the additive M to obtain a uniformly mixed material, wherein the additive M is Al2O3 and MgCO 3;
s5, desulfurization: the evenly mixed material is placed at a high temperature for burning, the burning temperature is set at 1250 ℃, so that sulfur element in the material is separated, and the manganous-manganic oxide material is formed;
s6, second addition: adding lithium carbonate into the manganous-manganic oxide material;
s7, mixing: and pouring the manganous-manganic oxide material and lithium carbonate into a stirrer to stir the manganous-manganic oxide material and the lithium carbonate, wherein the manganous-manganic oxide and the lithium carbonate are mixed according to the molar ratio of manganese element to lithium element of 2: 1.10, setting the rotating speed of a stirrer at 1000r/min, and setting the stirring and mixing time at 5h to fully mix the mangano-manganic oxide material and the lithium carbonate;
s8, sintering: putting the fully mixed trimanganese tetroxide material and lithium carbonate into a sintering chamber for sintering, wherein the sintering temperature is set at 800 ℃, the sintering time is set at 10 hours, and the formed trimanganese tetroxide material forms a trace molten state;
s9, cooling: and cooling a trace amount of molten state formed by the manganous manganic oxide material to obtain partial agglomerates, wherein the agglomerates of the trace amount of molten state material are easy to crush and disperse under the action of the additive M, and the particle size distribution D50 is enabled to be between 5 mu M through crushing and dispersing treatment to achieve the particle size distribution required by the lithium manganate material, so that the single-crystal state lithium manganate material is obtained.
EXAMPLE III
A preparation method of a single-crystal lithium manganate material comprises the following steps:
s1, crushing and grinding: respectively putting the pyrite and the manganese ore into a pulverizer to be pulverized, then pouring the pulverized pyrite and manganese ore into a grinding mill to be ground to obtain pyrite and manganese ore powder, pouring the pyrite and manganese ore powder into a stirrer, starting the stirrer, then slowly adding sulfuric acid into the stirrer, and reacting to obtain a manganese sulfate solution;
s2, crystallization: pouring the manganese sulfate solution into concentration equipment, concentrating the manganese sulfate solution, setting the concentration environment temperature at 300 ℃, putting the concentrated manganese sulfate solution into crystallization equipment, setting the temperature of the crystallization equipment at 600 ℃, setting the concentration time for 2 hours, and waiting until manganese sulfate is crystallized;
s3, first addition: adding an entering additive M into the manganese sulfate solid powder;
s4, crushing: pouring manganese sulfate solid powder and an additive M into a ball mill, starting the ball mill to crush and uniformly mix the manganese sulfate solid powder and the additive M to obtain a uniformly mixed material, wherein the additive M is Al2O3 and MgCO 3;
s5, desulfurization: the evenly mixed material is placed at a high temperature for burning, the burning temperature is set at 1250 ℃, so that sulfur element in the material is separated, and the manganous-manganic oxide material is formed;
s6, second addition: adding lithium carbonate into the manganous-manganic oxide material;
s7, mixing: and pouring the manganous-manganic oxide material and lithium carbonate into a stirrer to stir the manganous-manganic oxide material and the lithium carbonate, wherein the manganous-manganic oxide and the lithium carbonate are mixed according to the molar ratio of manganese element to lithium element of 2: 1.12, setting the rotating speed of a stirrer at 1000r/min, and setting the stirring and mixing time at 5h to fully mix the mangano-manganic oxide material and the lithium carbonate;
s8, sintering: putting the fully mixed trimanganese tetroxide material and lithium carbonate into a sintering chamber for sintering, wherein the sintering temperature is set at 800 ℃, the sintering time is set at 10 hours, and the formed trimanganese tetroxide material forms a trace molten state;
s9, cooling: and cooling a trace amount of molten state formed by the manganous manganic oxide material to obtain partial agglomerates, wherein the agglomerates of the trace amount of molten state material are easy to crush and disperse under the action of the additive M, and the particle size distribution D50 is enabled to be between 5 mu M through crushing and dispersing treatment to achieve the particle size distribution required by the lithium manganate material, so that the single-crystal state lithium manganate material is obtained.
In the first embodiment, the second embodiment and the third embodiment, the molar ratio of manganese element to lithium element is different between manganomanganic oxide and lithium carbonate, and the rest conditions are the same, and the experiment comparison shows that the effect in the third embodiment is good, and meanwhile, the comparison table of the method in the third embodiment and the traditional production method is as follows:
Figure DEST_PATH_IMAGE002
the cost of the manganese sulfate material adopted by the invention is obviously lower than that of the electrolytic manganese dioxide material, and is usually less than half of the cost, the invention adopts high-temperature desulfurization, avoids the adverse effect of sulfur element remained in the material on the final lithium ion battery, and the invention adopts a trimanganese tetroxide precursor of single crystal and similar single crystal, and can reduce the consumption of lithium element material; the process cost of the monocrystalline lithium manganate produced by the method is less than half of that of the monocrystalline lithium manganate produced by the conventional method.
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 single-crystal lithium manganate material is characterized by comprising the following steps: the method comprises the following steps:
s1, crushing and grinding: respectively putting the pyrite and the manganese ore into a pulverizer to be pulverized, and then pouring the pulverized pyrite and manganese ore into a grinding machine to be ground to obtain pyrite and manganese ore powder;
s2, crystallization: putting the concentrated solution of manganese sulfate solution into crystallization equipment until manganese sulfate is crystallized;
s3, first addition: adding an entering additive M into the manganese sulfate solid powder;
s4, crushing: pouring the manganese sulfate solid powder and the additive M into a ball mill, starting the ball mill to crush and uniformly mix the manganese sulfate solid powder and the additive M to obtain a uniformly mixed material;
s5, desulfurization: the uniformly mixed material is placed at a high temperature for firing, so that sulfur element in the material is separated, and a manganous-manganic oxide material is formed;
s6, second addition: adding lithium carbonate into the manganous-manganic oxide material;
s7, mixing: pouring the manganous-manganic oxide material and the lithium carbonate into a stirrer to stir the manganous-manganic oxide material and the lithium carbonate, and fully mixing the manganous-manganic oxide material and the lithium carbonate;
s8, sintering: putting the fully mixed trimanganese tetroxide material and lithium carbonate into a sintering chamber for sintering, wherein the formed trimanganese tetroxide material forms a trace molten state;
s9, cooling: and cooling a trace molten state formed by the manganous manganic oxide material to obtain a part of agglomerates, thereby obtaining the monocrystalline lithium manganate material.
2. The method for preparing a single-crystal lithium manganate material according to claim 1, characterized in that: in S4, the additive M is a compound of Al, Mg, Nb, Cr, Ti, Co, Ni and Zr.
3. The method for preparing a single-crystal lithium manganate material according to claim 1, characterized in that: in S9, the crushing and dispersing treatment is carried out, the particle size distribution D50 is between 3 and 8 mu m, and in S5, the ignition temperature of the uniformly mixed materials is set at 1200 ℃ and 1400 ℃.
4. The method for preparing a single-crystal lithium manganate material according to claim 1, characterized in that: in the step S7, the molar ratio of manganous manganic oxide to lithium carbonate is 2: 1.07-1.12.
5. The method for preparing a single-crystal lithium manganate material according to claim 1, characterized in that: in S8, the sintering temperature is set to be 850 ℃ in 700-.
6. The method for preparing a single-crystal lithium manganate material according to claim 1, characterized in that: in the step S2, the manganese sulfate solution is preferably concentrated before crystallization, and is poured into a concentration device for concentration, where the concentration ambient temperature is set at 200-.
7. The method for preparing a single-crystal lithium manganate material according to claim 1, characterized in that: and pouring the pyrite and manganese ore powder into a stirrer between the steps S1 and S2, starting the stirrer, slowly adding sulfuric acid into the stirrer, and reacting to obtain a manganese sulfate solution.
8. The method for preparing a single-crystal lithium manganate material according to claim 1, characterized in that: in the S9, due to the action of the additive M, the material blocks in a trace molten state are easy to crush and disperse, so that the required particle size distribution of the lithium manganate material is achieved.
9. The method for preparing a single-crystal lithium manganate material according to claim 1, characterized in that: in the step S5, a desulfurization solvent filtration and purification device is used to filter and purify the released sulfur, and an amine liquid desulfurization method is used in the desulfurization solvent filtration and purification device.
10. The method for preparing a single-crystal lithium manganate material according to claim 1, characterized in that: and S1, before crushing the pyrite and the manganese ore, firstly cleaning the pyrite and the manganese ore by using deionized water, after cleaning, quickly drying the pyrite and the manganese ore by using a hot air blower, washing the obtained pyrite and manganese ore powder by using deionized water again, and then drying the pyrite and manganese ore powder in a drying box.
CN202110299376.7A 2021-03-22 2021-03-22 Preparation method of single-crystal lithium manganate material Withdrawn CN113089095A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202110299376.7A CN113089095A (en) 2021-03-22 2021-03-22 Preparation method of single-crystal lithium manganate material
JP2022031996A JP7318037B2 (en) 2021-03-22 2022-03-02 Method for preparing single crystal lithium manganate material
KR1020220028815A KR20220131830A (en) 2021-03-22 2022-03-07 A method for preparing a single crystal lithium manganate material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110299376.7A CN113089095A (en) 2021-03-22 2021-03-22 Preparation method of single-crystal lithium manganate material

Publications (1)

Publication Number Publication Date
CN113089095A true CN113089095A (en) 2021-07-09

Family

ID=76668771

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110299376.7A Withdrawn CN113089095A (en) 2021-03-22 2021-03-22 Preparation method of single-crystal lithium manganate material

Country Status (3)

Country Link
JP (1) JP7318037B2 (en)
KR (1) KR20220131830A (en)
CN (1) CN113089095A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114775034A (en) * 2022-04-01 2022-07-22 安徽格派新能源有限公司 Preparation method of monocrystal lithium manganate cathode material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117105275B (en) * 2023-10-23 2024-01-12 湘潭电化科技股份有限公司 Spherical manganous-manganic oxide and preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000243382A (en) * 1999-02-23 2000-09-08 Toyota Central Res & Dev Lab Inc Manufacture of positive electrode active material for lithium secondary battery
JP4876371B2 (en) * 2004-01-29 2012-02-15 日亜化学工業株式会社 Positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode mixture for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
JP5229472B2 (en) * 2007-11-12 2013-07-03 戸田工業株式会社 Lithium manganate particles for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery
JP5670105B2 (en) * 2009-09-29 2015-02-18 日本碍子株式会社 Positive electrode active material and lithium secondary battery
KR101295974B1 (en) * 2011-05-02 2013-08-13 삼성정밀화학 주식회사 Method for preparing lithium manganese oxide positive active material for lithium ion secondary battery, positive active material prepared thereby, and lithium ion secondary battery including the same
KR20150013076A (en) * 2013-07-26 2015-02-04 주식회사 엘지화학 Polycrystal lithium manganese oxide particles, preparation method thereof, and cathode active material comprising the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114775034A (en) * 2022-04-01 2022-07-22 安徽格派新能源有限公司 Preparation method of monocrystal lithium manganate cathode material

Also Published As

Publication number Publication date
JP7318037B2 (en) 2023-07-31
KR20220131830A (en) 2022-09-29
JP2022146899A (en) 2022-10-05

Similar Documents

Publication Publication Date Title
CN110048118B (en) High-nickel cobalt lithium manganate single crystal precursor, preparation method thereof and high-nickel cobalt lithium manganate single crystal positive electrode material
KR20170102293A (en) Multicomponent materials having a classification structure for lithium ion batteries, a method for manufacturing the same, an anode of a lithium ion battery and a lithium ion battery
CN105800699A (en) Method for preparing high-sphericity-degree and large-particle cobaltosic oxide
JP7318037B2 (en) Method for preparing single crystal lithium manganate material
CN111908519A (en) High-capacity nickel-rich precursor, positive electrode material and preparation method thereof
CN110904495A (en) Preparation method of monocrystal polyhedral lithium manganate positive electrode material
CN107482192A (en) Monocrystalline tertiary cathode material and preparation method thereof and lithium ion battery
CN110233261B (en) Preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery
CN100527490C (en) Submicron secondary battery material and method for making same
CN113365946A (en) Lithium compound, nickel-based positive electrode active material, method for producing lithium oxide, method for producing nickel-based positive electrode active material, and secondary battery using same
CN102683668A (en) Spinel nickel manganese-based oxide cathode material and preparation process thereof
CN108155377B (en) Ternary material battery positive electrode and preparation method thereof and lithium ion battery
CN112952085A (en) Gradient high-nickel single crystal ternary material, preparation method thereof and battery using material
EP4443558A1 (en) Multi-element co-doped sodium-ion positive electrode material, and preparation method therefor and use thereof
KR20110108566A (en) Process for the production of lithium-manganese double oxide for lithium ion batteries and lithium-manganese double oxide for lithium ion batteries made by the same, and lithium ion batteries cotaining the same
CN114373920A (en) High-entropy oxide and preparation method and application thereof
WO2024179036A1 (en) Single-crystal manganese-based lithium battery positive electrode material and preparation method therefor
CN111139516A (en) Preparation method of single crystal type lithium manganate material and precursor thereof
CN117247051A (en) Positive electrode lithium supplementing agent material and preparation method and application thereof
CN112538652A (en) 8-series high-nickel NCM811 ternary positive electrode single crystal and preparation method thereof
CN112357972A (en) Low-nickel cobalt-free precursor, cathode material and preparation method thereof
CN116053445A (en) High-voltage P2 type layered positive electrode material and application thereof in sodium ion battery
JP2001185148A (en) Positive electrode material for 5 v-class lithium secondary battery and manufacturing method therefor
CN101950802A (en) Method for preparing lithium manganate battery cathode material
CN115295748B (en) Method for preparing monocrystal ternary cathode material of lithium ion battery by using multi-metal MOF precursor and product thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20210709

WW01 Invention patent application withdrawn after publication