CN111139516A - Preparation method of single crystal type lithium manganate material and precursor thereof - Google Patents
Preparation method of single crystal type lithium manganate material and precursor thereof Download PDFInfo
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- CN111139516A CN111139516A CN201911401361.6A CN201911401361A CN111139516A CN 111139516 A CN111139516 A CN 111139516A CN 201911401361 A CN201911401361 A CN 201911401361A CN 111139516 A CN111139516 A CN 111139516A
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- 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
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- 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
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- 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
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- 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
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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
- 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
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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
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- 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 discloses a preparation method of a monocrystal type lithium manganate material precursor, which comprises the following steps of S1, adopting manganese sulfate solid powder, burning at the temperature of 1200-1400 ℃ to separate sulfur element in the material, and forming a trimanganese tetroxide material; s2, forming a trace amount of molten trimanganese tetroxide material during high-temperature sintering, and cooling to generate partial agglomeration; and S3, crushing the block material to achieve the particle size distribution required by the lithium manganate material. And mixing the prepared precursor manganomanganic oxide material with lithium carbonate, and sintering at 780-850 ℃ for 5-15 hours to obtain the single-crystalline lithium manganate material. The invention solves the problems that the common Electrolytic Manganese Dioxide (EMD) has higher cost and is not beneficial to single crystallization during firing, and the mangano-manganic oxide precursor is adopted to produce the lithium manganate, so that the required lithium element material is less and the requirement on energy consumption is lower.
Description
Technical Field
The invention relates 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.
The method comprises the steps of carrying out single crystallization on the lithium manganate material, mixing electrolytic manganese dioxide serving as a precursor with lithium carbonate, and carrying out high-temperature solid-phase reaction to prepare the lithium manganate material. 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 ion materials is large, and the low-cost advantage of the lithium manganate material is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a preparation method of a single-crystal lithium manganate material, solves the problems that the conventional Electrolytic Manganese Dioxide (EMD) is high in cost and is not beneficial to single crystallization during firing, and meanwhile, the lithium manganate produced by adopting the trimanganese tetroxide precursor needs few lithium materials and has low energy consumption requirements.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of a single-crystal lithium manganate material precursor, which comprises the following steps:
s1, adopting manganese sulfate solid powder, and burning at 1200-1400 ℃ to separate sulfur element in the material to form manganous manganic oxide material;
s2, forming a trace amount of molten trimanganese tetroxide material during high-temperature sintering, and cooling to generate partial agglomeration;
and S3, crushing the block material to achieve the particle size distribution required by the lithium manganate material, and thus obtaining the lithium manganate material.
Preferably, in step S3, the bulk material is pulverized by a jet mill so that the particle size distribution D50 is 3-8 μm.
The invention also provides a method for preparing the single-crystal lithium manganate material by using the precursor of the single-crystal lithium manganate material, which comprises the steps of mixing the prepared precursor trimanganese tetroxide material with lithium carbonate, and sintering at 780-850 ℃ for 5-15 hours to obtain the single-crystal lithium manganate material.
Preferably, the molar ratio of the manganous manganic oxide to the lithium carbonate is 2: 1.05 to 1.07.
The invention has the following beneficial effects:
the manganese sulfate material adopted by the invention is crystallized from the solution by a physical method, and then is desulfurized at high temperature rapidly to obtain trimanganese tetroxide, the cost of the manganese sulfate material is obviously lower than that of electrolytic manganese dioxide material which consumes a large amount of electric energy, and the cost is usually less than half of the cost; 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; the invention adopts the trimanganese tetroxide precursor of single crystal and similar single crystal, which can reduce 4-6% of the consumption of lithium materials compared with the traditional method; 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 accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an SEM image of a single-crystal lithium manganate material prepared by the method of the invention;
FIG. 2 is an SEM image of a single-crystal lithium manganate material prepared by a conventional method;
FIG. 3 is a flow diagram of a process route of the present invention;
fig. 4 is a flow chart of a conventional process route.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1:
a method for preparing a single-crystal lithium manganate material comprises the following steps:
A. heating manganese sulfate to 1250 ℃ in a rotary kiln for desulfurization to generate manganous manganic oxide;
B. cooling the manganous-manganic oxide, and then crushing the manganous-manganic oxide in a jet mill to ensure that the particle size distribution D50 is between 3 and 8 mu m;
C. mixing the crushed trimanganese tetroxide and lithium carbonate according to the molar ratio of manganese to lithium elements of 2: 1.06, preparing materials and uniformly mixing;
D. and sintering the mixture at 820 ℃ for 10 hours, cooling, and crushing and screening the material. Obtaining the monocrystal lithium manganate.
Example 2:
a method for preparing a single-crystal lithium manganate material comprises the following steps:
A. heating manganese sulfate to 1250 ℃ in a rotary kiln for desulfurization to generate manganous manganic oxide;
B. cooling the manganous-manganic oxide, and then crushing the manganous-manganic oxide in a jet mill to ensure that the particle size distribution D50 is between 3 and 8 mu m;
C. mixing the crushed trimanganese tetroxide and lithium carbonate according to the molar ratio of manganese to lithium elements of 2: 1.06, preparing materials and uniformly mixing;
D. adding niobium pentoxide with the mass ratio of 0.5 percent into the mixture as an additive, and uniformly mixing;
E. sintering the mixture at 800 ℃ for 10 hours, cooling, and crushing and screening the materials. Obtaining the monocrystal lithium manganate.
FIG. 1 is an SEM image of a single-crystal lithium manganate material prepared by the method of the invention; FIG. 2 is an SEM image of a single-crystal lithium manganate material prepared by a conventional method; FIG. 3 is a flow diagram of a process route of the present invention; fig. 4 is a flow chart of a conventional process route. 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.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The preparation method of the single-crystal lithium manganate material precursor is characterized by comprising the following steps:
s1, adopting manganese sulfate solid powder, and burning at 1200-1400 ℃ to separate sulfur element in the material to form manganous manganic oxide material;
s2, forming a trace amount of molten trimanganese tetroxide material during high-temperature sintering, and cooling to generate partial agglomeration;
and S3, crushing the block material to achieve the particle size distribution required by the lithium manganate material, and thus obtaining the lithium manganate material.
2. The method for preparing the single-crystal lithium manganate material precursor of claim 1, wherein in step S3, the bulk material is pulverized by a jet mill to have a particle size distribution D50 of 3-8 μm.
3. A method for preparing a single-crystal lithium manganate material by using a single-crystal lithium manganate material precursor is characterized in that the prepared precursor manganous-manganic oxide material is mixed with lithium carbonate and sintered for 5-15 hours at 780-850 ℃ to obtain the single-crystal lithium manganate material.
4. The method for preparing a single-crystal lithium manganate material according to claim 3, wherein the molar ratio of manganous manganic oxide to lithium carbonate is 2: 1.05 to 1.07.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112795985A (en) * | 2020-12-29 | 2021-05-14 | 无锡晶石新型能源股份有限公司 | Preparation method of doped single crystal manganous-manganic oxide |
| CN112897583A (en) * | 2021-04-27 | 2021-06-04 | 四川青源新材料有限公司 | Device and method for preparing battery-grade single-crystal manganous-manganic oxide |
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