CN106711442B - Preparation method of tetradecahedron-shaped nano lithium manganate battery cathode material - Google Patents
Preparation method of tetradecahedron-shaped nano lithium manganate battery cathode material Download PDFInfo
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- CN106711442B CN106711442B CN201710159408.7A CN201710159408A CN106711442B CN 106711442 B CN106711442 B CN 106711442B CN 201710159408 A CN201710159408 A CN 201710159408A CN 106711442 B CN106711442 B CN 106711442B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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 tetrakaidecahedron-shaped nano lithium manganate battery cathode material, which comprises the steps of firstly preparing lithium manganate seed crystals by a microwave heating method, and then preparing nano lithium manganate by a hydrothermal method; according to the method, the obtained seed crystals are fine and uniform by utilizing the rapid heating effect of microwaves, and are used as crystal growth base points of subsequent hydrothermal steps, so that a product with small particle size and uniform size can be obtained, and in the hydrothermal process, amino acid is selected as a precipitator and a soft template agent, and the lithium manganate with a tetradecahedron structure is obtained by utilizing the slow release effect and the special steric effect of the amino acid. The tetradecahedron-shaped nano lithium manganate obtained by the invention is used as a lithium ion battery anode material, and due to the influence of the special morphology on ion diffusion and the influence on particle accumulation, the power density and the specific capacity of the battery are improved, and the tetradecahedron-shaped nano lithium manganate has wide application prospect.
Description
Technical Field
The invention relates to a preparation method of lithium manganate used as a battery anode material, in particular to a preparation method of a tetradecahedron-shaped nano lithium manganate battery anode material.
Background
In recent years, various electronic devices have been rapidly developed, and the requirement for batteries is higher and higher, and lithium ion batteries are regarded as the best novel energy sources, and are large enough to electric automobiles and small enough to notebooks and mobile phones.
Lithium manganate (L iMn)2O4) The lithium ion battery anode material has the characteristics of high voltage, low price, abundant resources, environmental friendliness and the like, is one of the most promising lithium ion battery anode materials, and is widely researched and applied. At present, the method for synthesizing lithium manganate mainly comprises a high-temperature solid phase method, a melt impregnation method, a hydrothermal synthesis method, a sol-gel method, a spray drying method and the like. The solid phase method has simple process, but has long synthesis reaction time, poor product uniformity, large environmental pollution due to the fact that a sol-gel method needs a large amount of organic reagents, and the spray drying method and the like have high requirements on equipment. The hydrothermal method in the existing preparation method is a method which is widely applied.
As a battery anode material, the electrochemical performance of lithium manganate has a large relationship with the preparation process, the crystal structure, the grain size, the morphology and the like of the material. The nano material is a hot point of research in recent years, the nano anode material has a large specific surface area, the contact degree of the material and an electrolyte is increased, the path of lithium ion solid phase diffusion is shortened due to small particle size, and the improvement of the power density of the material is facilitated. In addition, different morphologies and crystallinity degrees can bring great influence on the electrochemical performance, the regular particles can reduce agglomeration and particle bridging, and the particle alkaline washing during particle accumulation and filling is reduced, so that the specific capacity of the lithium ion battery is improved.
Disclosure of Invention
The invention aims to provide the nano lithium manganate in the shape of the decatetrahedron, which is beneficial to improving the power density and the specific capacity of a battery due to the unique morphology when used as the anode material of the lithium ion battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a tetrakaidecahedron-shaped nano lithium manganate battery cathode material is characterized by comprising the following steps:
(1) preparing seed crystals by a microwave method, namely dissolving a soluble lithium compound in deionized water to form a lithium ion solution with the concentration of 0.05-0.07 mol/L, dissolving a soluble manganese compound in deionized water to form a manganese ion solution with the concentration of 0.05-0.07 mol/L, mixing and uniformly stirring the two solutions according to the molar ratio of lithium ions to manganese ions of 1: 2, then adding a urea aqueous solution with the concentration of 0.1 mol/L, stirring to obtain a mixed solution, and carrying out microwave heating on the mixed solution to obtain a seed crystal solution, wherein the microwave heating power is 5kW, the frequency is 2450MHz, the time is 2-5 minutes, and the molar ratio of urea to lithium ions is 6-8: 1;
(2) dissolving a soluble lithium compound in deionized water to form a lithium ion solution with the concentration of 0.1-0.3 mol/L, dissolving a soluble manganese compound in deionized water to form a manganese ion solution with the concentration of 0.1-0.3 mol/L, mixing and uniformly stirring the two solutions according to the molar ratio of lithium ions to manganese ions of 1: 2, then adding the seed crystal solution obtained in the step (1) to fully stir, finally adding an amino acid aqueous solution with the concentration of 0.2 mol/L, putting the mixture into a hydrothermal reaction kettle to perform hydrothermal reaction at the temperature of 120-150 ℃ for 2-3 h, taking out a reaction product, filtering, washing and drying at the temperature of 60 ℃ to obtain tetradecahedron-shaped nano lithium manganate;
wherein the soluble lithium compound in the steps (1) and (2) is lithium nitrate or lithium acetate, the soluble manganese compound is manganese nitrate or manganese acetate, the amino acid solution in the step (2) is L-arginine aqueous solution or L-lysine aqueous solution, and the molar ratio of L-arginine or L-lysine to lithium ions is 7-10: 1.
The invention discloses a preparation method of a lithium manganate battery anode material, which prepares a product by a two-step method and has the following principle:
the first step is the preparation of seed crystal, that is, the prepared reaction raw material is heated by adopting a microwave method to obtain the seed crystal with fine particles, because the frequency of the selected microwave heating equipment is 2450MHz, the direction of polar molecules in the raw material is changed to 2.45 × 10 per second under the action of the polar molecules9Secondly, the molecules rotate back and forth, collide with the surrounding molecules and rub, the temperature is rapidly raised, and urea in the raw materials is used as a precipitator to release OH-And on the other hand, because of the uniformity of microwave heating and by controlling the reaction time and the concentration of reaction raw materials, the growth of the seed crystal is effectively avoided, and a large amount of fine lithium manganate seed crystal particles are obtained.
The second step is the preparation of nano lithium manganate product, namely, the seed crystal obtained in the previous step is mixed with reaction raw materials and reacts in a conventional hydrothermal reaction kettle to obtain the product decahedron-shaped nano lithium manganate, in the step, on the basis that a large number of fine seed crystals are used as growth base points, the raw materials of lithium ions and manganese ions react by a traditional hydrothermal method to obtain the product nano lithium manganate with uniform particle size distribution, in the step, the concentration of the lithium ions and the manganese ions is properly increased to accelerate the reaction and the crystal growth speed, and the water-soluble amino acid L-arginine or L-lysine is used as a precipitator with a slow release effect to ensure the reaction, on the other hand, L-arginine or L-lysine is also used as a soft template agent to promote the crystal growth of the lithium manganateAs to the mechanism by which the decahedron is obtained, the inventors hypothesize that this may be due to steric hindrance of L-arginine or L-lysine, or due to groups thereon, such as-COOH, -NH2And the nano lithium manganate is combined with hydrogen bonds and Van der Waals force in water to promote the assembly and the forming of the nano lithium manganate.
The tetradecahedron-shaped nano lithium manganate obtained by the invention is used as a lithium ion battery anode material, and due to the influence of the special morphology on ion diffusion and the influence on particle accumulation, the power density and the specific capacity of the battery are improved, and the tetradecahedron-shaped nano lithium manganate has wide application prospect.
Drawings
FIG. 1 is an XRD pattern of a tetradecahedron-shaped nano lithium manganate battery anode material obtained in example 1;
fig. 2 is an SEM image of the positive electrode material of the tetradecahedron-shaped lithium manganate battery obtained in example 1.
Detailed Description
The following are specific embodiments of the present invention for the purpose of illustration and description.
Example 1
A preparation method of a tetrakaidecahedron-shaped nano lithium manganate battery cathode material is characterized by comprising the following steps:
(1) dissolving lithium nitrate in deionized water to form a lithium ion solution with the concentration of 0.05 mol/L, dissolving manganese acetate in the deionized water to form a manganese ion solution with the concentration of 0.05 mol/L, mixing and uniformly stirring the two solutions according to the molar ratio of the lithium ions to the manganese ions of 1: 2, then adding a urea aqueous solution with the concentration of 0.1 mol/L according to the molar ratio of the urea to the lithium ions of 6: 1, stirring to obtain a mixed solution, and heating the mixed solution by microwaves for 5 minutes to obtain a seed crystal solution, wherein the microwave heating power is 5kW, and the frequency is 2450 MHz;
(2) preparing lithium manganate, namely dissolving lithium nitrate in deionized water to form a lithium ion solution with the concentration of 0.1 mol/L, dissolving manganese nitrate in deionized water to form a manganese ion solution with the concentration of 0.3 mol/L, mixing and uniformly stirring the two solutions according to the molar ratio of lithium ions to manganese ions of 1: 2, then adding the seed crystal solution obtained in the step (1) to stir fully, finally adding L-arginine aqueous solution with the concentration of 0.2 mol/L, putting the mixture into a hydrothermal reaction kettle to perform hydrothermal reaction at 150 ℃ for 2 hours, taking out a reaction product, filtering, washing and drying at 60 ℃ to obtain the tetradecahedral nano lithium manganate, wherein the molar ratio of L-arginine to lithium ions is 8: 1.
FIG. 1 is an XRD (X-ray diffraction) diagram of the prepared tetradecahedron-shaped nano lithium manganate, and compared with a standard diffraction diagram of the lithium manganate, the prepared product is determined to be lithium manganate with good crystallinity. From FIG. 2, it can be determined that the obtained lithium manganate particles have the particle size of about 600-800nm and regular morphology.
Example 2
A preparation method of a tetrakaidecahedron-shaped nano lithium manganate battery cathode material is characterized by comprising the following steps:
(1) preparing seed crystals by a microwave method, namely dissolving lithium acetate in deionized water to form a lithium ion solution with the concentration of 0.07 mol/L, dissolving manganese acetate in deionized water to form a manganese ion solution with the concentration of 0.07 mol/L, mixing and uniformly stirring the two solutions according to the molar ratio of the lithium ions to the manganese ions of 1: 2, then adding a urea aqueous solution with the concentration of 0.1 mol/L according to the molar ratio of the urea to the lithium ions of 8: 1, stirring to obtain a mixed solution, and heating the mixed solution for 2 minutes by microwaves to obtain a seed crystal solution, wherein the microwave heating power is 5kW, and the frequency is 2450 MHz;
(2) preparing lithium manganate, namely dissolving lithium nitrate in deionized water to form a lithium ion solution with the concentration of 0.3 mol/L, dissolving manganese nitrate in deionized water to form a manganese ion solution with the concentration of 0.3 mol/L, mixing the two solutions according to the molar ratio of lithium ions to manganese ions of 1: 2, uniformly stirring, adding the seed crystal solution obtained in the step (1), fully stirring, finally adding 0.2 mol/L of L-lysine aqueous solution, putting the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 3 hours, taking out a reaction product, filtering, washing, and drying at 60 ℃ to obtain the tetradecahedron-shaped nano lithium manganate, wherein the molar ratio of L-arginine to lithium ions is 10: 1.
Claims (1)
1. A preparation method of a tetrakaidecahedron-shaped nano lithium manganate battery cathode material is characterized by comprising the following steps:
(1) preparing seed crystals by a microwave method, namely dissolving a soluble lithium compound in deionized water to form a lithium ion solution with the concentration of 0.05-0.07 mol/L, dissolving a soluble manganese compound in deionized water to form a manganese ion solution with the concentration of 0.05-0.07 mol/L, mixing and uniformly stirring the two solutions according to the molar ratio of lithium ions to manganese ions of 1: 2, then adding a urea aqueous solution with the concentration of 0.1 mol/L, stirring to obtain a mixed solution, and carrying out microwave heating on the mixed solution to obtain a seed crystal solution, wherein the microwave heating power is 5kW, the frequency is 2450MHz, the time is 2-5 minutes, and the molar ratio of urea to lithium ions is 6-8: 1;
(2) dissolving a soluble lithium compound in deionized water to form a lithium ion solution with the concentration of 0.1-0.3 mol/L, dissolving a soluble manganese compound in deionized water to form a manganese ion solution with the concentration of 0.1-0.3 mol/L, mixing and uniformly stirring the two solutions according to the molar ratio of lithium ions to manganese ions of 1: 2, then adding the seed crystal solution obtained in the step (1) to fully stir, finally adding an amino acid aqueous solution with the concentration of 0.2 mol/L, putting the mixture into a hydrothermal reaction kettle to perform hydrothermal reaction at the temperature of 120-150 ℃ for 2-3 h, taking out a reaction product, filtering, washing and drying at the temperature of 60 ℃ to obtain tetradecahedron-shaped nano lithium manganate;
wherein the soluble lithium compound in the steps (1) and (2) is lithium nitrate or lithium acetate, the soluble manganese compound is manganese nitrate or manganese acetate, the amino acid solution in the step (2) is L-arginine aqueous solution or L-lysine aqueous solution, and the molar ratio of L-arginine or L-lysine to lithium ions is 7-10: 1.
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| CN102282701A (en) * | 2009-01-20 | 2011-12-14 | 户田工业株式会社 | Positive electrode active material for secondary batteries with nonaqueous electrolytic solution, process for the production of the active material, and secondary batteries with nonaqueous electrolytic solution |
| CN102522538A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Microwave preparation method for nano lithium manganese |
| CN103022469A (en) * | 2012-12-13 | 2013-04-03 | 青岛乾运高科新材料股份有限公司 | Method for preparing lithium manganate anode material through ultrasonic wave activation technology |
| CN103413943A (en) * | 2013-08-14 | 2013-11-27 | 宁波奈克斯特新材料科技有限公司 | Lithium manganese phosphate positive electrode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102282701A (en) * | 2009-01-20 | 2011-12-14 | 户田工业株式会社 | Positive electrode active material for secondary batteries with nonaqueous electrolytic solution, process for the production of the active material, and secondary batteries with nonaqueous electrolytic solution |
| CN102522538A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Microwave preparation method for nano lithium manganese |
| CN103022469A (en) * | 2012-12-13 | 2013-04-03 | 青岛乾运高科新材料股份有限公司 | Method for preparing lithium manganate anode material through ultrasonic wave activation technology |
| CN103413943A (en) * | 2013-08-14 | 2013-11-27 | 宁波奈克斯特新材料科技有限公司 | Lithium manganese phosphate positive electrode material and preparation method thereof |
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