CN109037613B - Ruthenium dioxide coated spinel lithium-rich lithium manganate and preparation method thereof - Google Patents
Ruthenium dioxide coated spinel lithium-rich lithium manganate and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- 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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Abstract
The invention discloses ruthenium dioxide coated spinel lithium-rich lithium manganate and a preparation method thereof. The preparation method comprises the following steps: performing microwave hydrothermal reaction on an aqueous solution of sodium hydroxide and manganese sesquioxide at the temperature of 160-; carrying out molten salt reaction on lithium nitrate, potassium chloride and a precursor at the temperature of 450-500 ℃ to obtain spinel lithium-rich lithium manganate; dispersing spinel lithium-rich lithium manganate into an aqueous solution of ruthenium chloride, then adding an aqueous solution of sodium hydroxide, and then reacting the separated solid at the temperature of 150 ℃ and 180 ℃. The ruthenium dioxide coated spinel lithium-rich lithium manganate prepared by the invention coats a layer of ruthenium dioxide on the surface of the lithium-rich lithium manganate, on one hand, RuO2Can increase surface Li+And conduction of electrons, RuO on the other hand2The direct contact between the lithium-rich lithium manganate and the electrolyte is avoided, the stability of a crystal structure is improved, and the high-temperature storage and cycle performance of the lithium-rich lithium manganate is further improved.
Description
Technical Field
The invention relates to ruthenium dioxide coated spinel lithium-rich lithium manganate and a preparation method thereof.
Background
The spinel lithium manganate has a stable structure and a three-dimensional rapid lithium ion diffusion channel, so that the spinel lithium manganate has excellent safety performance and rapid charge and discharge capacity, is rich in manganese element reserves, low in price and environment-friendly, and can be widely applied to the field of large power batteries.
At present, a surface coating method can be adopted to effectively prevent the dissolution problem of manganese and avoid Mn3+The part contacted with the electrolyte generates disproportionation reaction, thereby improving the electrochemical performance of the material. However, patent CN105914366A discloses a method for preparing spinel lithium-rich lithium manganate coated with boron oxide, and patent CN105958034A discloses a method for preparing spinel lithium-rich lithium manganate coated with silicon oxide, both of which adopt a method of directly mixing lithium-rich lithium manganate with an oxide to be coated, but the raw materials used by both of them are insoluble solid powders, and homogeneous mixing is difficult to achieve; in patent CN105932263A, the lithium-rich lithium manganate prepared by a solid-phase sintering method has poor crystallinity, which results in unsatisfactory overall performance of the coated material.
Therefore, the research and development of a spinel lithium-rich lithium manganate material with good electrochemical performance is a problem to be solved urgently.
Disclosure of Invention
The invention provides a ruthenium dioxide coated spinel lithium-rich lithium manganate and a preparation method thereof, and aims to overcome the defects that in the prior art, spinel lithium manganate has capacity attenuation and poor cycle performance due to Mn dissolution and other side reactions in the cycle process, and the poor crystallinity of the obtained lithium-rich lithium manganate caused by a solid-phase sintering method causes unsatisfactory overall performance of the coated material. The spinel lithium-rich lithium manganate prepared by the method has the advantages of small and uniform particle size, high crystallinity, higher specific capacity, simple preparation process, environmental friendliness, low post-treatment temperature and short reaction period; the ruthenium dioxide coated spinel lithium-rich lithium manganate prepared by the invention is coated with a layer of ruthenium dioxide, RuO on the surface of the lithium-rich lithium manganate2On the one hand, the surface Li can be increased+And the lithium-rich lithium manganate is conducted with electrons, on the other hand, the direct contact of the lithium-rich lithium manganate and the electrolyte is avoided, and the crystal structure is improvedThe stability of the lithium-rich lithium manganate is improved, and the high-temperature storage and cycle performance of the lithium-rich lithium manganate is further improved.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of spinel lithium-rich lithium manganate coated with ruthenium dioxide, which comprises the following steps:
(1) performing microwave hydrothermal reaction on an aqueous solution of sodium hydroxide and manganese sesquioxide at the temperature of 160-;
(2) carrying out molten salt reaction on lithium nitrate, potassium chloride and the precursor obtained in the step (1) at the temperature of 450-500 ℃ to obtain spinel lithium-rich lithium manganate;
(3) dispersing the spinel lithium-rich lithium manganate obtained in the step (2) into an aqueous solution of ruthenium chloride, then adding an aqueous solution of sodium hydroxide into the aqueous solution, and then reacting the solid obtained by separation at the temperature of 150-;
in the steps (1) and (2), the mass ratio of the manganese sesquioxide, the sodium hydroxide, the lithium nitrate and the potassium chloride is (0.8-1.2): (8-12): (0.56-0.84): (1.38-2.06);
in the step (3), the mass ratio of the spinel lithium-rich lithium manganate, the ruthenium chloride and the sodium hydroxide is 100: (1.56-15.6): (0.92-9.2).
In step (1), the concentration of the aqueous solution of sodium hydroxide may be conventional, and may be, for example, 4 to 6 mol/L.
In the step (1), the microwave hydrothermal reaction can be carried out in a microwave reaction kettle.
In the step (1), the microwave hydrothermal reaction time can be 5-7 hours, and can also be 6 hours. The temperature of the microwave hydrothermal reaction is preferably 180 ℃.
In the step (1), after the microwave hydrothermal reaction is finished, the obtained precursor can be washed with water to be neutral, and then dried. The operation and conditions of the drying may be conventional in the art, for example, the drying may be carried out in an oven. The drying temperature can be 75-85 ℃ and can also be 80 ℃.
In the step (2), the temperature for the molten salt reaction is preferably 480 ℃. The time of the molten salt reaction can be 8-12h, and can also be 10 h.
In the step (2), after the molten salt reaction is finished, the obtained spinel lithium-rich lithium manganate can be washed with water and dried. The operation and conditions of the drying may be conventional in the art, for example, the drying may be carried out in an oven. The temperature of the drying may be 75-85 ℃.
In step (2), the progress of the molten salt reaction can be monitored by a conventional test method in the field, and the reaction end point is generally determined when no chlorine exists in the filtrate after water washing.
In the steps (1) and (2), the mass ratio of the manganese sesquioxide, the sodium hydroxide, the lithium nitrate and the potassium chloride may be 1:10:0.7: 1.72.
In the step (3), the concentration of the aqueous solution of sodium hydroxide can be 1-1.5 mol/L.
In the step (3), in order to control the degree of reaction, the addition may be performed in a dropwise manner.
In the step (3), in order to make the reaction more complete, the aqueous solution of sodium hydroxide may be stirred after the addition is completed. The stirring time can be 1-2 h.
In the step (3), the step of separating may include filtering and washing.
In step (3), the reaction time may be conventional in the art, and may be, for example, 15 to 20 hours.
In the step (3), the mass ratio of the spinel lithium-rich lithium manganate, the ruthenium chloride and the sodium hydroxide can be 100: (8.0-9.0): (4.5-5.5), and also can be 100:8.58: 4.96.
In the invention, the aqueous solution of sodium hydroxide reacts with the ruthenium chloride to form ruthenium hydroxide in the dropping process, the ruthenium hydroxide can be uniformly coated on the surface of the spinel lithium-rich lithium manganate by stirring, and then the ruthenium hydroxide reacts at the temperature of 150-.
The invention also provides the ruthenium dioxide coated spinel lithium-rich lithium manganate material prepared by the preparation method.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the spinel lithium-rich lithium manganate prepared by the method has the advantages of small and uniform particle size, high crystallinity, higher specific capacity, simple preparation process, environmental friendliness, low post-treatment temperature and short reaction period; the ruthenium dioxide coated spinel lithium-rich lithium manganate prepared by the invention is coated with a layer of ruthenium dioxide, RuO on the surface of the lithium-rich lithium manganate2On the one hand, the surface Li can be increased+And the lithium-rich lithium manganate is conducted by electrons, so that the direct contact between the lithium-rich lithium manganate and an electrolyte is avoided, the stability of a crystal structure is improved, and the high-temperature storage and cycle performance of the lithium-rich lithium manganate is improved.
Drawings
FIG. 1 is a scanning electron micrograph of spinel lithium-rich lithium manganate produced in example 1 of the present invention.
FIG. 2 is an X-ray diffraction chart of spinel lithium-rich lithium manganate obtained in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples 1 to 3, the molten salt reaction was monitored by the following method: stopping the reaction, naturally cooling, taking out the sample, and carrying out suction filtration on the sample under the condition of cleaning by distilled water until no white precipitate appears after the filtrate is detected by 0.1mol/L silver nitrate solution, and determining that no chlorine exists, wherein the molten salt reaction is finished.
Comparative example 1
Weighing 1g of manganese oxide, adding the manganese oxide into 50mL of 5mol/L NaOH solution, stirring for 0.5h to obtain a precursor solution which is uniformly mixed, transferring the precursor solution into a microwave reaction kettle, heating for 6h at 180 ℃ by microwave, washing a product with water until the pH value is 7, and drying in an oven at 80 ℃. And mixing the product with 0.7g of lithium nitrate and 1.72g of potassium chloride, uniformly grinding, carrying out molten salt reaction at 480 ℃ for 10 hours, washing the product with water until no chlorine exists, and drying to obtain the spinel lithium-rich lithium manganate.
Example 1
Weighing 1g of manganese oxide, adding the manganese oxide into 50mL of 5mol/L NaOH solution, stirring for 0.5h to obtain a precursor solution which is uniformly mixed, transferring the precursor solution into a microwave reaction kettle, heating for 6h at 180 ℃ by microwave, washing a product with water until the pH value is 7, and drying in an oven at 80 ℃. And mixing the product with 0.7g of lithium nitrate and 1.72g of potassium chloride, uniformly grinding, carrying out molten salt reaction at 480 ℃ for 10 hours, washing the product with water until no chlorine exists, and drying to obtain the spinel lithium-rich lithium manganate. The high-power scanning electron microscope is shown in figure 1, and it can be seen from figure 1 that the spinel lithium-rich lithium manganate prepared by the method has complete crystal form and uniform particle size; the X-ray diffraction pattern is shown in FIG. 2, and it can be seen from FIG. 2 that the spinel lithium-rich lithium manganate obtained by the above method has no impurities and good crystallinity.
Weighing spinel lithium-rich lithium manganate in a mass ratio of: ruthenium chloride ═ 100: 1.56, firstly, dissolving ruthenium chloride in deionized water to prepare a solution, and uniformly dispersing spinel lithium-rich lithium manganate in ruthenium chloride (RuCl)3) Stirring the mixture for 1 to 2 hours at room temperature in the aqueous solution, dropwise adding 1mol/L sodium hydroxide solution into the mixture until the reaction is complete, continuing stirring the mixture for 1 to 2 hours, filtering and washing the mixture, and reacting the mixture for 15 to 20 hours in the air at the temperature of 150 ℃ to 180 ℃ to obtain the ruthenium dioxide coated spinel lithium-rich lithium manganate.
Wherein, the aqueous solution of sodium hydroxide reacts with ruthenium chloride in the dropping process to form ruthenium hydroxide, and the ruthenium hydroxide is uniformly coated on the surface of the spinel lithium-rich lithium manganate, and then the ruthenium dioxide-coated spinel lithium-rich lithium manganate is formed by reaction at the temperature of 150-.
Example 2
Weighing 1g of manganese oxide, adding the manganese oxide into 50mL of 5mol/L NaOH solution, stirring for 0.5h to obtain a precursor solution which is uniformly mixed, transferring the precursor solution into a microwave reaction kettle, heating for 6h at 180 ℃ by microwave, washing a product with water until the pH value is 7, and drying in an oven at 80 ℃. And mixing the product with 0.7g of lithium nitrate and 1.72g of potassium chloride, uniformly grinding, carrying out molten salt reaction at 480 ℃ for 10 hours, washing the product with water until no chlorine exists, and drying to obtain the spinel lithium-rich lithium manganate.
Weighing spinel lithium-rich lithium manganate in a mass ratio of: ruthenium chloride ═ 100:8.58, firstly, dissolving ruthenium chloride in deionized water to prepare a solution, and uniformly dispersing spinel lithium-rich lithium manganate in ruthenium chloride (RuCl)3) Stirring the mixture for 1 to 2 hours at room temperature in the aqueous solution, dropwise adding 1mol/L sodium hydroxide solution into the mixture until the reaction is complete, continuing stirring the mixture for 1 to 2 hours, filtering and washing the mixture, and reacting the mixture for 15 to 20 hours in the air at the temperature of 150 ℃ to 180 ℃ to obtain the ruthenium dioxide coated spinel lithium-rich lithium manganate.
Example 3
Weighing 1g of manganese oxide, adding the manganese oxide into 50mL of 5mol/L NaOH solution, stirring for 0.5h to obtain a precursor solution which is uniformly mixed, transferring the precursor solution into a microwave reaction kettle, heating for 6h at 180 ℃ by microwave, washing a product with water until the pH value is 7, and drying in an oven at 80 ℃. And mixing the product with 0.7g of lithium nitrate and 1.72g of potassium chloride, uniformly grinding, carrying out molten salt reaction at 480 ℃ for 10 hours, washing the product with water until no chlorine exists, and drying to obtain the spinel lithium-rich lithium manganate.
Weighing spinel lithium-rich lithium manganate in a mass ratio of: ruthenium chloride ═ 100: 15.6 dissolving ruthenium chloride in deionized water to prepare a solution, and uniformly dispersing spinel lithium-rich lithium manganate in ruthenium chloride (RuCl)3) Stirring the mixture for 1 to 2 hours at room temperature in the aqueous solution, dropwise adding 1mol/L sodium hydroxide solution into the mixture until the reaction is complete, continuing stirring the mixture for 1 to 2 hours, filtering and washing the mixture, and reacting the mixture for 15 to 20 hours in the air at the temperature of 150 ℃ to 180 ℃ to obtain the ruthenium dioxide coated spinel lithium-rich lithium manganate.
Effect example 1
The materials obtained in examples 1 to 4 were applied as positive electrode materials to CR2016 type button cells and then subjected to electrical property tests, the results of which are shown in table 1.
TABLE 1
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (15)
1. A preparation method of spinel lithium-rich lithium manganate coated with ruthenium dioxide is characterized by comprising the following steps:
(1) performing microwave hydrothermal reaction on an aqueous solution of sodium hydroxide and manganese sesquioxide at the temperature of 160-;
(2) carrying out molten salt reaction on lithium nitrate, potassium chloride and the precursor obtained in the step (1) at the temperature of 450-500 ℃ to obtain spinel lithium-rich lithium manganate;
(3) dispersing the spinel lithium-rich lithium manganate obtained in the step (2) into an aqueous solution of ruthenium chloride, then adding an aqueous solution of sodium hydroxide into the aqueous solution, and then reacting the solid obtained by separation at the temperature of 150-;
in the steps (1) and (2), the mass ratio of the manganese sesquioxide, the sodium hydroxide, the lithium nitrate and the potassium chloride is (0.8-1.2): (8-12): (0.56-0.84): (1.38-2.06);
in the step (3), the mass ratio of the spinel lithium-rich lithium manganate, the ruthenium chloride and the sodium hydroxide is 100: (1.56-15.6): (0.92-9.2).
2. The method according to claim 1, wherein in the step (1), the concentration of the aqueous solution of sodium hydroxide is 4 to 6 mol/L.
3. The preparation method according to claim 1, wherein in the step (1), the microwave hydrothermal reaction is carried out in a microwave reaction kettle;
in the step (1), the microwave hydrothermal reaction is carried out for 5-7 hours;
in the step (1), the temperature of the microwave hydrothermal reaction is 180 ℃;
in the step (1), after the microwave hydrothermal reaction is finished, the obtained precursor is washed to be neutral by water and then dried.
4. The preparation method according to claim 3, wherein the microwave hydrothermal reaction time in step (1) is 6 hours.
5. The method of claim 3, wherein the drying is performed in an oven;
the drying temperature is 75-85 ℃.
6. The method of claim 5, wherein the drying temperature is 80 ℃.
7. The method according to claim 1, wherein in the step (2), the molten salt is reacted at a temperature of 480 ℃;
in the step (2), the molten salt is reacted for 8-12 h;
and (2) after the molten salt reaction is finished, washing the obtained spinel lithium-rich lithium manganate with water, and drying.
8. The method according to claim 7, wherein in the step (2), the molten salt is reacted for 10 hours.
9. The method of claim 7, wherein the drying is performed in an oven; the drying temperature is 75-85 ℃.
10. The method according to claim 1, wherein in the step (3), the concentration of the aqueous solution of sodium hydroxide is 1 to 1.5 mol/L;
in the step (3), the adding mode is dropwise adding;
in the step (3), stirring the aqueous solution of sodium hydroxide after the addition is finished; in the step (3), the separation step comprises filtering and washing;
in the step (3), the reaction time is 15-20 h.
11. The method according to claim 10, wherein in the step (3), the stirring time is 1 to 2 hours.
12. The production method according to claim 1, wherein in steps (1) and (2), the mass ratio of the manganous oxide, the sodium hydroxide, the lithium nitrate and the potassium chloride is 1:10:0.7: 1.72.
13. The method according to claim 1, wherein in the step (3), the mass ratio of the spinel lithium-rich lithium manganate, the ruthenium chloride and the sodium hydroxide is 100: (8.0-9.0): (4.5-5.5).
14. The method according to claim 13, wherein in the step (3), the mass ratio of the spinel lithium-rich lithium manganate, the ruthenium chloride and the sodium hydroxide is 100:8.58: 4.96.
15. A ruthenium dioxide coated spinel lithium-rich lithium manganate material prepared by the preparation method according to any one of claims 1 to 9.
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