CN114853073A - Preparation method of linear MnOOH, negative electrode material and application - Google Patents
Preparation method of linear MnOOH, negative electrode material and application Download PDFInfo
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- CN114853073A CN114853073A CN202210598278.8A CN202210598278A CN114853073A CN 114853073 A CN114853073 A CN 114853073A CN 202210598278 A CN202210598278 A CN 202210598278A CN 114853073 A CN114853073 A CN 114853073A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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 provides a preparation method of linear MnOOH, a cathode material and application. The preparation method comprises the following steps: mixing an alcohol amine solution and a Mn source solution, and then aging to obtain the linear MnOOH, wherein the molar ratio of the alcohol amine substance to the Mn source is (0.1-2): (0.4 to 1). The method needs few raw materials, does not need high-pressure reaction equipment, and therefore reduces the preparation cost of MnOOH, the prepared MnOOH linear structure has a multi-dimensional ion channel, and the obtained MnOOH has battery activity and excellent discharge performance and cycle performance.
Description
Technical Field
The invention relates to the field of sodium-ion batteries, and discloses a preparation method of linear MnOOH, a negative electrode material and application.
Background
Sodium ion batteries have unique advantages in terms of resources and costs compared to lithium ion batteries, while also having great potential in terms of safety and cycle performance, and are therefore considered as the most promising electrochemical energy storage devices for large-scale applications. At present, common sodium ion negative electrode materials mainly comprise carbon-based negative electrode materials, alloy negative electrode materials, oxide negative electrode materials and the like, and development of novel sodium ion negative electrode materials is expected to expand application scenes of sodium ion batteries and promote commercial application processes of the sodium ion batteries.
MnOOH is a common manganese element compound, MnOOH materials can be applied to the fields of adsorption, catalysis, electrochemistry and the like, and in the electrochemistry field, MnOOH is often used as a precursor for preparing lithium manganese oxide spinel structure and other manganese oxides and is considered as the most simple and practical precursor for preparing manganese oxide.
CN109607619A discloses a preparation method of shape-controllable MnOOH nano-wires for treating phenol-containing wastewater, which takes ethylene glycol, CTAB and LAS as surfactants and KMnO 4 Mixing, and reacting the obtained solution at high temperature and high pressure to obtain the MnOOH nanowire.
CN109264786A discloses a preparation method and application of MnOOH. Mixing a manganese nitrate solution, urea, absolute ethyl alcohol and deionized water, and reacting in a high-pressure reaction kettle at 130-150 ℃ for 18-24 h to obtain gamma-MnOOH.
CN109455764A discloses a preparation method of MnOOH. Performing hydrothermal reaction on potassium permanganate and acetate, and controlling reaction conditions to prepare various types of MnOOH including linear MnOOH, rod-shaped MnOOH, flower-shaped MnOOH and the like.
In the method, the reaction needs to be carried out under the conditions of high temperature and high pressure, the reaction process is complex, and meanwhile, the raw materials used in CN109607619A and CN109455764A are potassium permanganate, so that the price is high, and the large-scale production application is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of linear MnOOH, a negative electrode material and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of linear MnOOH, which comprises the following steps:
mixing an alcohol amine solution and a Mn source solution, and then aging to obtain the linear MnOOH, wherein the molar ratio of the alcohol amine substance to the Mn source is (0.1-2): (0.4 to 1), wherein the molar ratio may be 0.1:0.4, 0.2:0.4, 0.4:0.4, 0.6:0.4, 0.8:0.4, 1:0.4, 1.2:0.4, 1.4:0.4, 1.6:0.4, 1.8:0.4, 2:0.4, 0.1:0.7, 0.2:0.7, 0.4:0.7, 0.6:0.7, 0.8:0.7, 1:0.7, 1.2:0.7, 1.4:0.7, 1.6:0.7, 1.8:0.7, 2:0.7, 0.1:1, 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.6:1, 1.8:1, 1.1: 1, 1.2:1, 1:1, 1.6:1, 1.8:1, or 1.8:1, or more, but the like values are not specifically recited in the same.
The method needs few raw materials, does not need high-pressure reaction equipment, thereby reducing the preparation cost of MnOOH, and the prepared MnOOH linear structure has a multi-dimensional ion channel.
As a preferred embodiment of the present invention, the alcohol amine solution includes any one of an ethanolamine solution, a diethanolamine solution or a triethanolamine solution or a combination of at least two thereof, wherein the combination is exemplified by, but not limited to: a combination of an ethanolamine solution and a diethanolamine solution, a combination of a diethanolamine solution and a triethanolamine solution, a combination of an ethanolamine solution and a triethanolamine solution, or the like.
Preferably, the Mn source solution comprises a divalent metal salt solution.
Preferably, the Mn source solution includes Mn (NO) 3 ) 2 Solution, MnCl 2 Solutions or MnSO 4 Any one or a combination of at least two of the solutions, wherein typical but non-limiting examples of such combinations are: mn (NO) 3 ) 2 Solution and MnCl 2 Combination of solutions, MnCl 2 Solution and MnSO 4 Combinations of solutions or Mn (NO) 3 ) 2 Solution and MnSO 4 Combinations of solutions, and the like.
In a preferred embodiment of the present invention, the concentration of the alkanolamine solution is 0.1 to 0.12mM, wherein the concentration may be 0.1mM, 0.11mM or 0.12mM, but is not limited to the values recited, and other values not recited within the above range are also applicable.
Preferably, the concentration of the Mn source solution is 0.1-0.6 mM, wherein the concentration can be 0.1mM, 0.2mM, 0.3mM, 0.4mM, 0.5mM, or 0.6mM, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the mixing also comprises an alkali liquor.
Preferably, the lye comprises sodium hydroxide.
Preferably, the concentration of the alkali solution is 0.1-0.12 mM, wherein the concentration can be 0.1mM, 0.11mM or 0.12mM, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferable technical scheme of the invention, the molar ratio of the alcohol amine substance, the Mn source and the alkali liquor is (0.1-2): (0.4-1): (0 to 0.5), wherein the molar ratio may be 0.2:0.4:0.1, 0.4:0.4:0.2, 0.6:0.4:0.3, 0.8:0.4:0.4, 1:0.4:0.5, 1.2:0.4:0.1, 1.4: 0.4:0.2, 1.6:0.4:0.3, 1.8: 0.4:0.4, 2:0.4:0.5, 0.2: 0.7:0.2, 0.4:0.7:0.3, 0.6:0.7:0.4, 0.8:0.7:0.5, 1.2:0.7:0.1, 1.4:0.7:0.2, 1.6:0.7:0.3, 1.8:0.7:0.4, 2:0.7:0.5, 0.2:1:0.1, 0.4:1:0.2, 0.6:1:0.3, 0.8:1:0.4, 1:1:0.5, 1.4:1:0.1, 1.6:1:0.2, 1.8:1:0.3, or 2:1:0.4, and the like, wherein alkali lye may not be contained but not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
In a preferred embodiment of the present invention, the mixing temperature is 5 to 35 ℃, wherein the temperature may be 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
Preferably, the mixing time is 3-30 min, wherein the time can be 3min, 5min, 10min, 15min, 20min, 25min or 30min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mixing is carried out at a pH of 7.0 to 9.5, wherein the pH can be 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, etc., but is not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred embodiment of the present invention, the aging is performed under sealed conditions.
The aging step is carried out under sealing, so that part of Mn element in the final product is prevented from being oxidized from trivalent to quadrivalent, and the purity of the product is influenced.
Preferably, the temperature of aging is 20 to 35 ℃, wherein the temperature can be 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃ or 35 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The aging temperature is too short, the reaction is insufficient, the aging time is too long, and the MnOOH structure can generate clustering phenomenon, thereby influencing the electrochemical performance.
Preferably, the aging time is 12-48 h, wherein the aging time can be 12h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48h, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the linear MnOOH has a diameter of 3 to 15nm, wherein the diameter may be 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, or 15nm, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
Preferably, the linear MnOOH has a length of 300 to 3000nm, wherein the length may be 300nm, 500nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000nm, or the like, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
The second purpose of the invention is to provide a negative electrode material, which comprises manganese oxide, wherein a precursor of the manganese oxide comprises linear MnOOH, and the linear MnOOH is prepared by the preparation method of the first purpose.
The third object of the present invention is to provide the negative electrode material of the second object, which is applied to the field of sodium ion batteries.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
the MnOOH prepared by the invention has battery activity, when the current density is 80mA/g, the initial discharge specific capacity is more than 490mAh/g, the coulombic efficiency is as high as more than 94%, and after 100 times of circulation, the capacity retention rate is more than 91%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of linear MnOOH, which comprises the following steps:
mixing the mixture at a concentration of 10ml0.8mM ethanolamine aqueous solution and 10ml of 0.4mM Mn (NO) 3 ) 2 And rapidly stirring the aqueous solution in a sealed reaction container, testing the pH value of the system during stirring, aging at room temperature for 24h after the pH value of the system reaches (8.0 +/-0.1), filtering and washing the reaction solution, and drying the obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain the linear MnOOH.
Example 2
The embodiment provides a preparation method of linear MnOOH, which comprises the following steps:
10ml of 0.6mM aqueous diethanolamine solution and 10ml of 0.4mM MnSO 4 Rapidly stirring the aqueous solution and 10ml of 0.1mM sodium hydroxide aqueous solution in a sealed reaction vessel, testing the pH of the system in the stirring process, aging at room temperature for 24h after the pH of the system reaches (8.0 +/-0.1), filtering and washing the reaction solution, and drying the obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain the linear MnOOH.
Example 3
The embodiment provides a preparation method of linear MnOOH, which comprises the following steps:
10ml of a 0.8mM triethanolamine aqueous solution and 10ml of 0.4mM Mn (NO) 3 ) 2 Rapidly stirring the aqueous solution and 2ml of 0.1mM sodium hydroxide aqueous solution in a sealed reaction vessel, testing the pH of the system in the stirring process, aging at room temperature for 24h after the pH of the system reaches (8.0 +/-0.1), filtering and washing the reaction solution, and drying the obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain the linear MnOOH.
Example 4
This example was carried out under the same conditions as in example 1 except that the aging was carried out at room temperature after the pH of the system reached (8.0. + -. 0.1) and was replaced with the aging at room temperature after the pH of the system reached (7.5. + -. 0.1).
Example 5
This example was carried out under the same conditions as in example 1 except that the aging was carried out at room temperature after the pH of the system reached (8.0. + -. 0.1) and was replaced with the aging at room temperature after the pH of the system reached (8.5. + -. 0.1).
Example 6
This example was carried out under the same conditions as example 1 except that aging at room temperature for 24 hours was replaced with aging at room temperature for 10 hours.
Example 7
This example was identical to example 1 except that aging at room temperature for 24 hours was replaced with aging at room temperature for 30 hours.
Example 8
This example was carried out under the same conditions as in example 1 except that the reaction conditions were changed to those in the open vessel instead of the sealed vessel.
Comparative example 1
This comparative example except that 10ml of an aqueous ethanolamine solution having a concentration of 0.8mM and 10ml of Mn (NO) having a concentration of 0.4mM were used 3 ) 2 The aqueous solution was replaced with 6.25ml of an aqueous solution of ethanolamine having a concentration of 0.8mM and 30ml of Mn (NO) having a concentration of 0.4mM 3 ) 2 The conditions other than the aqueous solution were the same as in example 1.
The linear MnOOH prepared in examples 1 to 8 and comparative example 1 was assembled as a sodium ion battery negative active material to perform a test of electrochemical performance, and the linear MnOOH prepared in examples 1 to 8 and comparative example 1 was subjected to a test of thickness and length, and the test results are shown in table 1.
In which, the linear MnOOH obtained in the present examples and comparative examples was used as an active material, acetylene black was used as a conductive agent, polyvinylidene fluoride was used as a binder, and N-methylpyrrolidone was used as a solvent. Preparing active substances, acetylene black and polyvinylidene fluoride into slurry according to the mass ratio of 8:1:1, uniformly coating the slurry on a copper foil, after vacuum drying, processing by using a slicing machine, cutting into a circular electrode slice with the diameter of 14mm, and placing the circular electrode slice in a vacuum drying oven at 120 ℃ for 12 hours. Assembling a battery in a glove box filled with argon, wherein the metal sodium is used as a counter electrode, and the electrolyte consists of electrolyte salt and an organic solvent, wherein the electrolyte salt is mainly NaPF 6 And the solvent is Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (volume ratio is 1: 1), the diaphragm is a glass fiber membrane, the foam nickel is used as a filler, the CR2025 button cell is assembled by the solvent and the foam nickel, and the first discharge specific capacity test, the coulombic efficiency test and the capacity retention rate test after 100 cycles of circulation are carried out under the current density of 80mA/g。
TABLE 1
Through the table, it can be found that by changing the test conditions such as reactant type, reaction pH, aging time, aging temperature, etc., MnOOH with different structural morphologies can be obtained, and the electrochemical performance of the MnOOH varies with the structure of the product. The molar ratio of the alcohol amine substance to the Mn source in comparative example 1 is 0.05: 1.2, linear MnOOH can not be obtained finally, so that the proper raw material proportion is the key for the success of the invention. From the test results of the embodiments 1 to 3, it can be seen that linear MnOOH can be obtained by adopting different alcohol amine systems and adjusting the mixture ratio of reactants, and when the obtained MnOOH is used as a negative electrode material of a sodium ion battery, the first discharge specific capacity, the coulombic efficiency and the capacity retention rate after 100 cycles of circulation of the MnOOH meet expectations, so that the material prepared by the invention has a good application prospect in the sodium ion battery.
It can be seen from the examples 4 and 5 that the shape of linear MnOOH can be controlled by controlling the pH at the beginning of aging, and the larger the pH at the beginning of aging is, the longer MnOOH is, and the change of the shape of the product finally influences the electrochemical performance of the material;
it can be seen from examples 6 and 7 that target products with different morphologies can be obtained by changing the aging time, and the longer the aging time is, the longer the obtained MnOOH is, the change of the morphology of the product can finally affect the electrochemical performance of the material.
Example 8 shows that the reaction system is changed from a sealed system to an open system, and the ideal target product is not obtained, which is related to the oxidation of trivalent Mn by oxygen in the air during the reaction, and it can be seen that the proper reaction conditions are also the key to the success of the invention.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of linear MnOOH is characterized by comprising the following steps:
mixing an alcohol amine solution and a Mn source solution, and then aging to obtain the linear MnOOH, wherein the molar ratio of the alcohol amine substance to the Mn source is (0.1-2): (0.4 to 1).
2. The method according to claim 1, wherein the alcohol amine solution comprises any one of an ethanolamine solution, a diethanolamine solution or a triethanolamine solution or a combination of at least two thereof;
preferably, the Mn source solution comprises a divalent metal salt solution;
preferably, the Mn source solution includes Mn (NO) 3 ) 2 Solution, MnCl 2 Solutions or MnSO 4 Any one of or a combination of at least two of the solutions.
3. The method according to claim 1 or 2, wherein the concentration of the alkanolamine solution is 0.1 to 0.12 mM;
preferably, the concentration of the Mn source solution is 0.1-0.6 mM.
4. The method according to any one of claims 1 to 3, wherein the mixing further comprises a lye;
preferably, the lye comprises sodium hydroxide;
preferably, the concentration of the alkali liquor is 0.1-0.12 mM.
5. The preparation method according to claim 4, wherein the molar ratio of the alcohol amine substance, the Mn source and the alkali liquor is (0.1-2): (0.4-1): (0 to 0.5).
6. The method according to any one of claims 1 to 5, wherein the mixing temperature is 5 to 35 ℃;
preferably, the mixing time is 3-30 min;
preferably, the mixing is carried out under a condition of pH 7.0-9.5.
7. The production method according to any one of claims 1 to 6, wherein the aging is performed under sealed conditions;
preferably, the aging temperature is 20-35 ℃;
preferably, the aging time is 12-48 h.
8. The method according to any one of claims 1 to 7, wherein the linear MnOOH has a diameter of 3 to 15 nm;
preferably, the length of the linear MnOOH is 300-3000 nm.
9. A negative electrode material, characterized in that the negative electrode material comprises manganese oxide, and a precursor of the manganese oxide comprises linear MnOOH prepared by the preparation method of any one of claims 1 to 8.
10. The use of the negative electrode material according to claim 9, wherein the negative electrode material is used in the field of sodium ion batteries.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041553A (en) * | 2010-12-21 | 2011-05-04 | 浙江大学 | Preparation method and application of crystalline-state beta-MnOOH nanowire |
| CN102219263A (en) * | 2011-05-20 | 2011-10-19 | 浙江大学 | Method for preparing Gamma-MnOOH nanometer rod |
| CN109455764A (en) * | 2018-11-08 | 2019-03-12 | 广东工业大学 | A kind of preparation method of MnOOH |
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- 2022-05-30 CN CN202210598278.8A patent/CN114853073A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041553A (en) * | 2010-12-21 | 2011-05-04 | 浙江大学 | Preparation method and application of crystalline-state beta-MnOOH nanowire |
| CN102219263A (en) * | 2011-05-20 | 2011-10-19 | 浙江大学 | Method for preparing Gamma-MnOOH nanometer rod |
| CN109455764A (en) * | 2018-11-08 | 2019-03-12 | 广东工业大学 | A kind of preparation method of MnOOH |
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