CN108630457B - Amorphous manganese dioxide and preparation method and application thereof - Google Patents
Amorphous manganese dioxide and preparation method and application thereof Download PDFInfo
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- CN108630457B CN108630457B CN201810437945.8A CN201810437945A CN108630457B CN 108630457 B CN108630457 B CN 108630457B CN 201810437945 A CN201810437945 A CN 201810437945A CN 108630457 B CN108630457 B CN 108630457B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/46—Metal oxides
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention relates to amorphous manganese dioxide and a preparation method and application thereofThe preparation method comprises the following steps: (1) mixing KMnO4Solution and Mn (CH)3COO)2·4H2Mixing the O solution to prepare a uniform solution; (2) adding a KOH solution into the uniform solution obtained in the step (1), and stirring to obtain a dark brown precipitate; (3) and (3) washing, drying, grinding and calcining the dark brown precipitate obtained in the step (2) to obtain an amorphous manganese dioxide material. The prepared amorphous manganese dioxide is used as a positive electrode material of a sodium ion battery. Compared with the prior art, the method has the advantages of simple synthesis process, simple reaction conditions and low requirement on reaction environment, and is suitable for large-scale industrialization. The amorphous manganese dioxide material is used as the positive electrode material of the sodium ion battery, has larger specific surface area, greatly improves the migration rate of sodium ions, and shows higher specific capacity and good cycling stability.
Description
Technical Field
The invention relates to the field of materials, in particular to a preparation method and application of amorphous manganese dioxide.
Background
Under the environment that the shortage of fossil fuels and the increasingly prominent environmental problems exist in the world at present, the development and the use of novel green energy are more and more paid more attention by people. The new energy systems which are researched most widely at present comprise energy systems such as solar energy, geothermal energy, wind energy and the like, but the systems have the intermittent problem, so that the systems cannot be effectively utilized on a large scale. The key point for solving the problem lies in the development of energy storage technology. Among the existing energy storage technologies, chemical energy storage is the most widely used energy storage method because of its advantages of simplicity and high efficiency. In chemical energy storage, lithium ion batteries are also the most concerned. The lithium ion battery has the advantages of high energy density, long service life, environmental friendliness and the like, and is applied and developed in the fields of portable mobile equipment, new energy automobiles, smart power grids and the like. Therefore it is superiorThe key to promote the development of lithium ion batteries is to change the existing electrode materials of lithium ion batteries and develop novel electrode materials. However, with the large-scale use of the lithium battery, the storage of the lithium resource on the earth is not ideal enough, which causes the problems of the shortage of the lithium resource and the subsequent lithium price up-regulation, etc., and the cost of the lithium ion battery is greatly increased, which will restrict the application of the lithium ion battery in the energy storage field. The metal sodium element and the metal lithium element are in the first main group in the periodic table, are similar to the lithium element in physical properties and chemical properties, and have abundant storage in the earth crust, so the sodium-ion battery is regarded as an energy storage system which is most likely to be an ideal substitute of the lithium-ion battery. For sodium ion batteries, the search for low-cost and high-performance anode and cathode materials is a current key problem. Manganese dioxide (MnO)2) The material has high theoretical specific capacity, wide raw material source, low price, environmental protection and the like, and is widely concerned in the application of the chemical power supply field.
Chinese patent CN102583562A discloses a preparation method of manganese dioxide as a supercapacitor electrode material, wherein pyrrole and potassium permanganate are mixed and stirred, and MnO is obtained after filtration, washing and drying2And the powder is used as an electrode material of a super capacitor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a positive electrode material of a sodium-ion battery and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
one of the purposes of the invention is to provide a preparation method of an amorphous manganese dioxide material, which comprises the following steps:
(1) mixing KMnO4Solution and Mn (CH)3COO)2·4H2Mixing the O solution to prepare a uniform solution;
(2) adding a KOH solution into the uniform solution obtained in the step (1), and stirring to obtain a dark brown precipitate;
(3) and (3) washing, drying, grinding and calcining the dark brown precipitate obtained in the step (2) to obtain an amorphous manganese dioxide material.
Preferably, in the step (1): KMnO4The concentration of the solution is 0.2mol/L, Mn (CH)3COO)2·4H2The concentration of the O solution was 0.3 mol/L.
Preferably, in the step (1): while stirring, the mixture was stirred in the direction of KMnO4Adding Mn (CH) dropwise into the solution3COO)2·4H2Adding dropwise O solution, and stirring for 5min, wherein KMnO solution is prepared4And Mn (CH)3COO)2·4H2The mass ratio of O is 1: 1.5.
Preferably, in the step (2): the concentration of KOH solution is 0.16g/L, and KOH and KMnO are added4The mass ratio of (A) to (B) is 0.0016: 1.58.
Preferably, in the step (2): stirring was carried out at room temperature for 4 h.
Preferably, in the step (3): the washing is carried out by using deionized water and absolute ethyl alcohol and washing for a plurality of times respectively.
Preferably, in the step (3): the drying temperature is 85 ℃, and the drying time is 12 h.
Preferably, in the step (3): the calcination is carried out in an air atmosphere, the calcination temperature is 400 ℃, and the calcination time is 3 h.
The invention also aims to provide the application of the amorphous manganese dioxide material in preparing the positive electrode material of the sodium-ion battery.
By mixing the above-synthesized amorphous MnO2The material and a conductive agent (graphite: carbon black is 4:6) are mixed according to the mass ratio of 7:2 and added into a ball milling tank, the mixture is dry-milled for two hours in a planetary ball mill, then, absolute ethyl alcohol is added as a dispersing agent to be wet-milled for two hours, and the obtained active substance is dried in a constant-temperature drying oven. 9mg of active material and Polytetrafluoroethylene (PTFE) are weighed and mixed into slurry according to the mass ratio of 9:1, and the slurry is coated on a positive electrode shell of a CR2016 type button cell welded with a stainless steel net. After being compacted, the mixture is placed in a vacuum drying oven and dried for 12 hours at the temperature of 100 ℃.
The invention limits the addition amount of KOH and keeps KOH and KMnO4The mass ratio of (A) to (B) is 0.0016: 1.58. KOH and KMnO at concentrations of 0.04, 0.08 and 0.12g/L4The amorphous manganese dioxide material synthesized at the mass ratio of 0.0004: 1.58, 0.0008: 1.58 and 0.0012: 1.58 can not maintain the amorphous structure after being calcined at 400 ℃, the sample with 0.04 and 0.08g/L of KOH is calcined at 200 ℃ to generate the crystal form transformation, and the manganese dioxide is transformed from the amorphous state into α -MnO with the bar-shaped crystal form2The samples with 0.12g/L KOH also underwent amorphous to rod-like manganese dioxide conversion after calcination at 400 ℃ and the rod-like form α -MnO compared to amorphous manganese dioxide2The specific capacity of the positive electrode material of the sodium ion battery is low, and the cycling stability is poor. The calcination temperature is limited in the invention and is kept at 400 ℃. The specific capacity of the sample after calcination at 200 ℃ and 600 ℃ is reduced, and the cycling stability is poor.
Compared with the prior art, the amorphous manganese dioxide is prepared by adopting the liquid-phase coprecipitation method, the synthesis process is simple, the reaction condition is simple, the requirement on the reaction environment is low, and the method is suitable for large-scale industrialization. The amorphous manganese dioxide material is used as the positive electrode material of the sodium ion battery, has larger specific surface area, greatly improves the migration rate of sodium ions, and shows higher specific capacity and good cycling stability.
Drawings
FIG. 1 is an SEM image of an amorphous manganese dioxide material of the present invention;
FIG. 2 is a TEM image of an amorphous manganese dioxide material of the present invention;
FIG. 3 is a selected area diffraction pattern of an amorphous manganese dioxide material of the present invention;
FIG. 4 is a specific capacity curve of an amorphous manganese dioxide material of the present invention as a positive electrode material for sodium ion batteries cycled 200 times at 0.1C charge-discharge rate;
fig. 5 is a capacity curve of an amorphous manganese dioxide material of the present invention used as a positive electrode material of a sodium ion battery at different rates.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Examples
1.58g of KMnO at room temperature4And 3.68g Mn (CH)3COO)2·4H2Preparing 50mL of solution from O by using deionized water respectively, and preparing KMnO4The solution was magnetically stirred and then Mn (CH)3COO)2·4H2The O solution was added dropwise to KMnO4The solution was stirred for 5 minutes to form a homogeneous solution. Preparing 10mL of KOH solution with the concentration of 0.16g/L, adding the KOH solution into the uniform solution, keeping magnetic stirring for 4 hours at room temperature to obtain dark brown precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for several times respectively, drying the precipitate in an oven at 85 ℃ for 12 hours, grinding the precipitate uniformly by using a mortar, and calcining the precipitate at 400 ℃ for 3 hours in an air atmosphere to obtain a sample manganese dioxide.
MnO to be synthesized2The material and a conductive agent (graphite: carbon black is 4:6) are mixed according to the mass ratio of 7:2 and added into a ball milling tank, the mixture is dry-milled for two hours in a planetary ball mill, then, absolute ethyl alcohol is added as a dispersing agent to be wet-milled for two hours, and the obtained active substance is dried in a constant-temperature drying oven. 9mg of active material and Polytetrafluoroethylene (PTFE) are weighed and mixed into slurry according to the mass ratio of 9:1, and the slurry is coated on a positive electrode shell of a CR2016 type button cell welded with a stainless steel net. After being compacted, the mixture is placed in a vacuum drying oven and dried for 12 hours at the temperature of 100 ℃.
Then, a metal sodium sheet is taken as a negative electrode in a glove box filled with argon, and the electrolyte is 1mol/L NaClO4(NaClO4Dissolved in EC: DMC in a volume ratio of 1: 1), and a CR2016 type button cell is assembled by using whatman GF/C type glass fiber as a diaphragm. And (3) carrying out constant-current charge and discharge test by using a Land battery test system, wherein the test temperature is constant at 25 ℃, and the test voltage is 2-4V.
Fig. 1 is an SEM image of the amorphous manganese dioxide of the present invention, from which it can be seen that the amorphous manganese dioxide is agglomerated in the form of spherical particles having a diameter of about 30 to 40nm and a uniform distribution. Fig. 2 is a TEM image of the amorphous manganese dioxide of the present invention, which can further confirm that the microstructure of the amorphous manganese dioxide is in a form of spheres, and the microstructure is in an amorphous form with short-range order and long-range disorder, and has no obvious lattice fringes and is a characteristic of an amorphous material when observed under a high magnification. The selected diffraction pattern of the material is shown in fig. 3, which shows a circle of confusion, which is a characteristic diffraction phenomenon of an amorphous material, and further verifies that the manganese dioxide material is in an amorphous form.
Fig. 4 is a specific capacity curve of amorphous manganese dioxide as a positive electrode material of a sodium ion battery, which is cycled for 200 times at a charge-discharge rate of 0.1C. It can be seen from the figure that except for the low initial discharge specific capacity, after 200 cycles, the discharge specific capacity of the active material can still be maintained at 180.8mAh/g, and the coulombic efficiency is always maintained at above 99%, which indicates that the material can still exhibit high specific capacity performance and good cycle stability performance even under a long charge-discharge process when used as a positive electrode material of a sodium ion battery.
Fig. 5 is a capacity curve of the material at different rates. After 5 times of short-cycle charge and discharge are respectively carried out under the multiplying power of 0.1C, 0.2C, 0.5C, 1C, 2C and 5C, the specific discharge capacity is kept at 180.2mAh/g, 157.5mAh/g, 120.8mAh/g, 95.5mAh/g, 71.4mAh/g and 47.1mAh/g, and the cycle stability is good.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A preparation method of amorphous manganese dioxide material is characterized by comprising the following steps:
(1) mixing KMnO4Solution and Mn (CH)3COO)2·4H2Mixing the O solution to prepare a uniform solution;
(2) adding a KOH solution into the uniform solution obtained in the step (1), and stirring to obtain a dark brown precipitate;
(3) washing, drying, grinding and calcining the dark brown precipitate obtained in the step (2) to obtain an amorphous manganese dioxide material;
in the step (2): the concentration of KOH solution is 0.16g/L, and KOH and KMnO are added4The mass ratio of (A) to (B) is 0.0016: 1.58;
in the step (3): the calcination is carried out in an air atmosphere, the calcination temperature is 400 ℃, and the calcination time is 3 h.
2. A method of producing an amorphous manganese dioxide material according to claim 1, wherein in step (1): KMnO4The concentration of the solution is 0.2mol/L, Mn (CH)3COO)2·4H2The concentration of the O solution was 0.3 mol/L.
3. A method of producing an amorphous manganese dioxide material according to claim 1, wherein in step (1): while stirring, the mixture was stirred in the direction of KMnO4Adding Mn (CH) dropwise into the solution3COO)2·4H2Adding dropwise O solution, and stirring for 5min, wherein KMnO solution is prepared4And Mn (CH)3COO)2·4H2The mass ratio of O is 1: 1.5.
4. A method of producing an amorphous manganese dioxide material according to claim 1, wherein in step (2): stirring was carried out at room temperature for 4 h.
5. A method of producing an amorphous manganese dioxide material according to claim 1, wherein in step (3): the washing is carried out by using deionized water and absolute ethyl alcohol and washing for a plurality of times respectively.
6. A method of producing an amorphous manganese dioxide material according to claim 1, wherein in step (3): the drying temperature is 85 ℃, and the drying time is 12 h.
7. Amorphous manganese dioxide, obtainable by the preparation process according to any one of claims 1 to 6.
8. Use of amorphous manganese dioxide according to claim 7 for the preparation of positive electrode material for sodium ion batteries.
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