CN113394388A - Preparation method of high-specific-capacity sodium-sulfur battery positive electrode material - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 27
- 239000011593 sulfur Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910021389 graphene Inorganic materials 0.000 claims description 19
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 241000219991 Lythraceae Species 0.000 description 1
- 229910014103 Na-S Inorganic materials 0.000 description 1
- 229910014147 Na—S Inorganic materials 0.000 description 1
- 235000014360 Punica granatum Nutrition 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
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- Electrochemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention belongs to the technical field of sodium-sulfur batteries, and particularly relates to a preparation method of a high-specific-capacity sodium-sulfur battery positive electrode material. The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material comprises the following steps: (1) preparing ZIF-67; (2) preparing ZIF-67@ rGO; (3) preparation of sulfur/ZIF-67 @ rGO. The method is simple in process, and the prepared ZIF-67@ rGO can be used for loading more active substances and accelerating the conversion of sodium polysulfide, so that the electrochemical performance of the sodium-sulfur battery is improved.
Description
Technical Field
The invention belongs to the technical field of sodium-sulfur batteries, and particularly relates to a preparation method of a high-specific-capacity sodium-sulfur battery positive electrode material.
Background
Efficient large-scale electrical energy storage systems are receiving wide attention in today's world and a variety of promising energy storage devices have been developed, including metal-ion batteries, metal-oxygen batteries, and metal-sulfur batteries. Through decades of research and development, the anode material (such as LiMn) of the traditional ion battery2O4、LiCoO2、LiNiO2、LiFePO4Etc.) have been widely used in cellular phones, notebook computers, digital cameras, and hybrid cars. However, as the demand for energy storage devices with high energy density, such as submersible vehicles, unmanned planes and grid-scale stationary storage, increases, the ion battery cannot meet the demand for high energy density devices due to its limited theoretical energy density, and is currently difficult to be applied and popularized.
In contrast, metal-sulfur batteries, such as sodium-sulfur (Na-S) batteries, are highly advantageous due to the low cost of sulfur resources and the high specific energy of the batteries. However, the following problems still exist at present, which severely restrict the development of the sodium-sulfur battery: intermediate polysulfides (Na)2Sn,4<n<8) Readily dissolved in the electrolyte and free to migrate between the anode and cathode regions, this "shuttle effect" can lead to irreversible sulfur depletion, anode passivation and coulombic inefficiency, which in turn leads to unstable and inefficient battery chemistry. In addition, the conductivity of sulfur is poor (room temperature conductivity is only 5X 10)-30S·m-1) Large changes in the volume of the active material during cycling (170%) can cause severe electrochemical polarization and greatly limit the utilization of sulfur.
Research shows that the shuttling problem of polysulfide in the sodium-sulfur battery is the root cause of poor cycle performance of the sodium-sulfur battery, and for the commercial development of the sodium-sulfur battery, the problem needs to be solved.
Disclosure of Invention
The invention aims to provide a preparation method of a high-specific-capacity sodium-sulfur battery positive electrode material for overcoming poor sulfur conductivity and shuttle effect in the sodium-sulfur battery charging and discharging process, the method is simple in process, and the prepared ZIF-67@ rGO can be used for loading more active substances and accelerating the conversion of sodium polysulfide, so that the electrochemical performance of the sodium-sulfur battery is improved.
The technical scheme of the invention is as follows: a preparation method of a high-specific-capacity sodium-sulfur battery positive electrode material comprises the following steps:
(1) preparation of ZIF-67: firstly, respectively dissolving dimethyl imidazole and cobalt nitrate hexahydrate in a methanol solution to prepare a dimethyl imidazole solution and a cobalt nitrate solution; then adding the dimethyl imidazole solution into the cobalt nitrate solution, fully stirring, standing, centrifuging, collecting precipitate, washing and drying to obtain ZIF-67;
(2) preparation of ZIF-67@ rGO: weighing the ZIF-67 prepared in the step (1), adding the ZIF-67 into a graphene oxide aqueous solution, carrying out ultrasonic treatment, and stirring to obtain a spray solution; carrying out spray drying treatment on the spray solution at the temperature of 100-300 ℃ to prepare ZIF-67@ rGO;
(3) preparation of sulfur/ZIF-67 @ rGO: and (3) mixing pure sulfur powder with the ZIF-67@ rGO obtained in the step (2), fully grinding, and placing the obtained mixture in a reaction kettle for hydrothermal reaction to obtain the sulfur/ZIF-67 @ rGO composite material.
The ZIF-67@ rGO prepared in the step (2) is rough in surface, is in a pomegranate shape and is 3-4 microns on average; the rGO with a lamellar structure is uniformly coated on the outer layer of the ZIF-67 particles, the ZIF-67 particles are regular polygonal nano particles, and the outline of the rhombic surface is clear.
In the step (1), 1-3 g of dimethyl imidazole and 1-3 g of cobalt nitrate hexahydrate are respectively dissolved in 100-300 mL of methanol solution.
Stirring for 30 minutes in the step (1), and standing for 24 hours; washed three times with ethanol and dried at 70 ℃ for 24 h.
In the step (2), ZIF-67 is 100-200 mg, and is added into 100mL of graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 2 mg/mL-1。
And (3) carrying out ultrasonic treatment for 1-3 hours in the step (2), and stirring for 24 hours.
Pure sulfur powder in the step (3) according to the mass ratio: ZIF-67@ rGO is 3: 1.
The temperature of the hydrothermal reaction in the step (3) is 155 ℃, and the time is 12 h.
The invention has the beneficial effects that: according to the invention, the structure of the ZIF-67 is reformed through spray drying, the rGO is covered outside the ZIF-67, a complex micro-nano hierarchical structure is provided, and the ZIF-67 polyhedrons are tightly gathered and fully wrapped by a reduced graphene oxide thin shell (ZIF-67@ rGO). The situation that the ZIF-67 is poor in conductivity can be improved by combining reduced graphene oxide (rGO) with good conductivity with the ZIF-67, the structural stability of the gathered ZIF-67 material is further improved due to the reduced graphene oxide, and the structural stability of the material is improved while the conductivity of the material is improved. The high specific surface area of the reduced graphene oxide can provide more sulfur active sites and better fix sulfur, so that the utilization rate of sulfur is improved, sodium polysulfide can be limited near a positive electrode material, the sodium polysulfide generated in the charge-discharge process of the battery can be captured, the good catalytic effect of the ZIF-67 on the sodium polysulfide is cooperated, the conversion of the sodium polysulfide near the positive electrode is accelerated, and the shuttle effect in the battery is further reduced. The battery performance is improved.
Meanwhile, the ZIF-67 material has a large specific surface area, can load sulfur (active substances participating in electrode reaction) as much as possible, accelerates the conversion of sodium polysulfide, and effectively relieves the problem of serious capacity attenuation of the sodium-sulfur battery, thereby improving the performance of the sodium-sulfur battery.
In conclusion, the invention has the substantial characteristics of providing the preparation method for synthesizing the excellent-performance sodium-sulfur battery positive electrode material (sulfur/ZIF-67 @ rGO) with simple preparation process and low cost. The existence of the redox graphene obviously improves the problem of poor conductivity of the ZIF-67, and can also provide a large number of exposed active sites for electrocatalytic reaction, thereby improving the cycle performance of the sodium-sulfur battery. The method has the advantages of simple process and low cost, and avoids introducing external pollutants in each link of the preparation process. The sulfur/ZIF-67 @ rGO material prepared by the method has good structural performance and electrochemical performance.
The sulfur/ZIF-67 @ rGO prepared by the method is expected to promote the practicability of the sodium-sulfur battery with excellent specific capacity and cycle performance due to the unique structural design and the simple preparation process.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of ZIF-67@ rGO of example 1.
FIG. 2 is a Transmission Electron Microscope (TEM) image of ZIF-67@ rGO in example 1.
FIG. 3 is a plot of the cycling capacity measured at 0.1C for sulfur/ZIF-67 @ rGO of example 1 as the positive electrode material for a sodium sulfur battery.
Detailed Description
The present invention will be described in detail below with reference to examples.
Example 1
The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material comprises the following steps:
(1) preparation of ZIF-67: firstly, respectively dissolving 1.64g of dimethylimidazole and 1.45g of cobalt nitrate hexahydrate in 125mL of methanol solution to prepare dimethylimidazole solution and cobalt nitrate solution; then adding the dimethyl imidazole solution into the cobalt nitrate solution, stirring for 30 minutes, standing for 24 hours, centrifuging, collecting precipitates, washing with ethanol for three times, and drying at 70 ℃ for 24 hours to obtain ZIF-67;
(2) preparation of ZIF-67@ rGO: weighing ZIF-67100mg prepared in step (1), adding into 100mL of graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 2mg & lt/EN & gt mL-1Stirring for 24 hours after ultrasonic treatment for 1 hour to obtain a spray solution; spray drying the spray solution at 200 ℃ to prepare ZIF-67@ rGO;
(3) preparation of sulfur/ZIF-67 @ rGO: and (3) mixing pure sulfur powder and the ZIF-67@ rGO obtained in the step (2) according to the mass ratio of 3:1, fully grinding to obtain a mixture, ventilating in a vacuum glove box, putting the mixture into a reaction kettle, and carrying out hydrothermal reaction at the temperature of 155 ℃ for 12 hours to obtain the sulfur/ZIF-67 @ rGO composite material.
SEM (SEM, S-4800, manufactured by Hitachi, Japan) and TEM (TEM, JEM-2100F, manufactured by JE, Japan) analyses were performed on the prepared samples.
As shown in FIG. 1, redox graphene is coated on the outer layer of ZIF-67 by a spray drying method to present a pomegranate-shaped appearance, the ZIF-67 is a regular polygonal nano-particle, and the diamond-shaped surface profile is clear. After spray drying, the structure of the rGO coated on ZIF-67 was lamellar. The surface of the prepared particles ZIF-67@ rGO was relatively rough, averaging about 3-4 μm. The latter tests are also reflected.
It can be confirmed from fig. 2 that the redox graphene is uniformly coated around the ZIF-67 particles.
Mixing the sulfur/ZIF-67 @ rGO composite cathode material obtained in the example 1, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8: 1: 1, fully grinding and mixing to prepare slurry, uniformly coating the slurry on a current collector for drying, cutting a dried positive plate into a circular plate with the diameter of 0.75cm, and assembling the positive plate and a negative plate to obtain the button cell. The prepared sample is subjected to electrochemical performance analysis (BTS-5V5mA, Xinwei), as can be seen from figure 3, under the current density of 0.2C, the discharge specific capacity of the positive electrode material of the sodium-sulfur battery in the first circulation is up to 876mAh/g, the specific capacity of the battery is continuously reduced along with the continuous circulation, 693mAh/g is still remained after 100 cycles of circulation, and the positive electrode material has excellent electrochemical cycle performance.
Example 2
The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material comprises the following steps:
(1) preparation of ZIF-67: firstly, respectively dissolving 2.05g of dimethylimidazole and 1.81g of cobalt nitrate hexahydrate in 175mL of methanol solution to prepare a dimethylimidazole solution and a cobalt nitrate solution; then adding the dimethyl imidazole solution into the cobalt nitrate solution, stirring for 30 minutes, standing for 24 hours, centrifuging, collecting precipitates, washing with ethanol for three times, and drying at 70 ℃ for 24 hours to obtain ZIF-67;
(2) preparation of ZIF-67@ rGO: weighing ZIF-67150mg prepared in step (1), adding into 100mL of graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 2mg & lt/EN & gt mL-1Carrying out ultrasonic treatment for 1.5 hours, and then stirring for 24 hours to obtain a spray solution; spray drying the spray solution at 200 ℃ to prepare ZIF-67@ rGO;
(3) preparation of sulfur/ZIF-67 @ rGO: and (3) mixing pure sulfur powder and the ZIF-67@ rGO obtained in the step (2) according to the mass ratio of 3:1, fully grinding, and placing the obtained mixture into a reaction kettle for hydrothermal reaction at the temperature of 155 ℃ for 12 hours to obtain the sulfur/ZIF-67 @ rGO composite material.
Example 3
The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material comprises the following steps:
(1) preparation of ZIF-67: firstly, respectively dissolving 2.46g of dimethylimidazole and 2.18g of cobalt nitrate hexahydrate in 200mL of methanol solution to prepare dimethylimidazole solution and cobalt nitrate solution; then adding the dimethyl imidazole solution into the cobalt nitrate solution, stirring for 30 minutes, standing for 24 hours, centrifuging, collecting precipitates, washing with ethanol for three times, and drying at 70 ℃ for 24 hours to obtain ZIF-67;
(2) preparation of ZIF-67@ rGO: weighing ZIF-67200mg prepared in step (1), adding into 100mL graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 2 mg/mL-1Carrying out ultrasonic treatment for 2 hours, and then stirring for 24 hours to obtain a spray solution; spray drying the spray solution at 250 ℃ to prepare ZIF-67@ rGO;
(3) preparation of sulfur/ZIF-67 @ rGO: and (3) mixing pure sulfur powder and the ZIF-67@ rGO obtained in the step (2) according to the mass ratio of 3:1, fully grinding, and placing the obtained mixture into a reaction kettle for hydrothermal reaction at the temperature of 155 ℃ for 12 hours to obtain the sulfur/ZIF-67 @ rGO composite material.
Claims (8)
1. A preparation method of a high-specific-capacity sodium-sulfur battery positive electrode material is characterized by comprising the following steps:
(1) preparation of ZIF-67: firstly, respectively dissolving dimethyl imidazole and cobalt nitrate hexahydrate in a methanol solution to prepare a dimethyl imidazole solution and a cobalt nitrate solution; then adding the dimethyl imidazole solution into the cobalt nitrate solution, fully stirring, standing, centrifuging, collecting precipitate, washing and drying to obtain ZIF-67;
(2) preparation of ZIF-67@ rGO: weighing the ZIF-67 prepared in the step (1), adding the ZIF-67 into a graphene oxide aqueous solution, carrying out ultrasonic treatment, and stirring to obtain a spray solution; carrying out spray drying treatment on the spray solution at the temperature of 100-300 ℃ to prepare ZIF-67@ rGO;
(3) preparation of sulfur/ZIF-67 @ rGO: and (3) mixing pure sulfur powder with the ZIF-67@ rGO obtained in the step (2), fully grinding, and placing the obtained mixture in a reaction kettle for hydrothermal reaction to obtain the sulfur/ZIF-67 @ rGO composite material.
2. The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material as claimed in claim 1, wherein the ZIF-67@ rGO prepared in the step (2) has a rough surface, is in a pomegranate-shaped appearance, and has an average size of 3-4 μm; the rGO with a lamellar structure is uniformly coated on the outer layer of the ZIF-67 particles, the ZIF-67 particles are regular polygonal nano particles, and the outline of the rhombic surface is clear.
3. The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material according to claim 1, wherein 1-3 g of dimethylimidazole and 1-3 g of cobalt nitrate hexahydrate in the step (1) are respectively dissolved in 100-300 mL of methanol solution.
4. The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material as claimed in claim 1, wherein in the step (1), the mixture is stirred for 30 minutes and is left standing for 24 hours; washed three times with ethanol and dried at 70 ℃ for 24 h.
5. The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material as claimed in claim 1, wherein the ZIF-67 in the step (2) is 100-200 mg, and the ZIF-67 is added into 100mL of graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 2mg & lt/EN & gt mL-1。
6. The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material as claimed in claim 1, wherein in the step (2), the ultrasonic treatment is performed for 1-3 hours, and the stirring is performed for 24 hours.
7. The preparation method of the high-specific-capacity sodium-sulfur battery positive electrode material as claimed in claim 1, wherein the step (3) comprises the following steps of (1) mixing pure sulfur powder: ZIF-67@ rGO is 3: 1.
8. The preparation method of the high-specific-capacity sodium-sulfur battery cathode material as claimed in claim 1, wherein the temperature of the hydrothermal reaction in the step (3) is 155 ℃ and the time is 12 hours.
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CN112201781A (en) * | 2020-10-16 | 2021-01-08 | 肇庆市华师大光电产业研究院 | Sodium-sulfur battery positive electrode material and preparation method thereof |
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CN107317013A (en) * | 2017-06-30 | 2017-11-03 | 武汉理工大学 | A kind of positive electrode of sodium-sulfur cell material and preparation method thereof |
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