CN111682168A - Cobalt diselenide particle with core-shell structure and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a cobalt diselenide particle with a core-shell structure, and a preparation method and application thereof. The preparation method of the cobalt diselenide particles with the core-shell structure comprises the following steps: 1) preparing ZIF-67; 2) preparing ZIF-67@ ZIF-8; 3) preparing ZIF-67@ ZIF-8@ ZIF-67; 4) preparing multilayer core-shell structure composite particles which take ZIF-67 as a core and are alternately coated with ZIF-8 and ZIF-67; 5) and uniformly mixing the multilayer core-shell structure composite particles and selenium powder, placing in a protective atmosphere, heating for annealing, and evaporating most of ZIF-8. The invention prepares the cobalt diselenide particles with the core-shell structure into the cathode material of the sodium ion battery and assembles the sodium ion battery. The cobalt diselenide particles with the core-shell structure have large specific surface area and stable structure, and can be used as a cathode material of a sodium ion battery to improve the specific capacity of the sodium ion battery and improve the cycling stability and the rate capability of the sodium ion battery.
Description
Technical Field
The invention relates to cobalt diselenide particles with a core-shell structure and a preparation method and application thereof, belonging to the technical field of sodium ion batteries.
Background
The storage capacity of the metal sodium on the earth is large, the distribution is wide, the extraction is simple, the sodium and the lithium are in the same main group in the periodic table of elements and have similar physical and chemical properties, the sodium ion battery has a similar working principle with the lithium ion battery, and the price of the metal sodium is much cheaper than that of the metal lithium, so the sodium ion battery is considered as a new generation energy storage device capable of replacing the lithium ion battery. The performance of the sodium ion battery is directly related to the performance of the negative electrode material, and the negative electrode material of the lithium ion battery cannot be directly converted into the sodium ion battery due to the fact that the radius of sodium ions is larger than that of lithium ions, so that the negative electrode material suitable for the sodium ion battery needs to be developed.
MOFs (metal organic framework compounds) are the most rapidly developed porous materials in the last two decades, contain transition metal elements and organic groups, have excellent pore channel structures and regular morphological characteristics, and porous carbon/metal compound composite materials prepared by taking the MOFs as precursors or sacrificial templates under the conditions of inert gases or ammonia gas and the like through a high-temperature carbonization technology can be used as electrode materials, so that the porous carbon/metal compound composite materials have good application prospects. However, the sodium ion battery assembled by using the material prepared from the MOFs as the negative electrode material of the sodium ion battery has the problems of low charge-discharge specific capacity, poor rate capability, poor cycle performance and the like, and cannot well meet the requirements of practical application.
Therefore, there is a need to develop a negative electrode material for sodium ion batteries with better performance.
Disclosure of Invention
The invention aims to provide cobalt diselenide particles with a core-shell structure and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of cobalt diselenide particles with core-shell structures comprises the following steps:
1) dispersing soluble cobalt salt and 2-methylimidazole in a solvent, and fully reacting to obtain a zeolite imidazolate framework material ZIF-67;
2) dispersing ZIF-67 in a solvent, adding soluble zinc salt and 2-methylimidazole, fully reacting, and coating a zeolitic imidazolate framework material ZIF-8 outside ZIF-67 to obtain ZIF-67@ ZIF-8;
3) dispersing ZIF-67@ ZIF-8 in a solvent, adding a soluble cobalt salt and 2-methylimidazole, fully reacting, and coating ZIF-67 outside ZIF-67@ ZIF-8 to obtain ZIF-67@ ZIF-8@ ZIF-67;
4) referring to the operations of the step 2) and the step 3), obtaining multilayer core-shell structure composite particles which take ZIF-67 as a core and are alternately coated by ZIF-8 and ZIF-67;
5) and uniformly mixing the multilayer core-shell structure composite particles and selenium powder, placing in a protective atmosphere, heating for annealing, and evaporating most of ZIF-8 to obtain the core-shell structure cobalt diselenide particles.
Preferably, the soluble cobalt salt is at least one of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetate.
Preferably, the soluble zinc salt is at least one of zinc nitrate, zinc sulfate, zinc chloride and zinc acetate.
Preferably, the molar ratio of cobalt ions to 2-methylimidazole in the soluble cobalt salt in the step 1) is 1: (4-8).
Preferably, the mass ratio of the ZIF-67 to the soluble zinc salt in the step 2) is 1: (1.5-2.0).
Preferably, the molar ratio of zinc ions to 2-methylimidazole in the soluble zinc salt in the step 2) is 1: (1.8-2.2).
Preferably, the mass ratio of the ZIF-67@ ZIF-8 in the step 3) to the soluble cobalt salt is 1: (1.5-2.0).
Preferably, the molar ratio of cobalt ions to 2-methylimidazole in the soluble cobalt salt in the step 3) is 1: (1.8-2.2).
Preferably, the number of the shell layers of the multilayer core-shell structure composite particle in the step 4) is 2 or 4 or 6 or 8.
Further preferably, the number of the shell layers of the multilayer core-shell structure composite particle in the step 4) is 4.
Preferably, the mass ratio of the multilayer core-shell structure composite particles to the selenium powder in the step 5) is 1: (1-3).
Preferably, the annealing in the step 5) is carried out at 500-700 ℃ for 2-4 h.
The invention has the beneficial effects that: the cobalt diselenide particles with the core-shell structure have large specific surface area and stable structure, and can be used as a cathode material of a sodium ion battery to improve the specific capacity of the sodium ion battery and improve the cycling stability and the rate capability of the sodium ion battery.
Specifically, the method comprises the following steps:
1) the cobalt diselenide particles with the core-shell structure have a multilayer structure, and cavities among layers can provide a larger specific surface area, are favorable for embedding and separating sodium ions, and can accelerate the migration of the sodium ions;
2) the cavity in the cobalt diselenide particle with the core-shell structure can reduce the volume expansion of the cathode material in the charging and discharging process of the sodium ion battery;
3) compared with the existing cathode material, the assembled sodium ion battery has higher specific capacity and cycling stability under the condition of high current density, and has higher stability in the charging and discharging processes.
Drawings
Fig. 1 is a schematic structural diagram of cobalt diselenide particles with core-shell structures in example 1.
FIG. 2 shows the core-shell cobalt diselenide particles of example 1 and CoSe of comparative example2@ZnSe2Scanning electron micrographs of the particles.
FIG. 3 is a sodium ion battery containing core-shell cobalt diselenide particles of example 1 and CoSe containing comparative example2@ZnSe2Figure for rate performance testing of sodium ion batteries of particles.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of cobalt diselenide particles with core-shell structures comprises the following steps:
1) dissolving 3mmol of cobalt nitrate into 30mL of methanol to obtain a methanol solution of cobalt nitrate, dissolving 12mmol of dimethylimidazole into 30mL of methanol to obtain a methanol solution of dimethylimidazole, quickly pouring the methanol solution of dimethylimidazole into the methanol solution of cobalt nitrate, magnetically stirring for 5min, standing at room temperature for 24h, centrifuging, washing the centrifuged solid with methanol for 3 times, and vacuum-drying at 60 ℃ for 12h to obtain a zeolitic imidazolate framework material ZIF-67;
2) ultrasonically dispersing 90mg of ZIF-67 in 30mL of methanol, adding 150mg of zinc nitrate and 10mL of methanol solution of 2-methylimidazole with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8;
3) ultrasonically dispersing 90mg of ZIF-67@ ZIF-8 in 30mL of methanol, adding 150mg of cobalt nitrate and 10mL of 2-methylimidazole methanol solution with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8@ ZIF-67;
4) ultrasonically dispersing 90mg of ZIF-67@ ZIF-8@ ZIF-67 in 30mL of methanol, adding 150mg of zinc nitrate and 10mL of a 32.8mg/mL methanol solution of 2-methylimidazole, stirring at room temperature for 24 hours, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8;
5) ultrasonically dispersing 90mg of ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8 in 30mL of methanol, adding 150mg of cobalt nitrate and 10mL of methanol solution of 2-methylimidazole with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8@ ZIF-67;
6) ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8@ ZIF-67 and selenium powder are uniformly mixed according to the mass ratio of 1:2, then the mixture is placed in a nitrogen atmosphere, the temperature is raised to 600 ℃ at the speed of 1 ℃/min, and the mixture is kept for 2 hours, so that the cobalt diselenide particles with the core-shell structure are obtained (the structural schematic diagram is shown in figure 1, the multilayer core-shell structure has two layers of cavities in the middle, the surface is rough and porous, and the whole body is a regular dodecahedron).
Example 2:
a preparation method of cobalt diselenide particles with core-shell structures comprises the following steps:
1) dissolving 3mmol of cobalt nitrate into 30mL of methanol to obtain a methanol solution of cobalt nitrate, dissolving 15mmol of dimethylimidazole into 30mL of methanol to obtain a methanol solution of dimethylimidazole, quickly pouring the methanol solution of dimethylimidazole into the methanol solution of cobalt nitrate, magnetically stirring for 5min, standing at room temperature for 24h, centrifuging, washing the centrifuged solid with methanol for 3 times, and vacuum-drying at 60 ℃ for 12h to obtain a zeolitic imidazolate framework material ZIF-67;
2) ultrasonically dispersing 90mg of ZIF-67 in 30mL of methanol, adding 150mg of zinc nitrate and 12mL of methanol solution of 2-methylimidazole with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8;
3) ultrasonically dispersing 90mg of ZIF-67@ ZIF-8 in 30mL of methanol, adding 150mg of cobalt nitrate and 10mL of 2-methylimidazole methanol solution with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8@ ZIF-67;
4) ultrasonically dispersing 90mg of ZIF-67@ ZIF-8@ ZIF-67 in 30mL of methanol, adding 150mg of zinc nitrate and 12mL of a 32.8mg/mL methanol solution of 2-methylimidazole, stirring at room temperature for 24 hours, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8;
5) ultrasonically dispersing 90mg of ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8 in 30mL of methanol, adding 150mg of cobalt nitrate and 10mL of methanol solution of 2-methylimidazole with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8@ ZIF-67;
6) uniformly mixing ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8@ ZIF-67 and selenium powder according to the mass ratio of 1:3, placing in a nitrogen atmosphere, heating to 600 ℃ at the speed of 2 ℃/min, and keeping for 3h to obtain the cobalt diselenide particles with the core-shell structure.
Example 3:
a preparation method of cobalt diselenide particles with core-shell structures comprises the following steps:
1) dissolving 3mmol of cobalt nitrate into 30mL of methanol to obtain a methanol solution of cobalt nitrate, dissolving 18mmol of dimethylimidazole into 30mL of methanol to obtain a methanol solution of dimethylimidazole, quickly pouring the methanol solution of dimethylimidazole into the methanol solution of cobalt nitrate, magnetically stirring for 5min, standing at room temperature for 24h, centrifuging, washing the centrifuged solid with methanol for 3 times, and vacuum-drying at 60 ℃ for 12h to obtain a zeolitic imidazolate framework material ZIF-67;
2) ultrasonically dispersing 90mg of ZIF-67 in 30mL of methanol, adding 150mg of zinc nitrate and 14mL of methanol solution of 2-methylimidazole with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8;
3) ultrasonically dispersing 90mg of ZIF-67@ ZIF-8 in 30mL of methanol, adding 150mg of cobalt nitrate and 10mL of 2-methylimidazole methanol solution with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8@ ZIF-67;
4) ultrasonically dispersing 90mg of ZIF-67@ ZIF-8@ ZIF-67 in 30mL of methanol, adding 150mg of zinc nitrate and 14mL of a 32.8mg/mL methanol solution of 2-methylimidazole, stirring at room temperature for 24 hours, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8;
5) ultrasonically dispersing 90mg of ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8 in 30mL of methanol, adding 150mg of cobalt nitrate and 10mL of methanol solution of 2-methylimidazole with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8@ ZIF-67;
6) uniformly mixing ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8@ ZIF-67 and selenium powder according to the mass ratio of 1:1, placing in a nitrogen atmosphere, heating to 600 ℃ at the speed of 3 ℃/min, and keeping for 4h to obtain the cobalt diselenide particles with the core-shell structure.
Comparative example:
CoSe2@ZnSe2A particle, the method of making comprising the steps of:
1) respectively preparing a methanol solution of cobalt nitrate and a methanol solution of 2-methylimidazole, quickly pouring the methanol solution of 2-methylimidazole into the methanol solution of cobalt nitrate according to the molar ratio of 1:4 of cobalt nitrate to 2-methylimidazole, magnetically stirring for 5min, standing for 24h at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times, and vacuum-drying at 60 ℃ for 12h to obtain a zeolitic imidazolate framework material ZIF-67;
2) ultrasonically dispersing 90mg of ZIF-67 in 30mL of methanol, adding 150mg of zinc nitrate and 14mL of methanol solution of 2-methylimidazole with the concentration of 32.8mg/mL, stirring for 24 hours at room temperature, centrifuging, washing the centrifuged solid with methanol for 3 times to obtain ZIF-67@ ZIF-8;
3) uniformly mixing ZIF-67@ ZIF-8 and selenium powder according to the mass ratio of 1:2, placing in a nitrogen atmosphere, heating to 600 ℃ at the speed of 5 ℃/min, and keeping for 1h to obtain CoSe2@ZnSe2And (3) granules.
And (3) performance testing:
1) core-shell cobalt diselenide particles of example 1 and CoSe of comparative example2@ZnSe2The scanning electron micrograph of the particles is shown in FIG. 2 (a is cobalt diselenide particles with core-shell structure, and b is CoSe2@ZnSe2Particles).
As can be seen from fig. 2: ZIF-67@ ZIF-8@ ZIF-67@ ZIF-8@ ZIF-67 still keeps a regular dodecahedron structure after annealing, and the surface is rough and porous.
2) Uniformly mixing the core-shell structure cobalt diselenide particles, acetylene black (a conductive agent) and sodium alginate (a binder) in the example 1 according to a mass ratio of 7:2:1, adding a proper amount of deionized water, grinding to prepare slurry, coating the slurry on a copper foil, performing vacuum drying for 12 hours to prepare a pole piece, taking a sodium piece as a reference electrode, and taking a sodium hexafluorophosphate solution with the concentration of 1mol/L as an electrolyte (the solvent is dimethyl carbonate and ethylene carbonate in a volume ratio of 1: 1; electrolyte solution was further added with 5% fluoroethylene carbonate), and glass fiber paper was used as a separator, and assembled into a half cell, and CoSe for the same operation was used2@ZnSe2Assembling half cell with the particles, and then applying the sodium ion cell containing the core-shell structure cobalt diselenide particles of example 1 and the CoSe containing the comparative example2@ZnSe2The rate performance test of the sodium ion battery with the particles is shown in fig. 3.
As can be seen from fig. 3: the sodium ion battery containing the cobalt diselenide particles with the core-shell structure in the embodiment 1 keeps stable capacity under the current density of 0.1-5A/g, the capacity reaches 250mAh/g when the current density is 5A/g, and the initial capacity can still be returned after the current density is finally returned to 0.1A/g.
The core-shell structure cobalt diselenide particles of the embodiments 2 and 3 are tested by referring to the above method, and the results show that the core-shell structure cobalt diselenide particles of the embodiments 2 and 3 have similar morphology structure and electrochemical performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of cobalt diselenide particles with core-shell structures is characterized by comprising the following steps: the method comprises the following steps:
1) dispersing soluble cobalt salt and 2-methylimidazole in a solvent, and fully reacting to obtain a zeolite imidazolate framework material ZIF-67;
2) dispersing ZIF-67 in a solvent, adding soluble zinc salt and 2-methylimidazole, fully reacting, and coating a zeolitic imidazolate framework material ZIF-8 outside ZIF-67 to obtain ZIF-67@ ZIF-8;
3) dispersing ZIF-67@ ZIF-8 in a solvent, adding a soluble cobalt salt and 2-methylimidazole, fully reacting, and coating ZIF-67 outside ZIF-67@ ZIF-8 to obtain ZIF-67@ ZIF-8@ ZIF-67;
4) referring to the operations of the step 2) and the step 3), obtaining multilayer core-shell structure composite particles which take ZIF-67 as a core and are alternately coated by ZIF-8 and ZIF-67;
5) and uniformly mixing the multilayer core-shell structure composite particles and selenium powder, placing in a protective atmosphere, heating for annealing, and evaporating most of ZIF-8 to obtain the core-shell structure cobalt diselenide particles.
2. The method of claim 1, wherein: the soluble cobalt salt is at least one of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetate; the soluble zinc salt is at least one of zinc nitrate, zinc sulfate, zinc chloride and zinc acetate.
3. The production method according to claim 1 or 2, characterized in that: the molar ratio of cobalt ions to 2-methylimidazole in the soluble cobalt salt in the step 1) is 1: (4-8).
4. The production method according to claim 1 or 2, characterized in that: step 2), the mass ratio of the ZIF-67 to the soluble zinc salt is 1: (1.5-2.0); the molar ratio of zinc ions to 2-methylimidazole in the soluble zinc salt in the step 2) is 1:
(1.8～2.2)。
5. the production method according to claim 1 or 2, characterized in that: step 3), the mass ratio of the ZIF-67@ ZIF-8 to the soluble cobalt salt is 1: (1.5-2.0); the mol ratio of cobalt ions to 2-methylimidazole in the soluble cobalt salt in the step 3) is 1: (1.8-2.2).
6. The production method according to claim 1 or 2, characterized in that: and step 5), the mass ratio of the multilayer core-shell structure composite particles to the selenium powder is 1: (1-3).
7. The production method according to claim 1 or 2, characterized in that: and 5) annealing at 500-700 ℃ for 2-4 h.
8. A cobalt diselenide particle with a core-shell structure is characterized in that: prepared by the method of any one of claims 1 to 7.
9. A sodium ion battery negative electrode material is characterized in that: the composition comprises the cobalt diselenide particles with the core-shell structure of claim 8.
10. A sodium ion battery, characterized by: the negative electrode is made of the negative electrode material of the sodium-ion battery of claim 9.
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| CN116632219A (en) * | 2023-07-19 | 2023-08-22 | 兰溪博观循环科技有限公司 | Metal phosphate composite material with core-shell structure, and preparation method and application thereof |
| CN116632219B (en) * | 2023-07-19 | 2023-10-24 | 兰溪博观循环科技有限公司 | Metal phosphate composite material with core-shell structure, and preparation method and application thereof |
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