CN109767926B - ZIF-67 framework-based double-shell sulfide and preparation method and application thereof - Google Patents
ZIF-67 framework-based double-shell sulfide and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ZIF-67 framework-based double-shell sulfide, and a preparation method and application thereof, which are expressed as CoS/MCo2S4Wherein the material of the inner shell is CoS, and the material of the outer shell is MCo2S4M may be Ni, Mn, Fe, Cu and Zn. The method specifically comprises the following steps: a. preparing ZIF-67; b. preparing a core-shell intermediate; c. preparing a double-shell sulfide electrode material; d. assembling: and (3) coating the prepared double-shell sulfide on the surface of the foamed nickel to assemble the supercapacitor. The invention has the structural characteristics of a ZIF-67 framework double-shell layer, contains two different sulfides, and has the characteristics of large specific surface area, many active sites and the like, thereby effectively improving the specific capacity of the supercapacitor. The structure of the invention has stable skeleton firmness and a cavity structure, and can slow down the structural collapse of the electrode material of the super capacitor in the charging and discharging processes, thereby remarkably improving the cycle stability of the super capacitor. In addition, the preparation method is simple to operate, good in reproducibility and suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of preparation of composite functional materials with special morphology structures, and particularly relates to a ZIF-67 framework-based double-shell sulfide and a preparation method and application thereof.
Background
The super capacitor is one of the most potential energy storage devices at present, and has the advantages of high power density, long cycle life, rapid charge and discharge, environmental friendliness and the like. The invention provides a preparation method of a high-performance double-shell sulfide based on a ZIF-67 framework structure and an application method of the high-performance double-shell sulfide in a super capacitor. The double-shell sulfide structure comprises a single metal sulfide and a double metal sulfide, the theoretical specific capacitance of the two sulfides is very high, and the double-shell sulfide structure can show a synergistic effect when applied to a super capacitor. The double-shell structure based on the ZIF-67 framework has a stable framework and cavity structure, and can slow down the structural collapse of an electrode material of the supercapacitor in the charging and discharging process, so that the circulating stability of the supercapacitor is remarkably improved. Moreover, the cavity structure of the double-shell layer also enables the material to have the characteristics of large specific surface area, more active sites and the like, and further improves the mass specific capacitance of the super capacitor.
In order to realize the structural characteristic, the invention utilizes the ZIF-67 framework to construct the double-shell sulfide CoS/MCo by a plasma etching method and a chemical vapor deposition method2S4The preparation technology is used as an electrode of the super capacitor and is used for improving the electrochemical performance of the super capacitor. With CoS/NiCo2S4For example, when a supercapacitor is assembled using the double-shell sulfide based on the ZIF-67 skeleton structure prepared by the preparation method of example 1 below as an electrode material: when the current density is 1A/g, the mass specific capacity is 1230F/g; after 9000 cycles, the specific capacity is kept above 76%. Therefore, the super capacitor with high specific capacity, long cycle life and low manufacturing cost is expected to be obtained by a simple and effective preparation method.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention provides a ZIF-67 framework-based double-shell sulfide as well as a preparation method and application thereof, and the first purpose of the invention is to provide a high-performance ZIF-67 framework-based double-shell sulfide for a supercapacitor; the second purpose of the invention is to provide a preparation method of the ZIF-67 framework structure double-shell sulfide.
The technical scheme is as follows: in order to achieve the aim, the invention constructs the double-shell sulfide CoS/MCo by using a ZIF-67 framework through a plasma etching method and a chemical vapor deposition method2S4Wherein the material of the inner shell is CoS, and the material of the outer shell is MCo2S4M can be one of Ni, Mn, Fe, Cu and Zn.
The invention is realized by the following technical scheme, and the steps comprise:
the nano-structure double-shell sulfide powder based on the ZIF-67 framework structure is uniformly mixed with PVDF and acetylene black in a mass ratio of 8:1:1, and the mixture is coated on pretreated foamed nickel with the mass ratio of about 1.5-2.5g/cm2. The coated nickel foam is used as an electrode to be applied to a super capacitor, so that the specific capacity and the cycle life of the super capacitor are improved.
Has the advantages that: compared with the prior art, the invention has the advantages that:
1.) double-shell structure based on ZIF-67 skeleton has stable skeleton and cavity structure, can slow down ultracapacitor system electrode material structure in charge-discharge process and collapse to show improvement ultracapacitor system's circulation stability.
2.) double-shell sulfide based on ZIF-67 skeleton structure has the characteristics of large specific surface area, many active sites and the like, and a certain synergistic effect is generated between the two sulfides of the inner shell and the outer shell, so that the electrochemical performance can be effectively improved, and the sulfide has excellent chemical performance.
3.) the preparation method of the ZIF-67 framework structure double-shell sulfide is simple and direct, avoids the uncertainty of a hydrothermal method, has high repeatability and low cost, and is suitable for large-scale production.
4.) the preparation method has wide application range, and the finally synthesized double-shell sulfide based on the ZIF-67 framework structure is represented as CoS/MCo2S4Wherein M can be one of Ni, Mn, Fe, Cu and Zn. The experimental method can be applied to the preparation of single metal/double metal double-shell sulfides with synergistic effect based on various double shells of ZIF-67 framework structures.
5.) the double-shell sulfide prepared by the method based on the ZIF-67 framework structure has excellent performance, and is made of CoS/NiCo2S4For example, when a supercapacitor was assembled using the double-shell sulfide based on the ZIF-67 skeleton structure prepared by the preparation method of example 1 below as an electrode material: at a current density of 1A/g, the massThe specific capacity is 1230F/g; after 9000 cycles, the specific capacity is kept above 76%.
Drawings
FIG. 1 is a schematic structural diagram of a double-shell sulfide based on a ZIF-67 framework structure;
FIG. 2 is a GCD diagram of the active material obtained in example 1;
FIG. 3 shows 9000 cycles of the active material obtained in example 1;
FIG. 4 is a GCD plot of the active material obtained in example 2;
FIG. 5 is a GCD plot of the active material obtained in example 3;
FIG. 6 is a GCD plot of the active material obtained in example 4;
FIG. 7 is a GCD plot of the active material obtained in example 5;
FIG. 8 is a GCD plot of the active material obtained in example 6.
Detailed Description
The invention prepares a double-shell sulfide based on a ZIF-67 framework structure for improving electrochemical performance of a super capacitor, and the material is represented as CoS/MCo2S4Wherein the material of the inner shell is CoS, and the material of the outer shell is MCo2S4M can be one of Ni, Mn, Fe, Cu and Zn.
The redox reaction occurring with the electrode material is the equation:
the GCD process calculation equation is as follows:
wherein Cs is mass specific capacitance, I is current during constant current charging and discharging, and the unit is A; m is the active material mass in g; Δ T is the discharge time in GCD in units of s; Δ V is the voltage window in units of V; GCD (galvanostatic charge-discharge) is constant current charging and discharging.
The invention is realized by the following technical scheme, and the experimental steps comprise:
a. preparing ZIF-67;
mixing the methanol solution of cobalt nitrate and the methanol solution of dimethyl imidazole, magnetically stirring for 30min, standing at room temperature, centrifuging, washing with methanol, and vacuum drying to obtain purple polyhedral ZIF-67 material
b. Preparing a core-shell intermediate;
putting the ZIF-67 powder prepared in the step a into M (NO)3)2After magnetic stirring, centrifugal cleaning and vacuum drying, the light purple intermediate powder is obtained: core-shell ZIF-67/double hydroxide of a binary metal.
c. Preparation of double-shell sulfide electrode material
Vulcanizing the light purple powder obtained in the step b by using a chemical vapor deposition method.
d. Assembly
The powder is coated on pretreated foamed nickel and used as an electrode for assembling a super capacitor.
Examples
The technical scheme of the invention is further explained by using CoS/NiCo2S4By way of example, CoS/MCo of other metal elements2S4The preparation method of the material is similar, and only the element nickel is replaced by other metal elements. The structural schematic diagram of the double-shell sulfide based on the ZIF-67 framework structure is shown in the figure1 is shown.
Example 1
a. Rapidly mixing 25ml of methanol solution containing 1mmol of cobalt nitrate with 25ml of methanol solution containing 4mmol of dimethyl imidazole, magnetically stirring for 30min, and standing for 9h at room temperature; then, centrifugation, methanol washing and vacuum drying were carried out to obtain purple polyhedral ZIF-67.
b. And (b) putting 50mg of purple powder prepared in the step (a) into 30ml of ethanol solution containing 100mg of nickel nitrate, performing magnetic stirring for 30min, performing centrifugal cleaning, and performing vacuum drying to obtain a light purple intermediate: ZIF-67/nickel cobalt double hydroxide.
c. And c, vulcanizing 50mg of the intermediate obtained in the step b by using a chemical vapor deposition method, wherein the vulcanizing temperature is 300 ℃, the vulcanizing time is 2h, the heating rate is 10 ℃/min, the sulfur source is sublimed sulfur, and the mass of the sublimed sulfur is 100 mg.
d. Uniformly mixing the powdery double-shell sulfide based on the ZIF-67 framework structure, PVDF and acetylene black in a mass ratio of 8:1:1, and coating the mixture on pretreated foamed nickel with the mass ratio of 1.5-2.5g/cm2. And the coated foamed nickel is used as an electrode for assembling the super capacitor.
The supercapacitor is assembled by using the double-shell sulfide based on the ZIF-67 framework structure prepared by the method of the embodiment as an electrode material, wherein a platinum sheet is a counter electrode, saturated calomel is a reference electrode, an active material is a working electrode, and CV and GCD tests are performed by using 2M KOH electrolyte. When the current density is 1A/g, the specific mass capacity of the material is 1230F/g; after 9000 cycles of GCD, the specific capacity remained above 76% compared to the initial value, see fig. 2 and 3.
Example 2
a. Rapidly mixing 25ml of methanol solution containing 1mmol of cobalt nitrate with 25ml of methanol solution containing 4mmol of dimethyl imidazole, magnetically stirring for 30min, and standing for 9h at room temperature; then, centrifugation, methanol washing and vacuum drying were carried out to obtain purple polyhedral ZIF-67.
b. And (b) putting 50mg of purple powder prepared in the step (a) into 30ml of ethanol solution containing 50mg of nickel nitrate, magnetically stirring for 60min, centrifugally cleaning, and drying in vacuum to obtain the light purple ZIF-67/nickel cobalt double hydroxide.
c. And c, vulcanizing 50mg of the intermediate obtained in the step b by using a chemical vapor deposition method, wherein the vulcanizing temperature is 300 ℃, the vulcanizing time is 4h, the heating speed is 10 ℃/min, the sulfur source is sublimed sulfur, and the mass of the sublimed sulfur is 50 mg.
d. Uniformly mixing the powdery double-shell sulfide based on the ZIF-67 framework structure, PVDF and acetylene black in a mass ratio of 8:1:1, and coating the mixture on pretreated foamed nickel with the mass ratio of 1.5-2.5g/cm2. And the coated foamed nickel is used as an electrode for assembling the super capacitor.
The supercapacitor is assembled by using the double-shell sulfide based on the ZIF-67 framework structure prepared by the method of the embodiment as an electrode material, wherein a platinum sheet is a counter electrode, saturated calomel is a reference electrode, an active material is a working electrode, and CV and GCD tests are performed by using 2M KOH electrolyte. At a current density of 1A/g, the material had a specific mass capacity of 624F/g, as shown in FIG. 4.
Example 3
a. Rapidly mixing 25ml of methanol solution containing 1mmol of cobalt nitrate with 25ml of methanol solution containing 4mmol of dimethyl imidazole, magnetically stirring for 30min, and standing for 9h at room temperature; then, centrifugation, methanol washing and vacuum drying were carried out to obtain purple polyhedral ZIF-67.
b. And (b) putting 50mg of purple powder prepared in the step (a) into 30ml of ethanol solution containing 150mg of nickel nitrate, magnetically stirring for 90min, centrifugally cleaning, and drying in vacuum to obtain the light purple ZIF-67/nickel cobalt double hydroxide.
c. And (c) vulcanizing the light purple powder obtained in the step (b) by using a chemical vapor deposition method, wherein the vulcanization temperature is 500 ℃, the vulcanization time is 2h, the heating speed is 10 ℃/min, the sulfur source is sublimed sulfur, and the mass of the sublimed sulfur is 150 mg.
d. Uniformly mixing the powdery double-shell sulfide based on the ZIF-67 framework structure, PVDF and acetylene black in a mass ratio of 8:1:1, and coating the mixture on pretreated foamed nickel with the mass ratio of 1.5-2.5g/cm2. And the coated foamed nickel is used as an electrode for assembling the super capacitor.
The supercapacitor is assembled by using the double-shell sulfide based on the ZIF-67 framework structure prepared by the method of the embodiment as an electrode material, wherein a platinum sheet is a counter electrode, saturated calomel is a reference electrode, an active material is a working electrode, and CV and GCD tests are performed by using 2M KOH electrolyte. At a current density of 1A/g, the material had a specific mass capacity of 512F/g, as shown in FIG. 5.
Example 4
a. Rapidly mixing 25ml of methanol solution containing 1mmol of cobalt nitrate with 25ml of methanol solution containing 4mmol of dimethyl imidazole, magnetically stirring for 30min, and standing for 9h at room temperature; then, centrifugation, methanol washing and vacuum drying were carried out to obtain purple polyhedral ZIF-67.
b. And (b) putting 50mg of purple powder prepared in the step (a) into 30ml of ethanol solution containing 200mg of nickel nitrate, magnetically stirring for 30min, centrifugally cleaning, and drying in vacuum to obtain the light purple ZIF-67/nickel cobalt double hydroxide.
c. And c, vulcanizing 50mg of the intermediate obtained in the step b by using a chemical vapor deposition method, wherein the vulcanizing temperature is 400 ℃, the vulcanizing time is 3h, the heating speed is 10 ℃/min, the sulfur source is sublimed sulfur, and the mass of the sublimed sulfur is 200 mg.
d. Uniformly mixing the powdery double-shell sulfide based on the ZIF-67 framework structure, PVDF and acetylene black in a mass ratio of 8:1:1, and coating the mixture on pretreated foamed nickel with the mass ratio of 1.5-2.5g/cm2. And the coated foamed nickel is used as an electrode for assembling the super capacitor.
The supercapacitor is assembled by using the double-shell sulfide based on the ZIF-67 framework structure prepared by the method of the embodiment as an electrode material, wherein a platinum sheet is a counter electrode, saturated calomel is a reference electrode, an active material is a working electrode, and CV and GCD tests are performed by using 2M KOH electrolyte. At a current density of 1A/g, the material had a mass to capacity of 862F/g, as shown in FIG. 6.
Example 5
a. Rapidly mixing 25ml of methanol solution containing 1mmol of cobalt nitrate with 25ml of methanol solution containing 4mmol of dimethyl imidazole, magnetically stirring for 30min, and standing for 9h at room temperature; then, centrifugation, methanol washing and vacuum drying were carried out to obtain purple polyhedral ZIF-67.
b. And (b) putting 50mg of purple powder prepared in the step (a) into 30ml of ethanol solution containing 100mg of nickel nitrate, magnetically stirring for 90min, centrifugally cleaning, and drying in vacuum to obtain the light purple ZIF-67/nickel cobalt double hydroxide.
c. And c, vulcanizing 50mg of the intermediate obtained in the step b by using a chemical vapor deposition method, wherein the vulcanizing temperature is 300 ℃, the vulcanizing time is 4h, the heating speed is 10 ℃/min, the sulfur source is sublimed sulfur, and the mass of the sublimed sulfur is 100 mg.
d. Uniformly mixing the powdery double-shell sulfide based on the ZIF-67 framework structure, PVDF and acetylene black in a mass ratio of 8:1:1, and coating the mixture on pretreated foamed nickel with the mass ratio of 1.5-2.5g/cm2. And the coated foamed nickel is used as an electrode for assembling the super capacitor.
The supercapacitor is assembled by using the double-shell sulfide based on the ZIF-67 framework structure prepared by the method of the embodiment as an electrode material, wherein a platinum sheet is a counter electrode, saturated calomel is a reference electrode, an active material is a working electrode, and CV and GCD tests are performed by using 2M KOH electrolyte. At a current density of 1A/g, the material had a specific mass capacity of 762F/g, see FIG. 7.
Example 6
a. Rapidly mixing 25ml of methanol solution containing 1mmol of cobalt nitrate with 25ml of methanol solution containing 4mmol of dimethyl imidazole, magnetically stirring for 30min, and standing for 9h at room temperature; then, centrifugation, methanol washing and vacuum drying were carried out to obtain purple polyhedral ZIF-67.
b. And (b) putting 50mg of purple powder prepared in the step (a) into 30ml of ethanol solution containing 150mg of nickel nitrate, performing magnetic stirring for 30min, performing centrifugal cleaning, and performing vacuum drying to obtain a light purple intermediate: ZIF-67/nickel cobalt double hydroxide.
c. And c, vulcanizing 50mg of the intermediate obtained in the step b by using a chemical vapor deposition method, wherein the vulcanizing temperature is 300 ℃, the vulcanizing time is 4h, the heating speed is 10 ℃/min, the sulfur source is sublimed sulfur, and the mass of the sublimed sulfur is 150 mg.
d. Uniformly mixing the powdery double-shell sulfide based on the ZIF-67 framework structure, PVDF and acetylene black in a mass ratio of 8:1:1Mixing, and coating on pretreated foam nickel at a concentration of 1.5-2.5g/cm2. And the coated foamed nickel is used as an electrode for assembling the super capacitor.
When the double-shell sulfide prepared by the method of the embodiment and based on the ZIF-67 framework structure is used as an electrode to assemble a supercapacitor, a platinum sheet is used as a counter electrode, saturated calomel is used as a reference electrode, an active material is used as a working electrode, and CV and GCD tests are performed by using 2M KOH electrolyte. At a current density of 1A/g, the specific mass capacity of the material was 963F/g, see FIG. 8.
According to the invention, a double-shell structure characteristic based on a ZIF-67 framework is developed, as shown in figure 1, the double-shell structure characteristic comprises two different sulfides, and has the characteristics of large specific surface area, many active sites and the like, so that the specific capacity of the supercapacitor is effectively improved. The double-shell structure based on the ZIF-67 framework has a stable framework and cavity structure, and can slow down the collapse of an electrode material structure of the supercapacitor in the charging and discharging process, so that the circulating stability of the supercapacitor can be remarkably improved. In addition, the preparation method is simple to operate, good in reproducibility and suitable for large-scale production.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (3)
1. A double-shell sulfide based on a ZIF-67 framework structure, which is characterized in that the double-shell sulfide is represented as CoS/MCo2S4Wherein the material of the inner shell is CoS, and the material of the outer shell is MCo2S4M is any one element including Ni, Mn, Fe, Cu and Zn;
the preparation method of the double-shell sulfide comprises the following steps:
a. preparation of ZIF-67:
mixing 0.04M of methanol solution of cobalt nitrate and 0.16M of methanol solution of dimethyl imidazole according to the volume ratio of 1:1, magnetically stirring, standing at room temperature, centrifuging, washing with methanol, and vacuum drying to obtain a purple polyhedral ZIF-67 material;
b. preparation of core-shell intermediates:
putting the ZIF-67 powder prepared in the step a into M (NO)3）2The amount of ethanol in the ethanol solution of (3) is 30mL per 50mgZIF-67 powder; and (3) after magnetic stirring for 30-120min, centrifugally cleaning, and drying in vacuum to obtain light purple intermediate powder: core-shell ZIF-67/binary metal hydroxide;
c. preparing a double-shell sulfide electrode material:
vulcanizing the light purple intermediate powder obtained in the step b by using a chemical vapor deposition method, wherein the vulcanization temperature is 300-;
d. and d, applying the double-shell sulfide based on the ZIF-67 framework structure obtained in the step c to the super capacitor.
2. The preparation method of double-shell sulfide based on ZIF-67 skeleton structure as claimed in claim 1, wherein, in the step b, ZIF-67 powder and M (NO) are mixed3）2The mass ratio of the crystal is 1: X, wherein X is 1, 2, 3 and 4.
3. The preparation method of the double-shell sulfide based on the ZIF-67 framework structure as claimed in claim 1, wherein in the step c, the sulfur source of the chemical vapor deposition method is sublimed sulfur, and the mass ratio of the intermediate to the sulfur source is 1: x, wherein X is 1, 2, 3 or 4.
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| CN110575842B (en) * | 2019-10-12 | 2020-08-11 | 福州大学 | Preparation method of adjustable and controllable yolk-shell structure nitrogen-carbon-doped cobalt molybdenum sulfide counter electrode catalyst |
| CN110797206B (en) * | 2019-10-31 | 2021-12-07 | 上海应用技术大学 | Co-Mn-S composite material and preparation method and application thereof |
| CN110957146B (en) * | 2019-11-12 | 2021-04-27 | 洛阳师范学院 | Preparation method of supercapacitor composite electrode material and electrode |
| CN112216520B (en) * | 2020-05-13 | 2022-02-15 | 江苏大学 | Preparation method and application of composite electrode with MOF-derived Ni-Co-S nanoparticles growing on carbon cloth |
| CN114725411B (en) * | 2022-04-02 | 2024-05-17 | 北京科技大学 | Cobalt-based oxygen reduction electrocatalytic material and preparation method thereof |
| CN115410831B (en) * | 2022-09-14 | 2024-03-19 | 桂林电子科技大学 | Preparation method and application of NiMo-LDH@Co-ZIF-67 porous core-shell structure composite material |
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