CN110415993B - Preparation method and application of Mn-Co-S/Co-MOF nano material - Google Patents

Preparation method and application of Mn-Co-S/Co-MOF nano material Download PDF

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CN110415993B
CN110415993B CN201910641506.3A CN201910641506A CN110415993B CN 110415993 B CN110415993 B CN 110415993B CN 201910641506 A CN201910641506 A CN 201910641506A CN 110415993 B CN110415993 B CN 110415993B
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mof
methanol
acetate tetrahydrate
nano material
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CN110415993A (en
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蒋继波
孙瑶馨
陈宇凯
胡晓敏
丛海山
王露露
刘凤茹
常宾
高丽
康佳玲
唐佳斌
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Shanghai Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01G11/30—Electrodes characterised by their material
    • 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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to a preparation method of a Mn-Co-S/Co-MOF nano material, which comprises the following steps: s1: dissolving manganese acetate tetrahydrate, cobalt acetate tetrahydrate, carbon disulfide and pentamethyldiethylenetriamine in methanol in sequence to obtain a solution A, and dissolving 2-methylimidazole in methanol to obtain a solution B; s2: adding the solution B into the solution A, and transferring the mixed solution of the solution B and the solution A into a reaction kettle for reaction; s3: and (4) centrifuging, washing and drying to obtain the Mn-Co-S/Co-MOF nano material. Compared with the prior art, the preparation method is environment-friendly, simple in process and convenient for large-scale production, and the obtained Mn-Co-S/Co-MOF nanosheet can obtain excellent electrochemical properties when applied to an electrode material.

Description

Preparation method and application of Mn-Co-S/Co-MOF nano material
Technical Field
The invention relates to the technical field of electrochemistry and nano materials, in particular to a preparation method and application of a Mn-Co-S/Co-MOF nano material.
Background
MOFs are compounds having a porous crystalline structure composed of metal ions and organic ligands, and the structure thereof has diversity. In recent years, due to the highly porous ordered structure, the pyrolysis of the MOFs becomes a new hot spot in the field of scientific research and shows a good development prospect. MOFs can be used as adsorbents in gas adsorption and separation and as supports for metal nanoparticles in heterogeneous catalysis. It is an important novel porous material and has wide application in the aspects of catalysis, energy storage, separation and the like. The structure and shape of the MOFs are diversified due to the diversity of metal species and organic ligands and the diversity of their assembly arrangement order. Due to structural diversity, high surface area, large pore volume and abundant organic species, MOFs can be used as a template/precursor to prepare highly porous carbon with bright prospect, and have very wide application in the aspects of energy and environment.
Manganese Cobalt Sulfide (MCS) is a BTMSs electrode material with great development prospect. The use of MCS in supercapacitors is less investigated, probably due to the fact that the heterogeneous growth process of multicomponent transition metal sulfides is difficult to control. Although BTMS electrodes have outstanding advantages, BTMS electrodes are susceptible to delays in the ion/electron transport process and significant volume changes during electrochemical measurements. These effects are the bottleneck to improve rate performance and cycle stability.
How to further improve the chemical performance of Manganese Cobalt Sulfide (MCS) through MOFs materials is a problem which needs to be solved at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method and application of a Mn-Co-S/Co-MOF nano material.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a Mn-Co-S/Co-MOF nano material comprises the following steps:
s1: dissolving manganese acetate tetrahydrate, cobalt acetate tetrahydrate, carbon disulfide and pentamethyldiethylenetriamine in methanol in sequence to obtain a solution A, and dissolving 2-methylimidazole in methanol to obtain a solution B;
s2: adding the solution B into the solution A, and transferring the mixed solution of the solution B and the solution A into a reaction kettle for reaction;
s3: and (4) centrifuging, washing and drying to obtain the Mn-Co-S/Co-MOF nano material.
Further, in step S1, the molar ratio of manganese acetate tetrahydrate to cobalt acetate tetrahydrate is 1: 2.
further, the volume ratio of the carbon disulfide to the pentamethyldiethylenetriamine in the step S1 is 1.2: 10.
further, in step S1, the molar concentration of manganese acetate tetrahydrate in methanol is 0.5mol/L, and the volume ratio of carbon disulfide to methanol is 1.2: 50.
further, the volume ratio of the solution a to the added solution B in step S2 is 1:1, further, the reaction temperature in the step S2 is 180 ℃, and the reaction time is 12 h.
The Mn-Co-S/Co-MOF nano material prepared by the method can be widely applied to electrode materials.
Further, the application method comprises the steps of drying and grinding the Mn-Co-S/Co-MOF nano material, and mixing the Mn-Co-S/Co-MOF nano material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, and uniformly mixing to obtain the electrode for the super capacitor.
Because the nano manganese and the nano cobalt have excellent pseudocapacitance, BTMSs with a three-dimensional structure are constructed, and the structure is favorable for providing a three-dimensional interconnection network for electronic conduction and mass transfer, so that the volume change is reduced, and the active interface position is maximized.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the three-dimensional nano honeycomb structure of the Mn-Co-S/Co-MOF nano array is synthesized through a simple hydrothermal reaction, and a stable structure and a larger surface area can be provided for electron conduction mass transfer in the charging and discharging processes.
2. The Mn-Co-S/Co-MOF nano material prepared by the invention is highly porous, regular and ordered, is convenient for electron transfer, and improves the electrochemical performance.
3. The Mn-Co-S/Co-MOF nano material prepared by the invention has good conductivity. All CV curves contain a strong redox peak, representing a typical faradaic redox reaction. Including Co in alkaline electrolytes2+/Co3 +And Mn2+/Mn4+The redox coupled electron transfer process, which corresponds to the following redox reaction:
Figure BDA0002132039750000021
drawings
FIG. 1 is an SEM image at 500nm of Mn-Co-S/Co-MOF nanomaterials made in example 1;
FIG. 2 is an SEM image at 1 μm of Mn-Co-S/Co-MOF nanomaterials made in example 1;
FIG. 3 is a CV diagram of Mn-Co-S/Co-MOF nanomaterials prepared in example 1;
FIG. 4 is a graph of Mn-Co-S/Co-MOF nanomaterials prepared in example 1 in GCD.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Adding 0.5mmol of Mn (Ac)2·4H2O，1mmol Co(Ac)2·4H2O，120μl CS2And 1ml of PMDTA dissolved in 5ml of methanol, called solution A. 102mg of 2-dimethylimidazole was dissolved in 5ml of methanol and designated as solution B. Dissolving B inDropwise adding the mixed solution into the solution A, and after the mixed solution is completely mixed, transferring the mixed solution into a 40ml stainless steel autoclave with a polytetrafluoroethylene lining for hydrothermal reaction, and keeping the temperature at 180 ℃ for 12 hours. And cooling after the reaction is finished, centrifuging, washing with deionized water and ethanol for multiple times, fully grinding the obtained Mn-Co-S/Co-MOF nano material, mixing with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, uniformly stirring, pressing on a foam nickel sheet (1cm multiplied by 1cm), and baking for 12 hours at the temperature of 60 ℃ to obtain the working electrode.
The Chenhua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant-current charging and discharging method to detect the specific capacitance and cyclic stability of the material, and the cyclic voltammetry tests show that the material has excellent oxidation-reduction capability. The high specific surface area of the metamaterial is provided with a foundation by using an electron scanning microscope (for representing the surface microstructure of the electrode material). The specific capacitance of the electrode material reaches 852F/g in 2mol/L KOH solution and at a current density of 1A/g. FIG. 1 and FIG. 2 show the microscopic morphology of Mn-Co-S/Co-MOF nanomaterials, exhibiting a highly porous ordered honeycomb structure that can provide a stable structure and a large surface area for electron conduction mass transfer during charging and discharging. The good electrochemical performance of the material is clearly shown in fig. 3 and 4, and the specific capacitance calculated according to fig. 4 can reach 852F/g.
Example 2
Adding 0.5mmol of Mn (Ac)2·4H2O，1mmol Co(Ac)2·4H2O，120μl CS2And 1ml of PMDTA was dissolved in 5ml of methanol, and the solution was transferred to a 40ml teflon-lined stainless steel autoclave for hydrothermal reaction, and kept at 180 ℃ for 12 hours. After the reaction is finished, cooling, centrifuging, washing with deionized water and ethanol for multiple times, fully grinding the obtained Mn-Co-S nano material, mixing with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, uniformly stirring, pressing on a foam nickel sheet (1cm multiplied by 1cm), and baking at 60 ℃ for 12 hours to obtain the working electrode, wherein the biggest difference between the embodiment 2 and the embodiment 1 is that the Co-MOF material is synthesized in the embodiment 1, and then the Mn-Co-S/Co-MOF nano material is synthesized, but only the Mn-Co-S material is synthesized in the embodiment 2.
The Chenhua CHI760e electrochemical workstation adopts cyclic voltammetry and constant-current charging and discharging methods to detect the specific capacitance and cyclic stability of the material, and cyclic voltammetry tests show that the material has excellent redox capability. The high specific surface area of the metamaterial is provided with a foundation by using an electron scanning microscope (for representing the surface microstructure of the electrode material). The specific capacitance of the electrode material reaches 589F/g in 2mol/L KOH solution and at a current density of 1A/g.
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 (3)

1. A preparation method of a Mn-Co-S/Co-MOF nano material is characterized by comprising the following steps:
s1: dissolving manganese acetate tetrahydrate, cobalt acetate tetrahydrate, carbon disulfide and pentamethyldiethylenetriamine in methanol in sequence to obtain a solution A, and dissolving 2-methylimidazole in methanol to obtain a solution B;
s2: adding the solution B into the solution A, and transferring the mixed solution of the solution B and the solution A into a reaction kettle for reaction;
s3: centrifuging, washing and drying to obtain a three-dimensional nano honeycomb structure material of the Mn-Co-S/Co-MOF nano array;
in the step S1, the molar ratio of the manganese acetate tetrahydrate to the cobalt acetate tetrahydrate is 1: 2, the volume ratio of the carbon disulfide to the pentamethyldiethylenetriamine is 1.2: 10, the molar concentration of manganese acetate tetrahydrate in methanol is 0.5mol/L, and the volume ratio of carbon disulfide to methanol is 1.2: 50;
the volume ratio of the solution A to the added solution B in the step S2 is 1:1, the reaction temperature in the step S2 is 180 ℃, and the reaction time is 12 h.
2. Use of a Mn-Co-S/Co-MOF nanomaterial prepared in claim 1 in an electrode material.
3. The application of the Mn-Co-S/Co-MOF nano material in the electrode material according to claim 2, wherein the Mn-Co-S/Co-MOF nano material is dried, ground and mixed with carbon black and polytetrafluoroethylene according to a mass ratio of 8:1:1, and uniformly mixing to obtain the electrode for the super capacitor.
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CN114618590A (en) * 2022-01-19 2022-06-14 华东理工大学 Preparation method of iron-based MOFs manganese sulfide composite material, composite material obtained by preparation method and application of composite material

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