CN111533178A - Method for preparing Zn-Co-S composite material based on multi-metal organic framework compound - Google Patents
Method for preparing Zn-Co-S composite material based on multi-metal organic framework compound Download PDFInfo
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- CN111533178A CN111533178A CN202010362788.6A CN202010362788A CN111533178A CN 111533178 A CN111533178 A CN 111533178A CN 202010362788 A CN202010362788 A CN 202010362788A CN 111533178 A CN111533178 A CN 111533178A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
Abstract
The invention discloses a method for preparing a Zn-Co-S composite material based on a multi-metal organic framework compound, wherein the Zn-Co-S composite material is prepared by taking the multi-metal organic framework compound as a precursor and then carrying out high-temperature heat treatment step by step, and the composition, the structure and the size of a Zn-Co-S heterostructure are adjusted by controlling the addition proportion and the addition sequence of zinc salt and cobalt salt in the reaction precursor and the calcining temperature, the calcining time and the vulcanizing condition in the step calcining process, so that the Zn-Co-S composite material with stable structure, adjustable composition, controllable appearance and controllable size is prepared. The preparation method disclosed by the invention is mild in preparation conditions, simple to operate, good in repeatability and capable of realizing large-scale production, and the obtained Zn-Co-S composite structure has a good application prospect in the fields of lithium ion batteries, electrocatalysis and the like.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a method for preparing a Zn-Co-S composite material by using a multi-metal organic framework compound.
Technical Field
With the development of society and the progress of science and technology, the shortage of energy and environmental pollution become important problems in the development of the current society. Therefore, human beings are more and more paying attention to the green sustainable development of energy, the field of electrochemical energy conversion and storage becomes a hot spot of current research, and the lithium ion battery technology and the electro-catalysis technology are paid attention to by people due to unique advantages. With the continuous improvement of the energy demand of people, the existing materials can not meet the requirements of people on high performance, high stability, low cost and the like of electrode materials and electrocatalysts of lithium ion batteries.
The multi-element metal sulfide has excellent electrochemical performance and relatively low price, a large number of researches show that the multi-element metal sulfide has the advantages of high theoretical specific capacity, high electronic conductivity, high catalytic intrinsic activity and the like, and different metals of the multi-element metal sulfide have certain synergistic effect, so that the volume effect of active substances can be reduced to a certain degree, HER and OER are facilitated, the multi-element metal sulfide shows higher electrochemical performance and better catalytic activity than corresponding multi-element metal oxides, selenides and single metal sulfides, and meanwhile, the existing Zn and Co multi-element metal sulfide shows superior electrochemical performance and catalytic activity. The stability and performance of materials in electrochemical and catalytic reactions still need to be further optimized.
The Metal-organic framework (MOF) is a multi-dimensional periodic porous framework material, is mainly formed by complexing transition Metal ions and organic ligands, and has the characteristics of porosity, high specific surface area, easiness in modification, easiness in functionalization and the like. The material obtained by adjusting the components, the size, the morphology, the structure and the high-temperature treatment conditions of the MOF precursor has different components, sizes, morphologies and structures and has respective characteristics in performance. Based on the analysis, the invention provides a simple and safe universal method for preparing a multi-metal sulfide heterostructure material with adjustable structure, shape, size and components.
Disclosure of Invention
The invention aims to overcome the defects of the traditional preparation process of the multi-element metal sulfide and provides a preparation method of a Zn-Co-S composite material with adjustable structure, shape, size and components. The method is simple, feasible, safe and stable, has short synthesis period, is easy for large-scale production, and has good application prospect in electrocatalysis and battery systems.
The purpose of the invention is realized by the following technical scheme:
firstly, preparing a multi-metal organic framework compound by a coprecipitation method, and then carrying out high-temperature treatment reaction on the prepared multi-metal organic framework compound and sulfur powder in an argon atmosphere to obtain a target product. The method comprises the following specific steps:
the method comprises the following steps: respectively dispersing zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole in methanol, stirring or ultrasonically dispersing uniformly, and respectively marking as solution A, solution B and solution C. Then stirring and mixing the three, stirring and reacting at room temperature, collecting a sample through centrifugation, washing the sample with methanol for three times, and drying to obtain dry powder;
further, the proportion of zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole in the step one is 1: 2: 4, or 1: 1: 2, or 2: 1: 4, or 1: 1: 1;
further, in the step one, stirring and mixing are carried out, namely, the solution A and the solution B are stirred and mixed for 5min and then poured into the solution C for stirring reaction, or the solution A is poured into the solution C for stirring and mixing for 1min to 15min and then the solution B is poured into the mixed solution of the solution A and the solution C for stirring reaction, or the solution B is poured into the solution C for stirring and mixing for 1min to 5min and then the solution A is poured into the mixed solution of the solution B and the solution C for stirring reaction, wherein the stirring speed is 500-;
further, the reaction in the first step is stirred at room temperature for 24 hours; when the sample is centrifugally collected, the centrifugal rotating speed is 8000r/min, and the drying condition is 60 ℃ for drying in a vacuum drying oven for 12 hours;
step two: placing a certain proportion of sulfur powder and the powder obtained in the first step at two ends of a porcelain boat, calcining under a closed condition by taking argon as protective gas, and obtaining a multi-metal sulfide heterostructure material after the reaction is finished;
further, in the second step, the mass ratio of the sulfur powder to the dry powder is 1-10: 1, sulfur powder is arranged at a gas inlet of gas, and dry powder is arranged at a gas outlet of the gas;
further, in the second step, the calcination temperature of Ar atmosphere is 500-800 ℃, the calcination time is 1-4 h, and the heating rate is 1-10 ℃/min.
The invention takes a multi-element coordination metal organic framework compound as a precursor, obtains a multi-element metal sulfide heterostructure material after one-step high-temperature treatment, and adjusts the composition, structure, size and morphology of the multi-element metal sulfide heterostructure material by controlling the adding proportion, adding sequence and adding interval time of zinc nitrate hexahydrate and cobalt nitrate hexahydrate in the reaction precursor and controlling the calcining temperature, time and heating rate in the calcining treatment.
Drawings
FIG. 1 is an SEM image of a multi-metal sulfide heterostructure material prepared in example 1 of the present invention.
FIG. 2 is an XRD pattern of the multi-metal sulfide heterostructure material prepared in example 1 of the present invention.
FIG. 3 is a SAED diagram of the multi-metal sulfide heterostructure material prepared in example 1 of the present invention.
The specific implementation mode is as follows:
the following further describes embodiments of the present invention with reference to the drawings, but the present invention is not limited to the scope described below.
Example 1:
2.48g of zinc nitrate hexahydrate and 5.83g of cobalt nitrate hexahydrate are weighed and respectively dispersed in 100mL of methanol and stirred for 5min to be uniformly dispersed, and respectively marked as solution A and solution B, 8.73g of 2-methylimidazole is weighed and dispersed in 200mL of methanol and stirred for 5min to be uniformly dispersed, and marked as solution C. The solution A and the solution B are stirred and mixed for 5 min. And then adding the solution C into the mixed solution of the solution A and the solution B, stirring and reacting for 24h, centrifuging for 8min, collecting a sample, centrifuging at the rotating speed of 8000r/min, washing with methanol for three times, and drying in an oven at the temperature of 60 ℃ for 12h to obtain dry powder. Transferring the dried powder into a tube furnace, and mixing the dried powder and the powder in a mass ratio of 6: 1, placing the sulfur powder and the dry powder at two ends of a porcelain boat, enabling the sulfur powder to be at a gas inlet of a gas, enabling the dry powder to be at a gas outlet of the gas, calcining under a closed condition by taking argon as protective gas, heating to 550 ℃ at a speed of 3 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a final product.
The SEM image of the multi-metal sulfide heterostructure material obtained in this example is shown in fig. 1, and it can be seen from fig. 1 that the product prepared by the method is a polyhedron structure, the surface of which is covered with a layer of tubes, and the particle size is about 300 nm. The XRD pattern of the multi-element metal sulfide heterostructure material obtained in the example is shown in FIG. 2, and the prepared product can be seen from FIG. 2 to be composed of ZnS and CoS. The SAED pattern of the zinc-cobalt multi-metal sulfide heterostructure material obtained in this example is shown in fig. 3, and it is observed from fig. 3 that a plurality of diffraction rings correspond to the (111) crystal plane of ZnS and the (101) and (102) crystal planes of CoS, respectively, and the SAED pattern is consistent with the XRD result.
Example 2:
4.96g of zinc nitrate hexahydrate and 5.83g of cobalt nitrate hexahydrate are weighed and respectively dispersed in 100mL of methanol and stirred for 5min to be uniformly dispersed, and respectively marked as solution A and solution B, 8.73g of 2-methylimidazole is weighed and dispersed in 200mL of methanol and stirred for 5min to be uniformly dispersed, and marked as solution C. Adding the solution C into the solution A, and stirring for reaction for 5 min. And then adding the solution B into the mixed solution of the solution A and the solution C, stirring and reacting for 24h, centrifuging for 8min, collecting a sample, centrifuging at the rotating speed of 8000r/min, washing with methanol for three times, and drying in an oven at the temperature of 60 ℃ for 12h to obtain dry powder. Transferring the dried powder into a tube furnace, and mixing the dried powder and the powder in a mass ratio of 3: 1, placing the sulfur powder and the dry powder at two ends of a porcelain boat, enabling the sulfur powder to be at a gas inlet of a gas, enabling the dry powder to be at a gas outlet of the gas, calcining under a closed condition by taking argon as protective gas, heating to 600 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a final product.
Example 3:
4.96g of zinc nitrate hexahydrate and 2.92g of cobalt nitrate hexahydrate are weighed and respectively dispersed in 100mL of methanol and stirred for 5min to be uniformly dispersed, and respectively marked as solution A and solution B, 8.73g of 2-methylimidazole is weighed and dispersed in 200mL of methanol and stirred for 5min to be uniformly dispersed, and marked as solution C. Adding the solution C into the solution B, and stirring for reaction for 2 min. And then adding the solution A into the mixed solution of the solution B and the solution C, stirring and reacting for 24h, centrifuging for 8min, collecting a sample, centrifuging at the rotating speed of 8000r/min, washing with methanol for three times, and drying in an oven at the temperature of 60 ℃ for 12h to obtain dry powder. Transferring the dried powder into a tube furnace, and mixing the dried powder and the powder in a mass ratio of 5: the sulfur powder and the dry powder of 1 are placed at two ends of a porcelain boat, the sulfur powder is arranged at a gas inlet of a gas, the dry powder is arranged at a gas outlet of the gas, calcination treatment is carried out under a closed condition by taking argon as protective gas, the temperature is raised to 800 ℃ by 8 ℃/min, heat preservation is carried out for 1h, and the final product is obtained after natural cooling to room temperature.
Example 4:
2.48g of zinc nitrate hexahydrate and 2.92g of cobalt nitrate hexahydrate are weighed and respectively dispersed in 100mL of methanol and stirred for 5min to be uniformly dispersed, and respectively marked as solution A and solution B, 8.73g of 2-methylimidazole is weighed and dispersed in 200mL of methanol and stirred for 5min to be uniformly dispersed, and marked as solution C. Adding the solution C into the solution B, and stirring for reaction for 2 min. And then adding the solution A into the mixed solution of the solution B and the solution C, stirring and reacting for 24h, centrifuging for 8min, collecting a sample, centrifuging at the rotating speed of 8000r/min, washing with methanol for three times, and drying in an oven at the temperature of 60 ℃ for 12h to obtain dry powder. Transferring the dried powder into a tube furnace, and mixing the dried powder and the powder in a mass ratio of 8: the sulfur powder and the dry powder of 1 are placed at two ends of a porcelain boat, the sulfur powder is placed at a gas inlet of a gas, the dry powder is placed at a gas outlet of the gas, calcination treatment is carried out under a closed condition by taking argon as protective gas, the temperature is raised to 500 ℃ by 2 ℃/min, heat preservation is carried out for 4 hours, and the final product is obtained after natural cooling to room temperature.
While the foregoing specification and examples have described the principles of the invention and processes for the best mode thereof, the invention contemplates the use of other metal compound frameworks and such variations and modifications as fall within the scope of the claimed invention without departing from the spirit and principles of the invention.
Claims (3)
1. A method for preparing Zn-Co-S composite material based on multi-metal organic framework compound is characterized in that:
preparing a multi-metal organic framework compound by using a coprecipitation method, and then carrying out high-temperature treatment reaction on the prepared multi-metal organic framework compound and sulfur powder in an argon atmosphere to obtain a target product;
the method comprises the following specific steps:
the method comprises the following steps: respectively dispersing zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole in methanol, stirring or ultrasonically dispersing them uniformly, respectively marking them as solution A, solution B and solution C,
then stirring and mixing the three, stirring and reacting at room temperature, collecting a sample through centrifugation, washing the sample with methanol for three times, and drying to obtain dry powder;
step two: and (3) placing a certain proportion of sulfur powder and the powder obtained in the step one at two ends of a porcelain boat, calcining under a closed condition by taking argon as protective gas, and obtaining the multi-metal sulfide heterostructure material after the reaction is finished.
2. The method for preparing Zn-Co-S composite material based on multi-metal organic framework compound as claimed in claim 1, wherein: in the first step, the proportion of zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole is 1: 2: 4, or 1: 1: 2, or 2: 1: 4, or 1: 1: 1;
stirring and mixing in the first step is to stir and mix the solution A and the solution B for 5min and then pour the solution C into the solution C for stirring and reacting, or to pour the solution A into the solution C for stirring and mixing for 1min to 15min and then pour the solution B into the mixed solution of the solution A and the solution C for stirring and reacting, or to pour the solution B into the solution C for stirring and mixing for 1min to 5min and then pour the solution A into the mixed solution of the solution B and the solution C for stirring and reacting, wherein the stirring speed is 500-;
the reaction in the step one is stirred at room temperature for 24 hours; when the samples are collected by centrifugation, the centrifugal speed is 8000r/min, and the drying condition is 60 ℃ for drying in a vacuum drying oven for 12 h.
3. The method for preparing Zn-Co-S composite material based on multi-metal organic framework compound as claimed in claim 1, wherein: in the second step, the mass ratio of the sulfur powder to the dry powder is 1-10: 1, sulfur powder is arranged at a gas inlet of gas, and dry powder is arranged at a gas outlet of the gas;
further, in the second step, the calcination temperature of Ar atmosphere is 500-800 ℃, the calcination time is 1-4 h, and the heating rate is 1-10 ℃/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113097464A (en) * | 2021-03-31 | 2021-07-09 | 新疆大学 | ZnS-SnS @3DC composite material and preparation method and application thereof |
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