CN109081377B - Three-dimensional molybdenum disulfide flower ball array and preparation method and application thereof - Google Patents
Three-dimensional molybdenum disulfide flower ball array and preparation method and application thereof Download PDFInfo
- Publication number
- CN109081377B CN109081377B CN201811223136.3A CN201811223136A CN109081377B CN 109081377 B CN109081377 B CN 109081377B CN 201811223136 A CN201811223136 A CN 201811223136A CN 109081377 B CN109081377 B CN 109081377B
- Authority
- CN
- China
- Prior art keywords
- molybdenum disulfide
- ball array
- dimensional
- molybdenum
- flower ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a three-dimensional molybdenum disulfide flower ball array and a preparation method and application thereof. The preparation method comprises the following steps: s1: dissolving a molybdenum source and a sulfur source to obtain a mixed solution; the molar ratio of the sulfur element in the sulfur source to the molybdenum element in the molybdenum source is 3: 1-6: 1; s2: and adding a titanium wire mesh into the mixed solution S1, carrying out hydrothermal reaction for 8-24 h at 200-220 ℃ in a closed environment, cooling, taking out the wire mesh, rinsing, and drying to obtain the three-dimensional molybdenum disulfide ball array. The preparation method provided by the invention has simple process, and can quickly synthesize a large amount of three-dimensional molybdenum disulfide flower ball arrays with large specific surface area and stable structure; the three-dimensional molybdenum disulfide ball array synthesized by the method is expected to be widely applied in the fields of lithium ion battery electrode materials, electro-catalysts and the like.
Description
Technical Field
The invention relates to the field of preparation of inorganic micro-nano materials, in particular to a three-dimensional molybdenum disulfide flower ball array and a preparation method and application thereof.
Background
With the progress of economic globalization and the heavy use of fossil fuels, the problems of environmental pollution and energy shortage are becoming prominent. In order to reduce the pollution of fossil fuel in the using process, develop wind, light and electricity sustainable renewable energy sources, novel power batteries and efficient energy storage systems, realize reasonable configuration and power regulation of the renewable energy sources, and have important strategic significance for improving the resource utilization efficiency, solving the energy crisis and protecting the environment. The lithium ion battery has the advantages of high specific energy, low self-discharge, good cycle performance, no memory effect, environmental protection and the like, and is a high-efficiency secondary battery with the greatest development prospect and a chemical energy storage power source with the fastest development. The graphite material has good conductivity, high crystallinity and stable charge and discharge platform, and is the lithium ion battery cathode material with the highest degree of commercialization at present.
However, hard carbon has been limited in its application as a negative electrode material due to low cycle efficiency, large voltage variation with capacity, and lack of a stable discharge plateau. Recently, the synthesis and the photoelectric property research of the layered transition metal sulfide micro-nano structure are widely concerned by people.
Molybdenum disulfide (MoS)2) Having a graphite-like layered structure, MoS due to the anisotropic structural features2Easily form the nano-sheet with a two-dimensional structure. The scattered nanosheets are easy to stack or fold when in use, so that the available specific surface area is greatly reduced. Researches show that the nanosheets form a three-dimensional hierarchical structure in a certain mode, so that the nanosheets not only have larger specific surface areas and more ion-transferring channels, but also have better structural stability. In addition, the uniform nano structure can improve the ion diffusion rate, thereby improving the electrochemical performance of the ion diffusion layer. The advantage of this structure is that each nanostructure element is directly connected to a current collector, which eliminates the need for binders and conductive additives that are typically used in the preparation of electrodes. In addition, the self-assembled nanostructures provide numerous conductive pathways for electron transport to the current collector, thereby improving electrochemical performance.
Currently MoS2The preparation of the nano material mainly comprises the preparation of two-dimensional MoS growing on carbon paper, carbon cloth and titanium metal sheet2The nano-sheets are scattered and stacked easily during use, so that the available specific surface area is greatly reduced. Therefore, a simple and low-cost preparation method is needed to prepare the MoS with large specific surface area and high stability2A three-dimensional nanostructure.
Disclosure of Invention
The invention aims to overcome the defects of small specific surface area and poor structural stability of a two-dimensional molybdenum disulfide nano structure prepared by the prior art, and provides a preparation method of a three-dimensional molybdenum disulfide flower ball array. The preparation method provided by the invention has simple process, and can quickly synthesize a large amount of three-dimensional molybdenum disulfide flower ball arrays with large specific surface area and stable structure; the three-dimensional molybdenum disulfide ball array synthesized by the method is expected to be widely applied in the fields of lithium ion battery electrode materials, electro-catalysts and the like.
The invention also aims to provide a three-dimensional molybdenum disulfide flower ball array prepared by the method.
The invention also aims to provide the application of the three-dimensional molybdenum disulfide flower ball array in the field of electrochemistry.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a three-dimensional molybdenum disulfide flower ball array comprises the following steps:
s1: dissolving a molybdenum source and a sulfur source to obtain a mixed solution; the molar ratio of the sulfur element in the sulfur source to the molybdenum element in the molybdenum source is 3: 1-6: 1;
s2: and adding the titanium wire mesh into the mixed solution S1, carrying out hydrothermal reaction for 8-24 h at 200-220 ℃ in a closed environment, cooling, taking out the titanium wire mesh, rinsing, and drying to obtain the three-dimensional molybdenum disulfide flower ball array.
The above-mentioned specific molar ratio of elemental sulfur to elemental molybdenum in the molybdenum source ensures the formation of a three-dimensional array of molybdenum disulfide flower spheres.
The inventor finds that by selecting a titanium wire mesh as a substrate, molybdenum disulfide generated by the reaction is in a flower-ball-shaped structure. Other metals such as Ni, Cu, Co or Fe are not selected because of the reaction, and the carbon fiber net and the like can only obtain the molybdenum disulfide with a sheet structure. The titanium silk screen serving as the substrate is relatively low in cost, easy to obtain and free from reaction with a solution, and the obtained flower ball is more uniform in size and appearance and more stable in structure.
The specific reaction time and reaction temperature can ensure that the product is a three-dimensional molybdenum disulfide flower ball array with large specific surface area and stable structure.
Molybdenum and sulfur sources conventional in the art may be used in the present invention.
The molybdenum source in S1 is one or more of ammonium molybdate, sodium molybdate or potassium molybdate; the sulfur source is one or two of thioacetamide or thiourea.
Preferably, the concentration of the molybdenum element in the mixed solution in S1 is 0.02-0.05 mol/L.
The specific concentration range can make the appearance of the prepared three-dimensional molybdenum disulfide ball array more uniform and the structure more stable.
Preferably, the molar ratio of the sulfur element in the sulfur source to the molybdenum element in the molybdenum source in S1 is 4: 1-6: 1.
The specific molar ratio of the sulfur element to the molybdenum element in the molybdenum source can ensure the sufficient reduction and vulcanization of the molybdenum, avoid the generation of impurities such as molybdenum oxide and the like, and avoid the danger caused by too high pressure of the reaction kettle.
Preferably, the hydrothermal reaction temperature in S2 is 200 ℃ and the time is 16 h.
The specific reaction temperature and time can make the size of the prepared three-dimensional molybdenum disulfide ball array more uniform.
Rinsing agents, dry environments are all conventional in the art.
Preferably, the selected reagents for rinsing in S2 are deionized water and absolute ethanol; the drying process comprises the following steps: and drying at 60-80 ℃ in a vacuum environment.
A three-dimensional molybdenum disulfide flower ball array is obtained through the preparation method.
The three-dimensional molybdenum disulfide ball array obtained by the preparation method has the advantages of uniform size and appearance, large specific surface area and stable structure.
The application of the three-dimensional molybdenum disulfide flower ball array in the field of electrochemical materials is also within the protection scope of the invention.
Preferably, the three-dimensional molybdenum disulfide ball array is applied to the fields of electrocatalysts and lithium ion battery electrode materials.
Compared with the prior art, the invention has the following beneficial effects:
the preparation process is simple, and the three-dimensional molybdenum disulfide flower ball array with large specific surface area and stable structure can be rapidly synthesized in a large amount; the three-dimensional molybdenum disulfide ball array synthesized by the method is expected to be widely applied in the fields of lithium ion battery electrode materials, electro-catalysts and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of a three-dimensional molybdenum disulfide flower ball array provided in example 1;
FIG. 2 is a scanning electron microscope and a transmission electron microscope image of the three-dimensional molybdenum disulfide flower ball array provided in example 1;
FIG. 3 is a scanning electron micrograph of a three-dimensional molybdenum disulfide flower ball array provided in example 2;
FIG. 4 is a scanning electron microscope image of a titanium plate-loaded molybdenum disulfide nanosheet provided in comparative example 1;
fig. 5 is a scanning electron microscope of the molybdenum disulfide nanosheet provided in comparative example 2.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
The embodiment provides a three-dimensional molybdenum disulfide flower ball array. The preparation method comprises the following steps:
dissolving 1.5mmol of sodium molybdate and 9mmol of thiourea in 60m L of deionized water under stirring to form a solution, finally transferring the solution to a 100m L stainless steel reaction kettle with a polytetrafluoroethylene lining, inclining a 4 x 2cm titanium wire mesh against the wall surface of the lining of the reaction kettle, placing the reaction kettle in a drying box, carrying out hydrothermal reaction for 12 hours at 200 ℃, then naturally cooling to room temperature, rinsing the titanium wire mesh with deionized water and absolute ethyl alcohol for three times respectively, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain the three-dimensional molybdenum disulfide flower ball array.
The X-ray diffraction pattern of the three-dimensional molybdenum disulfide flower ball array is shown in figure 1, wherein the positions and intensities of diffraction peaks of molybdenum disulfide are consistent with those of a standard diffraction card (JCPDS 37-1492).
A scanning electron microscope of the three-dimensional molybdenum disulfide flower ball array is shown in figure 2, a figure 2 (a) shows a full-view image of a titanium wire mesh, and a figure 2 (b) is a single titanium wire image, and a layer of sample deposited on the titanium wire can be seen; figure 2 (c) shows that the samples deposited on the titanium wire are arrays of nanoflowers with fairly uniform size and morphology, with an average diameter of about 800 nm. FIG. 2 (d) shows that the flower ball is assembled by a plurality of nano-sheets, and the surface structure of the flower ball is distributed with a plurality of nano-sheets which are arranged in a staggered way.
Testing the performance of the electrocatalytic hydrogen evolution reaction: and (3) punching the molybdenum disulfide flower ball array titanium wire mesh after the hydrothermal reaction into a wafer with the diameter of 7.5mm as a testing working electrode. The electrolyte is 0.5M sulfuric acid aqueous solution, the reference electrode is a saturated calomel electrode, a platinum sheet is used as a counter electrode, the electrocatalytic performance of the material on the hydrogen evolution reaction is tested by linear potential scanning on a CHI760E electrochemical workstation, and the scanning speed is 5 mV/s.
The test result shows that the current density of the electrochemical catalytic hydrogen evolution reaction on the molybdenum disulfide flower ball array electrode is 107mA/cm under the potential of-0.30 Vvs2The catalyst has high hydrogen evolution reaction electrocatalytic performance (calculated by actual load area).
Example 2
The embodiment provides a three-dimensional molybdenum disulfide flower ball array. The preparation method comprises the following steps:
dissolving 2mmol of sodium molybdate and 9mmol of thiourea in 60m L of deionized water under stirring to form a solution, finally transferring the solution to a 100m L stainless steel reaction kettle with a polytetrafluoroethylene lining, leaning a 4 x 2cm titanium wire mesh against the wall surface of the lining of the reaction kettle, placing the reaction kettle in a drying box, carrying out hydrothermal reaction for 16 hours at 200 ℃, then naturally cooling to room temperature, rinsing the titanium wire mesh with deionized water and absolute ethyl alcohol respectively for three times, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain the three-dimensional molybdenum disulfide ball array.
A scanning electron microscope of the three-dimensional molybdenum disulfide flower ball array is shown in figure 3, a full-view image of a titanium wire mesh is shown in figure 3 (a), and a single titanium wire image is shown in figure 3 (b), so that more layers of samples are deposited on the titanium wire; FIG. 3 (c) shows that the sample deposited on the titanium wire is a nano flower ball array with fairly uniform size and morphology, and the average diameter is about 1.4 μm. FIG. 2 (d) shows that the flower ball is assembled by a plurality of nano-sheets, and the surface structure of the flower ball is distributed with a plurality of nano-sheets which are arranged in a staggered way.
Testing the performance of the electrocatalytic hydrogen evolution reaction: and (3) punching the molybdenum disulfide flower ball array titanium wire mesh after the hydrothermal reaction into a wafer with the diameter of 7.5mm as a testing working electrode. The electrolyte is 0.5M sulfuric acid aqueous solution, the reference electrode is a saturated calomel electrode, a platinum sheet is used as a counter electrode, the electrocatalytic performance of the material on the hydrogen evolution reaction is tested by linear potential scanning on a CHI760E electrochemical workstation, and the scanning speed is 5 mV/s.
The test result shows that the current density of the electrochemical catalytic hydrogen evolution reaction on the molybdenum disulfide flower ball array electrode is 159mA/cm under the potential of-0.30 Vvs2The catalyst has high hydrogen evolution reaction electrocatalytic performance (calculated by actual load area).
Example 3
The embodiment provides a three-dimensional molybdenum disulfide flower ball array. The preparation method comprises the following steps:
dissolving 1.5mmol of sodium molybdate and 9mmol of thiourea in 60m L of deionized water under stirring to form a solution, finally transferring the solution to a 100m L stainless steel reaction kettle with a polytetrafluoroethylene lining, inclining a 4 x 2cm titanium wire mesh against the wall surface of the lining of the reaction kettle, placing the reaction kettle in a drying box, carrying out hydrothermal reaction for 20 hours at 220 ℃, then naturally cooling to room temperature, rinsing the titanium wire mesh with deionized water and absolute ethyl alcohol for three times respectively, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain the three-dimensional molybdenum disulfide flower ball array.
The size and the appearance of the obtained three-dimensional molybdenum disulfide flower ball array are quite uniform, and the average diameter is about 2.3 mu m.
Testing the performance of the electrocatalytic hydrogen evolution reaction: and (3) punching the molybdenum disulfide flower ball array titanium wire mesh after the hydrothermal reaction into a wafer with the diameter of 7.5mm as a testing working electrode. The electrolyte is 0.5M sulfuric acid aqueous solution, the reference electrode is a saturated calomel electrode, a platinum sheet is used as a counter electrode, the electrocatalytic performance of the material on the hydrogen evolution reaction is tested by linear potential scanning on a CHI760E electrochemical workstation, and the scanning speed is 5 mV/s.
The test result shows that the current density of the electrochemical catalytic hydrogen evolution reaction on the molybdenum disulfide flower ball array electrode is 109mA/cm under the potential of-0.30 Vvs2The catalyst has high hydrogen evolution reaction electrocatalytic performance (calculated by actual load area).
Example 4
The embodiment provides a three-dimensional molybdenum disulfide flower ball array. In the preparation method, except that the molybdenum source is replaced by 1.5mmol of ammonium molybdate, the sulfur source is replaced by 4.5mmol of thioacetamide, and the addition amount of deionized water is 75 ml; the hydrothermal temperature was 220 ℃, the duration was 8 hours, and the drying temperature was 70 ℃, and the other operations and conditions were the same as those in example 1.
The size and the appearance of the three-dimensional molybdenum disulfide flower ball array prepared by the embodiment are similar to those of the embodiment 1.
Testing the performance of the electrocatalytic hydrogen evolution reaction: and (3) punching the molybdenum disulfide flower ball array titanium wire mesh after the hydrothermal reaction into a wafer with the diameter of 7.5mm as a testing working electrode. The electrolyte is 0.5M sulfuric acid aqueous solution, the reference electrode is a saturated calomel electrode, a platinum sheet is used as a counter electrode, the electrocatalytic performance of the material on the hydrogen evolution reaction is tested by linear potential scanning on a CHI760E electrochemical workstation, and the scanning speed is 5 mV/s.
The test result shows that the current density of the electrochemical catalytic hydrogen evolution reaction on the molybdenum disulfide flower ball array electrode is 82mA/cm under the potential of-0.30 Vvs2The catalyst has high hydrogen evolution reaction electrocatalytic performance (calculated by actual load area).
Example 5
The embodiment provides a molybdenum disulfide flower ball. In the preparation method, except that the molybdenum source is replaced by 0.214mmol of ammonium molybdate, the sulfur source is replaced by 6mmol of thioacetamide, and the addition amount of deionized water is 30 ml; the drying temperature was not more than 80 ℃ and the other operations and conditions were the same as in example 1.
The size and the appearance of the three-dimensional molybdenum disulfide flower ball array prepared by the embodiment are similar to those of the embodiment 1.
Testing the performance of the electrocatalytic hydrogen evolution reaction: and (3) punching the molybdenum disulfide flower ball array titanium wire mesh after the hydrothermal reaction into a wafer with the diameter of 7.5mm as a testing working electrode. The electrolyte is 0.5M sulfuric acid aqueous solution, the reference electrode is a saturated calomel electrode, a platinum sheet is used as a counter electrode, the electrocatalytic performance of the material on the hydrogen evolution reaction is tested by linear potential scanning on a CHI760E electrochemical workstation, and the scanning speed is 5 mV/s.
The test result shows that the current density of the electrochemical catalytic hydrogen evolution reaction on the molybdenum disulfide flower ball array electrode is 116mA/cm under the potential of-0.30 Vvs2The catalyst has high hydrogen evolution reaction electrocatalytic performance (calculated by actual load area).
Example 6
The embodiment provides a molybdenum disulfide flower ball. The preparation method is the same as that of the embodiment 1 except that the molybdenum source is replaced by potassium molybdate, the sulfur source is replaced by 9mmol thioacetamide, and the hydrothermal time is 24 h.
The size and the appearance of the three-dimensional molybdenum disulfide flower ball array prepared by the embodiment are similar to those of the embodiment 1.
Testing the performance of the electrocatalytic hydrogen evolution reaction: and (3) punching the molybdenum disulfide flower ball array titanium wire mesh after the hydrothermal reaction into a wafer with the diameter of 7.5mm as a testing working electrode. The electrolyte is 0.5M sulfuric acid aqueous solution, the reference electrode is a saturated calomel electrode, a platinum sheet is used as a counter electrode, the electrocatalytic performance of the material on the hydrogen evolution reaction is tested by linear potential scanning on a CHI760E electrochemical workstation, and the scanning speed is 5 mV/s.
The test result shows that the current density of the electrochemical catalytic hydrogen evolution reaction on the molybdenum disulfide flower ball array electrode is 131mA/cm under the potential of-0.30 Vvs2The catalyst has high hydrogen evolution reaction electrocatalytic performance (calculated by actual load area).
Comparative example 1
The embodiment provides a titanium plate-supported molybdenum disulfide nanosheet. In the preparation method, the operation and conditions were the same as those in example 1 except that the titanium mesh was changed to titanium plate.
The molybdenum disulfide nanosheet loaded with the titanium plate prepared in this example is shown in fig. 4, and a stable three-dimensional molybdenum disulfide flower ball array is not generated.
Comparative example 2
The embodiment provides a molybdenum disulfide nanosheet. In the preparation method, the operation and conditions were the same as those in example 1 except that no titanium mesh was added.
The molybdenum disulfide nanosheets prepared in this example are scattered as shown in fig. 5, and a stable three-dimensional molybdenum disulfide flower-ball array is not generated.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (6)
1. A preparation method of a three-dimensional molybdenum disulfide flower ball array is characterized by comprising the following steps:
s1: dissolving a molybdenum source and a sulfur source to obtain a mixed solution; the molar ratio of the sulfur element in the sulfur source to the molybdenum element in the molybdenum source is 3: 1-6: 1;
s2: and adding the titanium wire mesh into the mixed solution S1, carrying out hydrothermal reaction for 8-24 h at 200-220 ℃ in a closed environment, cooling, taking out the titanium wire mesh, rinsing, and drying to obtain the three-dimensional molybdenum disulfide flower ball array.
2. The method for preparing the three-dimensional molybdenum disulfide flower ball array according to claim 1, wherein the molybdenum source in S1 is one or more of ammonium molybdate, sodium molybdate or potassium molybdate; the sulfur source is one or two of thioacetamide or thiourea.
3. The method for preparing the three-dimensional molybdenum disulfide ball array according to claim 1, wherein the concentration of molybdenum element in the mixed solution in S1 is 0.02-0.05 mol/L.
4. The method for preparing the three-dimensional molybdenum disulfide flower ball array according to claim 1, wherein the molar ratio of the sulfur element in the sulfur source to the molybdenum element in the molybdenum source in S1 is 4: 1-6: 1.
5. The method for preparing the three-dimensional molybdenum disulfide flower ball array according to claim 1, wherein the hydrothermal reaction temperature in S2 is 200 ℃ and the time is 16 h.
6. The method for preparing the three-dimensional molybdenum disulfide ball array according to claim 1, wherein the reagents selected for rinsing in S2 are deionized water and absolute ethyl alcohol; the drying process comprises the following steps: and drying at 60-80 ℃ in a vacuum environment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811223136.3A CN109081377B (en) | 2018-10-19 | 2018-10-19 | Three-dimensional molybdenum disulfide flower ball array and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811223136.3A CN109081377B (en) | 2018-10-19 | 2018-10-19 | Three-dimensional molybdenum disulfide flower ball array and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109081377A CN109081377A (en) | 2018-12-25 |
| CN109081377B true CN109081377B (en) | 2020-07-28 |
Family
ID=64843976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811223136.3A Active CN109081377B (en) | 2018-10-19 | 2018-10-19 | Three-dimensional molybdenum disulfide flower ball array and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109081377B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002500B (en) * | 2019-03-28 | 2021-04-02 | 岭南师范学院 | Method for preparing molybdenum disulfide flower balls with assistance of sodium polyacrylate and application of method |
| CN114768530B (en) * | 2022-04-29 | 2023-03-28 | 中国工程物理研究院材料研究所 | Application of molybdenum disulfide in hydrogen isotope electrolytic separation |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100548891C (en) * | 2007-07-03 | 2009-10-14 | 浙江大学 | A kind of method for preparing flower-shaped molybdenum disulfide micro-balloon |
| CN106521460A (en) * | 2016-10-31 | 2017-03-22 | 华南理工大学 | A preparing method for a hydrogen production composite catalytic electrode |
| CN106684352A (en) * | 2016-12-26 | 2017-05-17 | 北京工业大学 | Preparation method of titanium dioxide nano-tube array immobilized spherical molybdenum disulfide negative electrode material for lithium battery |
| CN106803589B (en) * | 2017-02-26 | 2019-08-09 | 桂林理工大学 | A kind of monodisperse class flower ball-shaped MoS2Raw powder's production technology |
| CN106986387B (en) * | 2017-06-02 | 2018-08-10 | 岭南师范学院 | A kind of three-dimensional molybdenum disulfide bouquet and preparation method thereof |
| CN108155028B (en) * | 2017-12-29 | 2020-03-17 | 安徽大学 | Preparation method of flower-like molybdenum disulfide high-performance supercapacitor electrode |
| CN108557793B (en) * | 2018-02-12 | 2021-05-07 | 西北工业大学 | Flower-shaped titanium phosphate microsphere assembled by nanosheets and preparation method thereof |
| CN108404937B (en) * | 2018-03-22 | 2020-10-30 | 南昌航空大学 | Nanocomposite MoS2/Ag/TiO2Preparation method of NTs |
-
2018
- 2018-10-19 CN CN201811223136.3A patent/CN109081377B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109081377A (en) | 2018-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105914374B (en) | Composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure and its preparation method and application | |
| CN110444408A (en) | A kind of vanadium nitride nanometer sheet flexible composite electrode material and the preparation method and application thereof | |
| Yang et al. | Perovskite-type La1− xCaxMnO3 manganese oxides as effective counter electrodes for dye-sensitized solar cells | |
| CN107140699B (en) | NiS2Meso-porous nano ball material and its preparation method and application | |
| CN109967100A (en) | A kind of metal-doped CoP3, preparation method and application | |
| CN107275105A (en) | Electrode material for super capacitor and preparation method thereof | |
| CN108630444A (en) | The preparation method of porous Ni-Mo-Co ternary hydroxides nanometer sheet super capacitor material | |
| CN109786742B (en) | Se-doped MXene battery negative electrode material and preparation method and application thereof | |
| CN109616331A (en) | A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof | |
| CN110371936A (en) | A kind of preparation method and applications of interlamellar spacing adjustable sodium-ion battery copper selenide nano-chip arrays | |
| CN107188230A (en) | A kind of molybdenum disulfide carbon is combined bouquet and its preparation method and application | |
| CN110316761A (en) | A kind of MnO for water system Zinc ion battery2Nano-fiber material and preparation method thereof | |
| CN110010359A (en) | A kind of preparation method of nickel cobalt/hydroxide combination electrode material | |
| CN106025234A (en) | Preparation method of no-adhesive Ni3S2/Ni sodium ion battery anode | |
| CN109712818A (en) | A kind of manganese-base oxide composite and flexible electrode material and preparation method thereof | |
| Tawalbeh et al. | Insights on the applications of metal oxide nanosheets in energy storage systems | |
| CN107146711A (en) | A kind of conductive substrates growth nano lamellar metal compound electrode material and its preparation and application | |
| Prasankumar et al. | Functional carbons for energy applications | |
| CN109081377B (en) | Three-dimensional molybdenum disulfide flower ball array and preparation method and application thereof | |
| Li et al. | Unique 3D bilayer nanostructure basic cobalt carbonate@ NiCo–layered double hydroxide nanosheets on carbon cloth for supercapacitor electrode material | |
| CN111646509A (en) | Sodium-ion battery curled vanadium tetrasulfide nanosheet negative electrode material and preparation method and application thereof | |
| CN111268745A (en) | NiMoO4@Co3O4Core-shell nano composite material, preparation method and application | |
| CN106757367A (en) | The preparation method of high length-diameter ratio nickel sulfide monocrystal nano line array | |
| CN109950503A (en) | A kind of CoMoOx/ carbon/sulphur composite nano materials preparation method, negative electrode of lithium ion battery and lithium ion half-cell | |
| CN106783196B (en) | Preparation method of polyhedral ferric oxide nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |