CN109285992B - Molybdenum sulfide flexible electrode material and preparation method and application thereof - Google Patents

Molybdenum sulfide flexible electrode material and preparation method and application thereof Download PDF

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CN109285992B
CN109285992B CN201710590354.XA CN201710590354A CN109285992B CN 109285992 B CN109285992 B CN 109285992B CN 201710590354 A CN201710590354 A CN 201710590354A CN 109285992 B CN109285992 B CN 109285992B
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molybdenum
electrode material
cotton
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hydrothermal reaction
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CN109285992A (en
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谭强强
夏青
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Institute of Process Engineering of CAS
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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
    • H01M4/362—Composites
    • 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
    • H01G11/30—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
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The invention relates to a molybdenum sulfide flexible electrode material and a preparation method and application thereof, wherein the method comprises the following steps: spraying elemental metal on the surface of a cotton carbon source, mixing the elemental metal with a molybdenum source, ammonium fluoride and urea, carrying out hydrothermal reaction, carrying out solid-liquid separation after the reaction is finished to obtain a precursor material, mixing the precursor material with a sulfur source, carrying out secondary hydrothermal reaction, carrying out solid-liquid separation after the reaction is finished, and carrying out heat treatment to obtain the molybdenum sulfide flexible electrode material. The invention directly uses waste cotton materials or most cotton materials as carbon sources and templates, thus being economic and environment-friendly; the metal is used as a catalyst, and a two-step vulcanization method is adopted, so that the generation temperature of molybdenum sulfide is reduced, and the flexibility and the integrity of the cotton material are kept; when the prepared molybdenum sulfide flexible electrode material is used as a lithium ion battery cathode material, the prepared molybdenum sulfide flexible electrode material has excellent electrochemical performance, the first charge-discharge reversible specific capacity of the material can reach 800-1400mAh/g, and the material has wide application prospect.

Description

Molybdenum sulfide flexible electrode material and preparation method and application thereof
Technical Field
The invention relates to the field of nano material preparation, in particular to a molybdenum sulfide flexible electrode material and a preparation method and application thereof.
Background
The rise of flexible wearable electronic devices has pushed the rapid development of flexible energy storage technologies. As the most central part of the flexible energy storage device, the preparation and assembly of the flexible electrode directly determines the performance level of the flexible energy storage device. The cotton material has good flexibility, is light and thin, has low price, is environment-friendly, can be carbonized through high-temperature heat treatment, has good conductivity, and can be used as a substrate of the material.
Molybdenum sulfide (MoS)2) The graphene-like two-dimensional layered structure is provided, and is an ideal lithium ion battery cathode material. However, during the circulation process, as the molybdenum disulfide is completely reacted into molybdenum and lithium sulfide, a large volume change is caused, and the circulation stability is reduced. In addition, the intrinsic electronic conductivity of molybdenum disulfide is poor, so that the rate performance of the molybdenum disulfide is poor.
The cotton material is a biological material widely existing in nature, can be carbonized at high temperature to obtain a carbon material with high conductivity, simultaneously retains the original appearance of the carbon material, and provides a good biological template for preparing the composite electrode material. The method has the advantages that the cotton material is used as the carbon source, so that the problem of recycling cotton clothes and the like can be greatly solved, meanwhile, the low-cost carbon source is provided for preparing the composite electrode material, the method is green and environment-friendly, and the requirement of low-carbon development is met. The cotton material is used as the molybdenum sulfide substrate, so that the molybdenum sulfide can directly grow on the surface of the cotton fiber, the electronic conductivity of the material is improved, and meanwhile, the flexible electrode material with certain mechanical strength is obtained. However, the synthesis temperature of molybdenum sulfide is high, and the cotton cloth is easy to break under the high-temperature and high-pressure hydrothermal environment, so that the shape is difficult to maintain.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a molybdenum sulfide flexible electrode material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a molybdenum sulfide flexible electrode material, wherein the method comprises the following steps:
(1) spraying elemental metal on the surface of the cotton carbon source;
(2) mixing the material obtained in the step (1) with a molybdenum source, ammonium fluoride and urea, carrying out hydrothermal reaction, and carrying out solid-liquid separation after the reaction is finished to obtain a precursor material;
(3) mixing the precursor material obtained in the step (2) with a sulfur source, carrying out a secondary hydrothermal reaction, and carrying out solid-liquid separation after the reaction is finished;
(4) and (4) carrying out heat treatment on the material obtained in the step (3) to obtain the molybdenum sulfide flexible electrode material.
The cotton material is mostly in a hollow fiber structure, can be carbonized into the carbon micron tube through heat treatment, has a capillary effect, and can make molybdenum sulfide directly grow on the surface of the carbon micron tube by utilizing the capillary effect and the surface bonding effect. The obtained molybdenum sulfide flexible electrode material has a hollow fiber interweaving structure, is beneficial to full infiltration of electrolyte, can shorten the transmission path of lithium ions and electrons, increase the contact area with the electrolyte, provide more reactive sites, and simultaneously buffer the volume change of the material in the circulating process to a certain extent, thereby improving the rate capability and the circulating stability of the material.
The invention firstly sprays a layer of metal on the surface of cotton material, utilizes the high catalytic activity of the metal and adopts a two-step vulcanization mode to complete the exchange process of sulfide ions and oxygen ions, thus obtaining the molybdenum sulfide flexible electrode material. The elemental metal has higher catalytic property, and by utilizing the catalytic property, the synthesis temperature of the molybdenum sulfide can be reduced, and the flexibility of the cotton material is kept, so that the molybdenum sulfide flexible electrode material is obtained.
According to the invention, the cotton carbon source in the step (1) is a cotton material, preferably any one or a combination of at least two of clothes, towels, cotton cloth and dust-free cloth; for example, the fabric may be any one of clothes, towels, cotton cloth or dust-free cloth, and a typical but non-limiting combination is clothes and towels; clothing and cotton cloth; towels and cotton; cotton cloth and dust-free cloth; clothing, towels, and cotton cloth; towels, cotton and dust-free cloths, etc., are not exhaustive for the purpose of space and simplicity.
According to the invention, the elementary metal in the step (1) is any one of gold, silver, copper, nickel or iron.
According to the invention, the mass ratio of the elementary metal to the cotton carbon source in the step (1) is (0.001-10) to 1, preferably (0.01-0.5) to 1; for example, 1:1000, 1:500, 1:100, 1:50, 1:10, 1:5, 1:2, 1:1, 2:1, 5:1, or 10:1, and the specific points between the above values, are not exhaustive for the invention and are not intended to be limiting for brevity and conciseness.
Generally, in the step (1), a layer of elemental metal may be sputtered on the surface of the cotton carbon source, or multiple layers may be sputtered on the surface of the cotton carbon source, which is not particularly limited.
According to the invention, the molybdenum source in the step (2) is any one or a combination of at least two of ammonium molybdate, sodium molybdate, ammonium thiomolybdate, molybdenum chloride or molybdenum acetylacetonate; for example, it may be any one of ammonium molybdate, sodium molybdate, ammonium thiomolybdate, molybdenum chloride or molybdenum acetylacetonate, with a typical but non-limiting combination being: ammonium molybdate and sodium molybdate; ammonium thiomolybdate and molybdenum chloride; ammonium molybdate and molybdenum chloride; molybdenum chloride and molybdenum acetylacetonate; ammonium molybdate and ammonium thiomolybdate; ammonium molybdate, sodium molybdate and ammonium thiomolybdate; ammonium thiomolybdate, molybdenum chloride, molybdenum acetylacetonate, and the like, are not exhaustive for the purposes of space and brevity.
According to the invention, the mass ratio of the molybdenum source in the step (2) to the cotton carbon source in the step (1) is (0.1-40):1, preferably (0.5-4): 1; for example, 1:10, 1:5, 1:2, 1:1, 2:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, or 40:1, and the specific values therebetween, are not intended to be exhaustive for the sake of brevity and clarity.
According to the invention, the molar ratio of the molybdenum source to the ammonium fluoride in the step (2) is 1 (0.05-20), preferably 1 (0.1-10); for example, 20:1, 15:1, 10:1, 5:1, 2:1, 1:2, 1:5, 1:10, 1:15, or 1:20, and the specific point values between the above values, are not intended to be exhaustive for the sake of brevity and clarity.
According to the invention, the molar ratio of the molybdenum source to the urea in the step (2) is 1 (0.1-20), preferably 1 (0.5-10); for example, 10:1, 5:1, 2:1, 1:2, 1:5, 1:10, 1:15, or 1:20, and the specific values therebetween, are not intended to be exhaustive for the sake of brevity and clarity.
According to the invention, the temperature of the hydrothermal reaction in the step (2) is 90-200 ℃, preferably 100-150 ℃; for example, it may be 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, and the specific values therebetween, are limited by space and for brevity, and are not exhaustive.
Preferably, the pressure of the hydrothermal reaction in the step (2) is 2-30MPa, preferably 5-20 MPa; for example, 2MPa, 5MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa, 23MPa, 25MPa, 28MPa or 30MPa, and the specific values therebetween, are limited by space and for brevity and are not exhaustive.
Preferably, the hydrothermal reaction time of the step (2) is 2-72h, preferably 15-30 h; for example, the values may be 2h, 5h, 10h, 15h, 18h, 20h, 25h, 28h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h or 72h, and the specific values therebetween are limited by space and for brevity, the present invention is not exhaustive.
According to the invention, the sulfur source in the step (3) is any one or a combination of at least two of sodium sulfide, sodium thiosulfate or thiourea; for example, it may be any one of sodium sulfide, sodium thiosulfate or thiourea, and a typical but non-limiting combination is: sodium sulfide and sodium thiosulfate; sodium sulfide and thiourea; sodium thiosulfate and thiourea; sodium sulfide, sodium thiosulfate, and thiourea.
According to the invention, the molar ratio of the sulfur source in the step (3) to the molybdenum source in the step (2) is 1 (0.5-10), preferably 1 (1-5); for example, 2:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, and the specific point values between the above values, are not exhaustive for the invention and are not intended to be limiting for brevity and conciseness.
According to the invention, the temperature of the secondary hydrothermal reaction in the step (3) is 80-150 ℃, preferably 90-120 ℃; for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃ and the specific values therebetween, are limited to the space and the simplicity, and the present invention is not exhaustive.
According to the invention, the pressure of the secondary hydrothermal reaction in the step (3) is 2-30MPa, preferably 5-20 MPa; for example, 2MPa, 5MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa, 23MPa, 25MPa, 28MPa or 30MPa, and the specific values therebetween, are limited by space and for brevity and are not exhaustive.
According to the invention, the time of the secondary hydrothermal reaction in the step (3) is 2-20h, preferably 5-12 h; for example, 2h, 5h, 8h, 10h, 12h, 15h, 18h or 20h, and the specific values therebetween, are limited by space and for brevity, and are not exhaustive.
According to the invention, the temperature of the heat treatment in the step (4) is 500-1000 ℃, preferably 700-900 ℃; for example, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C, or 1000 deg.C, and the specific values therebetween, are not intended to be exhaustive for purposes of brevity and brevity.
According to the invention, the time of the heat treatment in the step (4) is 0.5-10h, preferably 1-4 h; for example, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10h, and the specific values therebetween, are not intended to be exhaustive for reasons of brevity and clarity.
The solid-liquid separation according to the present invention is performed by means known in the art, such as filtration, suction filtration, centrifugation, etc., but not limited thereto, and is convenient for operation in the actual operation process.
In a second aspect, the invention provides a molybdenum sulfide flexible electrode material prepared by the method in the first aspect.
In a third aspect, the present invention provides a use of the molybdenum sulfide flexible electrode material according to the second aspect as a negative electrode material of a lithium ion battery, a negative electrode material of a sodium ion battery, an electrode material of a super capacitor, or a hydrogen evolution material.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the preparation process directly uses waste cotton materials or most cotton materials as carbon sources and templates, is green and environment-friendly, and greatly reduces the production cost.
(2) The metal is used as a catalyst, and a two-step sulfurization method is adopted, so that the generation temperature of molybdenum sulfide is reduced, and the flexibility and the integrity of the cotton material are kept.
(3) The prepared molybdenum sulfide flexible electrode material has excellent electrochemical performance when being used as a lithium ion battery cathode material, has the first charge-discharge reversible specific capacity of 800-1400mAh/g, and can also be used as a sodium ion battery cathode material or a supercapacitor electrode material to be applied to the field of energy storage.
(4) The preparation process is simple and flexible to operate, mild in reaction conditions, suitable for industrial production and wide in application prospect.
Drawings
Fig. 1 is a charge-discharge curve of the molybdenum sulfide flexible electrode material obtained in example 1 of the present invention as a negative electrode material of a lithium ion battery, in which the abscissa represents cycle number and the ordinate represents specific capacity.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
(1) Spraying a layer of gold on the surface of the cotton cloth, wherein the mass ratio of the gold to the cotton cloth is 1: 5;
(2) mixing the material obtained in the step (1) with ammonium molybdate, ammonium fluoride and urea, wherein the mass ratio of cotton cloth to ammonium molybdate is 1:1, and the molar ratio of ammonium molybdate, ammonium fluoride and urea is 1:2:4, transferring the mixture into a closed reaction kettle, carrying out hydrothermal treatment in an oven at 150 ℃ for 24h, carrying out solid-liquid separation after the reaction is finished, and cleaning to obtain a precursor;
(3) mixing the precursor obtained in the step (2) with sodium sulfide, wherein the molar ratio of the sodium sulfide to the ammonium molybdate is 1:4, transferring the mixture into a closed reaction kettle again, carrying out hydrothermal treatment for 10 hours in an oven at 100 ℃, carrying out solid-liquid separation after the reaction is finished, and cleaning;
(4) and (4) carrying out heat treatment on the material obtained in the step (3) at 750 ℃ for 3h to obtain the molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material obtained in the embodiment is directly used as a lithium ion battery cathode material for electrochemical performance test, and the CR2032 type button battery is prepared. The test was carried out at a voltage window of 0.01-3.0V and a current density of 100 mA/g.
As shown in fig. 1, the molybdenum sulfide flexible electrode material obtained in this example shows a relatively high reversible specific capacity when used as a negative electrode material of a lithium ion battery. The first cyclic discharge specific capacity is 1450mAh/g, and the charge specific capacity is 1100 mAh/g. The specific discharge capacity of the second circulation is 1100mAh/g, and the specific charge capacity is 1050 mAh/g.
Example 2
(1) A layer of silver is sprayed on the surface of the dust-free cloth, and the mass ratio of the silver to the dust-free cloth is 1: 8;
(2) mixing the material obtained in the step (1) with ammonium thiomolybdate, ammonium fluoride and urea, wherein the mass ratio of the ammonium thiomolybdate to the dust-free cloth is 4:1, and the molar ratio of the ammonium thiomolybdate to the ammonium fluoride to the urea is 1:3:5, transferring the mixture into a closed reaction kettle, carrying out hydrothermal treatment for 5 hours in an oven at 200 ℃, carrying out solid-liquid separation after the reaction is finished, and cleaning to obtain a precursor;
(3) mixing the precursor obtained in the step (2) with sodium thiosulfate, wherein the molar ratio of the sodium thiosulfate to the ammonium thiomolybdate is 1:2, transferring the mixture into a closed reaction kettle again, carrying out hydrothermal reaction for 8 hours in an oven at 120 ℃, carrying out solid-liquid separation after the reaction is finished, and cleaning;
(4) and (4) carrying out heat treatment on the material obtained in the step (3) at 800 ℃ for 2.5h to obtain the molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material obtained in the embodiment is directly used as a lithium ion battery cathode material for electrochemical performance test, and the test method is the same as that in embodiment 1.
The result shows that the molybdenum sulfide flexible electrode material obtained in the embodiment shows higher reversible specific capacity when being used as a negative electrode material of a lithium ion battery. The first cyclic discharge specific capacity is 1050mAh/g, and the charge specific capacity is 1000 mAh/g. The specific discharge capacity of the second circulation is 970mAh/g, and the specific charge capacity is 950 mAh/g.
Example 3
(1) Spraying a layer of copper on the surface of the cotton cloth, wherein the mass ratio of the copper to the dust-free cloth is 1: 10;
(2) mixing the material obtained in the step (1) with sodium molybdate, ammonium fluoride and urea, wherein the mass ratio of the sodium molybdate to the dust-free cloth is 3:1, and the molar ratio of the sodium molybdate to the ammonium fluoride to the urea is 1:10:10, transferring the mixture into a closed reaction kettle, performing hydrothermal treatment in an oven at 120 ℃ for 20h, performing solid-liquid separation after the reaction is finished, and cleaning to obtain a precursor;
(3) mixing the precursor obtained in the step (2) with sodium sulfide, wherein the molar ratio of the sodium sulfide to the sodium molybdate is 1:3, transferring the mixture into a closed reaction kettle again, carrying out hydrothermal treatment at 90 ℃ in an oven for 12 hours, carrying out solid-liquid separation after the reaction is finished, and cleaning;
(4) and (4) carrying out heat treatment on the material obtained in the step (3) at 1000 ℃ for 1h to obtain the molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material obtained in the embodiment is directly used as a lithium ion battery cathode material for electrochemical performance test, and the test method is the same as that in embodiment 1.
The result shows that the molybdenum sulfide flexible electrode material obtained in the embodiment shows higher reversible specific capacity when being used as a negative electrode material of a lithium ion battery. The first cycle discharge specific capacity is 1480mAh/g, and the charge specific capacity is 1360 mAh/g. The specific discharge capacity of the second cycle is 1320mAh/g, and the specific charge capacity is 1300 mAh/g.
Example 4
(1) Spraying a layer of nickel on the surface of the clothes, wherein the mass ratio of the nickel to the clothes is 1: 20;
(2) mixing the material obtained in the step (1) with molybdenum chloride, ammonium fluoride and urea, wherein the mass ratio of the molybdenum chloride to clothes is 2:1, and the molar ratio of the molybdenum chloride to the ammonium fluoride to the urea is 1:1:5, transferring the mixture into a closed reaction kettle, carrying out hydrothermal treatment in an oven at 140 ℃ for 18h, carrying out solid-liquid separation after the reaction is finished, and cleaning to obtain a precursor;
(3) mixing the precursor obtained in the step (2) with thiourea, wherein the molar ratio of thiourea to molybdenum chloride is 1:5, transferring the mixture into a closed reaction kettle again, performing hydrothermal treatment in an oven at 80 ℃ for 20 hours, and performing solid-liquid separation and cleaning after the reaction is finished;
(4) and (4) carrying out heat treatment on the material obtained in the step (3) at 900 ℃ for 1.5h to obtain the molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material obtained in the embodiment is directly used as a lithium ion battery cathode material for electrochemical performance test, and the test method is the same as that in embodiment 1.
The result shows that the molybdenum sulfide flexible electrode material obtained in the embodiment shows higher reversible specific capacity when being used as a negative electrode material of a lithium ion battery. The first cyclic discharge specific capacity is 960mAh/g, and the charge specific capacity is 900 mAh/g. The specific discharge capacity of the second circulation is 850mAh/g, and the specific charge capacity is 840 mAh/g.
Example 5
(1) Spraying a layer of iron on the surface of the cotton cloth, wherein the mass ratio of the iron to the cotton cloth is 1: 15;
(2) mixing the material obtained in the step (1) with ammonium molybdate, ammonium fluoride and urea, wherein the mass ratio of ammonium molybdate to cotton cloth is 1:1, and the molar ratio of ammonium molybdate to urea is 1:3:6, transferring the mixture into a closed reaction kettle, carrying out hydrothermal treatment for 15h in an oven at 150 ℃, carrying out solid-liquid separation after the reaction is finished, and cleaning to obtain a precursor;
(3) mixing the precursor obtained in the step (2) with thiourea, wherein the molar ratio of thiourea to ammonium molybdate is 1:1, transferring the mixture into a closed reaction kettle again, carrying out hydrothermal treatment at 100 ℃ in an oven for 10 hours, carrying out solid-liquid separation after the reaction is finished, and cleaning;
(4) and (4) carrying out heat treatment on the material obtained in the step (3) at 850 ℃ for 2.5h to obtain the molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material obtained in the embodiment is directly used as a lithium ion battery cathode material for electrochemical performance test, and the test method is the same as that in embodiment 1.
The result shows that the molybdenum sulfide flexible electrode material obtained in the embodiment shows higher reversible specific capacity when being used as a negative electrode material of a lithium ion battery. The first cyclic discharge specific capacity is 1100mAh/g, and the charge specific capacity is 1020 mAh/g. The specific discharge capacity of the second circulation is 1050mAh/g, and the specific charge capacity is 1000 mAh/g.
Comparative example 1
Compared with example 1, except that step 1 was removed, the other steps and conditions were the same as example 1, that is, the cotton cloth was directly mixed with ammonium molybdate, ammonium fluoride and urea, and the operation of spraying gold was not performed.
The molybdenum sulfide electrode material obtained in the comparative example is directly used as a lithium ion battery cathode material for electrochemical performance test, and the test method is the same as that in example 1.
The results show that the molybdenum sulfide electrode material obtained by the comparative example is used as the negative electrode material of the lithium ion battery. The first cyclic discharge specific capacity is 850mAh/g, and the charge specific capacity is 790 mAh/g. The specific discharge capacity of the second circulation is 700mAh/g, and the specific charge capacity is 690 mAh/g.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (32)

1. A preparation method of a molybdenum sulfide flexible electrode material is characterized by comprising the following steps:
(1) spraying elemental metal on the surface of a cotton carbon source, wherein the cotton carbon source is a cotton material, and the elemental metal is any one of gold, silver, copper, nickel or iron;
(2) mixing the material obtained in the step (1) with a molybdenum source, ammonium fluoride and urea, carrying out hydrothermal reaction, and carrying out solid-liquid separation after the reaction is finished to obtain a precursor material;
(3) mixing the precursor material obtained in the step (2) with a sulfur source, carrying out a secondary hydrothermal reaction, and carrying out solid-liquid separation after the reaction is finished;
(4) and (4) carrying out heat treatment on the material obtained in the step (3) to obtain the molybdenum sulfide flexible electrode material.
2. The method of claim 1, wherein the cotton-based carbon source in step (1) is any one of clothes, towels, cotton cloth and dust-free cloth or a combination of at least two of the clothes, the towels, the cotton cloth and the dust-free cloth.
3. The method of claim 1, wherein the mass ratio of the elemental metal to the cotton-based carbon source in step (1) is (0.001-10): 1.
4. The method of claim 1, wherein the mass ratio of the elemental metal to the cotton-based carbon source in step (1) is (0.01-0.5): 1.
5. The method of claim 1, wherein the molybdenum source in step (2) is any one of ammonium molybdate, sodium molybdate, ammonium thiomolybdate, molybdenum chloride or molybdenum acetylacetonate or a combination of at least two thereof.
6. The method of claim 1, wherein the mass ratio of the molybdenum source in step (2) to the cotton-based carbon source in step (1) is (0.1-40): 1.
7. The method of claim 6, wherein the mass ratio of the molybdenum source in step (2) to the cotton-based carbon source in step (1) is (0.5-4): 1.
8. The method of claim 1, wherein the molar ratio of the molybdenum source to the ammonium fluoride in step (2) is 1 (0.05-20).
9. The method of claim 8, wherein the molar ratio of the molybdenum source to the ammonium fluoride in step (2) is 1 (0.1-10).
10. The method of claim 1, wherein the molar ratio of the molybdenum source to the urea in step (2) is 1 (0.1-20).
11. The method of claim 10, wherein the molar ratio of the molybdenum source to the urea in step (2) is 1 (0.5-10).
12. The method of claim 1, wherein the hydrothermal reaction of step (2) is at a temperature of 90-200 ℃.
13. The method as claimed in claim 12, wherein the hydrothermal reaction in step (2) is carried out at a temperature of 100-150 ℃.
14. The method of claim 1, wherein the hydrothermal reaction of step (2) is carried out at a pressure of 2 to 30 MPa.
15. The method of claim 14, wherein the hydrothermal reaction of step (2) is at a pressure of 5 to 20 MPa.
16. The method of claim 1, wherein the hydrothermal reaction time in step (2) is 2-72 hours.
17. The method of claim 16, wherein the hydrothermal reaction of step (2) is carried out for a time period of 15 to 30 hours.
18. The method of claim 1, wherein the sulfur source in step (3) is any one of sodium sulfide, sodium thiosulfate or thiourea, or a combination of at least two of them.
19. The method of claim 1, wherein the molar ratio of the sulfur source in step (3) to the molybdenum source in step (2) is 1 (0.5-10).
20. The method of claim 19, wherein the molar ratio of the sulfur source of step (3) to the molybdenum source of step (2) is 1 (1-5).
21. The method of claim 1, wherein the temperature of the second hydrothermal reaction in step (3) is 80-150 ℃.
22. The method of claim 21, wherein the temperature of the second hydrothermal reaction in step (3) is 90-120 ℃.
23. The method of claim 1, wherein the pressure of the second hydrothermal reaction in step (3) is 2 to 30 MPa.
24. The method of claim 23, wherein the pressure of the second hydrothermal reaction in step (3) is 5 to 20 MPa.
25. The method of claim 1, wherein the time of the second hydrothermal reaction in step (3) is 2-20 h.
26. The method of claim 25, wherein the time of the second hydrothermal reaction in step (3) is 5-12 h.
27. The method as claimed in claim 1, wherein the temperature of the heat treatment in the step (4) is 500-1000 ℃.
28. The method as claimed in claim 27, wherein the temperature of the heat treatment in the step (4) is 700-900 ℃.
29. The method of claim 1, wherein the heat treatment of step (4) is performed for a time period of 0.5 to 10 hours.
30. The method of claim 29, wherein the heat treatment of step (4) is performed for a period of 1-4 hours.
31. A molybdenum sulphide flexible electrode material produced by the method of any one of claims 1 to 30.
32. The use of the molybdenum sulfide flexible electrode material according to claim 31, wherein the molybdenum sulfide flexible electrode material is used as a lithium ion battery negative electrode material, a sodium ion battery negative electrode material, a supercapacitor electrode material, or a hydrogen evolution material.
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