CN105932252B - A kind of sulphur selenizing molybdenum/carbon nano tube compound material and its preparation and application - Google Patents
A kind of sulphur selenizing molybdenum/carbon nano tube compound material and its preparation and application Download PDFInfo
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- CN105932252B CN105932252B CN201610392009.0A CN201610392009A CN105932252B CN 105932252 B CN105932252 B CN 105932252B CN 201610392009 A CN201610392009 A CN 201610392009A CN 105932252 B CN105932252 B CN 105932252B
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- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 134
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 134
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 82
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 74
- 239000005864 Sulphur Substances 0.000 title claims abstract description 73
- 239000011733 molybdenum Substances 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 71
- -1 carbon nano tube compound Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- XACAZEWCMFHVBX-UHFFFAOYSA-N [C].[Mo] Chemical compound [C].[Mo] XACAZEWCMFHVBX-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 11
- 229910052711 selenium Inorganic materials 0.000 claims description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 239000011669 selenium Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- VBNIGYNNILMQRE-UHFFFAOYSA-N O.NN.[Se] Chemical compound O.NN.[Se] VBNIGYNNILMQRE-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000006396 nitration reaction Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 235000015393 sodium molybdate Nutrition 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000011684 sodium molybdate Substances 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 229910018113 Se—Mo—Se Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- DORQJBTVNDGTEY-UHFFFAOYSA-N selanylidenemolybdenum Chemical compound [Se].[Mo] DORQJBTVNDGTEY-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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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
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- 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
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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
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- 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
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Abstract
The present invention relates to a kind of sulphur selenizing molybdenum/carbon nano tube compound material and its preparation and application, the sulphur selenizing molybdenum/carbon nano tube compound material is the uniform enveloped carbon nanometer tube of sulphur selenizing molybdenum nanometer sheet.It prepares:Nitration mixture handles carbon nanotube, and then by solvent-thermal method, growth in situ selenizing molybdenum obtains selenizing molybdenum carbon nano tube compound material on the carbon nanotubes;By high temperature replace reaction realize sulphur to the doping of selenizing molybdenum nanometer sheet to get.Application of the composite material in electro-catalysis water decomposition device, lithium ion battery, ultracapacitor.Selenizing molybdenum and carbon nanotube progress is effectively compound, good synergistic effect between the two can be realized, and its electronic structure is regulated and controled by sulfur doping, to prepare the sulphur selenizing molybdenum carbon nano tube compound material of electrochemical performance.
Description
Technical field
The invention belongs to carbon nano tube compound material and its preparation and application field, more particularly to a kind of sulphur selenizing molybdenum/carbon
Nanometer tube composite materials and its preparation and application.
Background technology
Carbon nanotube has unique one-dimensional nano structure, big specific surface area, superpower mechanical performance, high thermostabilization
Property and good conductive capability, people widely concern and research have just been obtained since self-discovery.As conductive filler
It is added among other electrode materials, can not only improve the electronics and ion transport capability of combination electrode material, it can also be notable
Enhance the mechanical performances such as the film forming of electrode material, it is made all to have in the fields such as energy conversion and memory device, electronic sensor
There is extremely wide application prospect, becomes one of the research hotspot in carbon nanomaterial field.
For selenizing molybdenum as one of typical Transition-metal dichalcogenide, structure is similar to molybdenum sulfide, is by two six sides
The class graphene layer structure of layered crystal structure composition.Wherein, each molybdenum atom is by two selenium atom packets on triangular prism
It encloses.Mainly by being covalently keyed in Se-Mo-Se layers, interlayer is connected by weaker Van der Waals force, this unique crystalline substance
Body structure makes it receive the highest attention of people in fields such as electro-chemical water decomposition catalyst, ultracapacitor and lithium batteries.
Studies have shown that the active edge of selenizing molybdenum exposure has catalytic activity for hydrogen evolution, and its hydrogen absorption Gibbs free energy compares curing
Molybdenum is closer to thermo-neutrality, therefore selenizing molybdenum theory overpotential of hydrogen evolution is lower, and catalytic activity of hydrogen evolution is better.But pure selenium molybdenum is easy
In reunion, lamella internal flaw is less and inhibits the exposure of active site, and poor as semiconducting electrical conductivity, thus
Limit its application in fields such as catalysis.Both therefore, selenizing molybdenum and the base material of other high conductivity is compound, solve
Dispersibility and surface in the base can more effectively play the advantage of the two various aspects in conjunction with problem.
Invention content
Technical problem to be solved by the invention is to provide a kind of sulphur selenizing molybdenum/carbon nano tube compound material and its prepare and
Using the present invention is sulphur selenizing molybdenum-carbon nano tube compound material of low cost, electrochemical performance;Preparation process is simple,
It is easily operated, it is a kind of effective efficiently preparation method;The present invention passes through solvent-thermal method growth in situ selenizing on the carbon nanotubes
Molybdenum nanometer sheet, then a kind of sulphur selenizing molybdenum-carbon nano tube compound material is prepared by high temperature vulcanized method.Prepared by the present invention
Sulphur selenizing molybdenum-carbon nano tube compound material have the characteristics that morphology controllable, the electric conductivity for making full use of carbon nanotube excellent and
High specific surface area makes few layer selenizing molybdenum nanometer sheet uniform load on the carbon nanotubes, effectively inhibits selenizing molybdenum nanometer sheet certainly
The reunion of body and stacking;It, can be with the band structure of Effective Regulation selenizing molybdenum, while in nanometer sheet again by high temperature vulcanized method
Defect is introduced in layer, obtains the sulphur selenizing molybdenum-carbon nano tube compound material with more exposure active sites.Prepared by the present invention
Sulphur selenizing molybdenum-carbon nano tube compound material is expected to as a kind of promising high performance electrode material, in electrochemical decomposition water, lithium
The energy fields such as ion battery, ultracapacitor are widely used.
A kind of sulphur selenizing molybdenum/carbon nano tube compound material of the present invention, it is characterised in that:The sulphur selenizing molybdenum/carbon nanometer
Pipe composite material is the uniform enveloped carbon nanometer tube of sulphur selenizing molybdenum nanometer sheet.
A kind of preparation method of sulphur selenizing molybdenum/carbon nano tube compound material of the present invention, including:
(1) carbon nanotube is dispersed in acid solution, is stirred, centrifuge washing, it is dry, obtain the carbon nanotube of acid processing;
(2) in organic solvent by the carbon nanotube dispersion of above-mentioned acid processing, ultrasound obtains carbon nano tube dispersion liquid;
(3) selenium powder is dissolved in hydrazine hydrate, stirs, obtains selenium-hydrazine hydrate mixed liquor;
(4) molybdate is soluble in water, ultrasonic disperse obtains molybdate dispersion liquid;
(5) by above-mentioned carbon nano tube dispersion liquid, selenium-hydrazine hydrate mixed liquor, molybdate dispersion liquid, mixing carries out solvent heat
Reaction, reaction temperature are 160-220 DEG C, and reaction time 10-48h is washed out, dry, and it is multiple to obtain selenizing molybdenum/carbon nanotube
Condensation material;
(6) it is 1 by mass ratio:2-1:6 selenizing molybdenum/carbon nanotube is ground with sulphur powder, then in inert gas item
Under part, 250-650 DEG C of vulcanization reaction 0.5-4h is to get sulphur selenizing molybdenum/carbon nano tube compound material.
It is 4 that acid solution, which is volume ratio, in the step (1):1-1:10 concentrated sulfuric acid and the mixed liquor of concentrated nitric acid, wherein it is preferred that
Volume ratio is 3:1-1:1;
Carbon nanotube is dispersed in a concentration of 10-100mg/mL in acid solution, preferably 20-40mg/mL.
Under the conditions of stirring is 60-120 DEG C in the step (1), it is stirred to react 1-24h.
It is preferred that:Stirring is 70-90 DEG C, under the conditions of, it is stirred to react 6-12h.
Organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- crassitudes in the step (2)
One kind in ketone;A concentration of 0.1-5mg/mL of carbon nano tube dispersion liquid, preferably 1-2mg/mL;The volume of carbon nano tube dispersion liquid
It is preferred that 10-50mL.
In the step (3) in selenium-hydrazine hydrate mixed liquor, a concentration of 0.5-6mg/mL of selenium, preferably 1-4mg/mL;Hydration
The preferred 10-30mL of volume of hydrazine.
Molybdate is ammonium molybdate, sodium molybdate, magnesium molybdate and zinc molybdate etc., preferably sodium molybdate in the step (4).
Sodium molybdate need to be only completely dissolved by the dosage of aqueous solvent in step (4).
The mass ratio of carbon nanotube and selenium powder is 1 in step (5):1-1:3, the molar ratio of molybdate and selenium is 1:2.
Solvent thermal reaction is in the step (5):It carries out in a kettle, preferably:Reaction temperature is 180-200 DEG C, instead
It is 12-24h between seasonable.
Selenizing molybdenum-carbon nano tube compound material and the mass ratio of sulphur powder are preferably 1 in step (6):4.
Inert gas is high-purity argon gas or high pure nitrogen in the step (6);It is preferred that:Reaction temperature is 350-550 DEG C, when
Between be 1-3h.
A kind of application of sulphur selenizing molybdenum/carbon nano tube compound material of the present invention, sulphur selenizing molybdenum-carbon nano tube compound material
Application in electro-catalysis water decomposition device, lithium ion battery, ultracapacitor.
It is prepared by the present invention:Nitration mixture handles carbon nanotube;By solvent-thermal method, growth in situ selenizing molybdenum obtains on the carbon nanotubes
To selenizing molybdenum-carbon nano tube compound material;Reaction is replaced by high temperature and realizes doping of the sulphur to selenizing molybdenum nanometer sheet, obtains sulphur selenium
Change molybdenum-carbon nano tube compound material.
A kind of novel sulphur selenizing molybdenum/carbon nano tube compound material is prepared by simple technological design in the present invention.
The composite material has following advantage:(1) oxygen-containing functional group that the carbon nano tube surface of acid processing is rich in can be that selenizing molybdenum carries
For more growing site, effectively inhibits reunion and the stacking of selenizing molybdenum, selenizing molybdenum nanometer sheet is made to expose more active edges
Edge site;(2) the excellent electric conductivity of carbon nanotube is conducive to the transmission of electronics, promotes faster evolving hydrogen reaction dynamics, bright
It is aobvious to reduce overpotential;(3) sulfur doping is realized by high temperature method of replacing, so that sulphur is occupied catalytic activity edge, can effectively reduces hydrogen
Gibbs free energy is adsorbed, while causing point defect at edge, the catalytic activity of electrode material can be significantly improved;(4) the sulphur selenium
The specific surface area of bigger can be provided by changing the multilevel hierarchy of molybdenum-carbon nano tube compound material, be conducive to the entrance of electrolyte, can be bright
It is aobvious to improve electrode material surface proton and interelectric transmittability, show superior electrochemistry Hydrogen Evolution Performance.Therefore, will
Selenizing molybdenum and carbon nanotube progress are effectively compound, can realize good synergistic effect between the two, and regulate and control it by sulfur doping
Electronic structure, to prepare sulphur selenizing molybdenum-carbon nano tube compound material of electrochemical performance.
Institute of the present invention is characterized using scanning electron microscope (SEM), X-ray diffractometer (XRD) and electrochemical workstation
The structure and morphology and electrochemistry catalytic activity of hydrogen evolution, result of sulphur selenizing molybdenum-carbon nano tube compound material obtained are as follows:
(1) SEM test results show:Prepared sulphur selenizing molybdenum-carbon nano tube compound material has unique multistage knot
Structure, sulphur selenizing molybdenum homoepitaxial is on the carbon nanotubes.In sulphur selenizing molybdenum-carbon nano tube compound material, the high ratio of carbon nanotube
The functional group that surface area and surface are rich in provides more growth sites for sulphur selenizing molybdenum, makes sulphur selenizing molybdenum nanometer sheet equably
Cladding on the carbon nanotubes, inhibits the reunion of sulphur selenizing molybdenum itself, to make the sulphur selenizing molybdenum nanoscale twins with catalytic activity
Edge adequately exposed.
(2) XRD test results show that diffraction maximum of the carbon nanotube at 2 θ=25.8,43.4 ° corresponds respectively to it
(002), (100) crystal face.Diffraction maximum of the selenizing molybdenum at 2 θ=13.4,32.9 and 56.7 ° corresponds respectively to hexagonal structure 2H phases
(002) of selenizing molybdenum, (100) and (110) crystal face.Prepared intermediate selenizing molybdenum-carbon nano tube compound material is shown
The characteristic peak of selenizing molybdenum illustrates that selenizing molybdenum nanometer sheet is successfully carried in carbon nanotube;And (002) of selenizing molybdenum nanometer sheet is brilliant
Face is weakened, and shows that the presence of carbon nanotube inhibits the stacking of selenizing molybdenum nanometer sheet and its crystallinity is poor.By selenizing molybdenum-
After carbon nano tube compound material is reacted with sulphur progress high temperature displacement, the diffraction maximum at 2 θ=56.6 ° moves to 57.8 °, is attributed to
The radius of sulphur atom is less than selenium atom, so that sulphur selenizing molybdenum crystal structure is finer and close after sulphur substitution.
(3) Electrochemical results show compared with single selenizing molybdenum, selenizing molybdenum-carbon nano tube compound material performance
Go out apparent excellent catalytic activity for hydrogen evolution, starting overpotential is 150mV, and current density can reach at η=200mV
10mA/cm2, it is attributed to molybdenum sulfide nanometer sheet and is evenly coated in carbon nanotube, it is suppressed that and the reunion of selenizing molybdenum nanometer sheet itself,
To expose more selenizing molybdenum activity edges.After selenizing molybdenum-carbon nano tube compound material is realized part sulfur doping, sulphur selenizing
The electro catalytic activity of molybdenum/carbon nano tube compound material has a further raising, and starting overpotential only has 120mV, and η=
Current density can reach 10mA/cm under 170mV2, this may be attributed in sulphur selenizing molybdenum/carbon nano tube compound material, and sulphur accounts for
According to catalytic activity edge, hydrogen absorption Gibbs free energy can be effectively reduced, makes proton be easier to be adsorbed on electrode material surface, together
When at edge cause point defect, the catalytic activity of electrode material itself can be obviously improved.
Advantageous effect
(1) preparation process of the present invention is simple, easily operated, is a kind of effective efficiently preparation method;
(2) experimental design is ingenious:
First, the substrate of the sulphur selenizing molybdenum growth of selection is carbon nanotube, the official that unique draw ratio is rich in surface
It can roll into a ball and impart its high specific surface area, the growth for sulphur selenizing molybdenum nanometer sheet provides more sites, and sulphur selenizing molybdenum is made to receive
Rice piece is uniformly coated in carbon nanotube, inhibits the reunion of sulphur selenizing molybdenum itself, to make the sulphur selenizing with catalytic activity
The edge of molybdenum nanometer sheet is adequately exposed;And carbon nanotube has excellent electric conductivity, during making electrochemical catalysis
Electronics and ion can be transmitted efficiently and effectively, can further improve the catalytic hydrogen evolution activity of sulphur selenizing molybdenum;
Second, realize that sulphur receives selenizing molybdenum in intermediate selenizing molybdenum-carbon nano tube compound material by high temperature method of replacing
The Effective Doping of rice piece, makes a certain number of sulphur atoms occupy catalytic activity edge, effectively reduces hydrogen and adsorbs Gibbs free energy,
Cause point defect at sulphur selenizing molybdenum nanometer sheet edge simultaneously, the catalytic activity of electrode material itself can be obviously improved;
Third realizes quasi one-dimensional material carbon nanotube by simple solvent thermal process and is received with two-dimensional material sulphur selenizing molybdenum
Rice piece it is compound, build with hierarchical structure sulphur selenizing molybdenum-carbon nano tube compound material, composite material bigger can be provided
Specific surface area is conducive to the entrance of electrolyte ion, can significantly improve material surface substance and interelectric transmittability, show
Go out superior electrochemistry Hydrogen Evolution Performance;
Therefore, sulphur selenizing molybdenum and carbon nanotube progress is effectively compound, it can realize good synergistic effect between the two so that
The advantage of the two is given full play to, to prepare sulphur selenizing molybdenum-carbon nano tube compound material of electrochemical performance;
(3) sulphur selenizing molybdenum-carbon nano tube compound material prepared by the present invention is expected to as a kind of promising high-performance
Electrode material is widely used in energy fields such as liberation of hydrogen catalyst, lithium ion battery, ultracapacitors.
Description of the drawings
Fig. 1 is the SEM figures of sulphur selenizing molybdenum-carbon nano tube compound material in embodiment 1;
Fig. 2 is the XRD diagram of sulphur selenizing molybdenum-carbon nano tube compound material in the present invention;
Fig. 3 is the linear voltammetric scan curve of sulphur selenizing molybdenum-carbon nano tube compound material in embodiment 1;
Fig. 4 is the linear volt-ampere of sulphur selenizing molybdenum-carbon nano tube compound material prepared by different states of cure (vulcanization) in the present invention
Scanning curve.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) 3g carbon nanotubes are dispersed in the 100mL concentrated sulfuric acids-concentrated nitric acid (volume ratio 2:1) in mixed solution, at 80 DEG C
At a temperature of be stirred to react 8h, obtain acid processing carbon nanotube mixed acid solution;
(2) it waits for that carbon nanotube mixed acid solution is cooled to room temperature, is centrifuged, respectively washed twice with deionized water and ethyl alcohol,
It is dry in 50 DEG C of vacuum drying ovens, obtain the carbon nanotube powder of acid processing;
(3) carbon nanotube powder that 50mg acid is handled is scattered in 25mL n,N-Dimethylformamide, when one section ultrasonic
Between, obtain the organic dispersions of carbon nanotube;
(4) 50mg selenium powders are dissolved in 25mL hydrazine hydrates, stirring a period of time, are allowed to be uniformly dispersed;
(5) 76.61mg sodium molybdates are dissolved in 0.2mL water, ultrasound is allowed to fully dissolve, and is allowed to be uniformly dispersed;
(6) mixed liquor containing carbon nanotube, molybdate, selenium and hydrazine hydrate is poured into 100mL water heating kettles, at 180 DEG C
Lower solvent thermal reaction 12h is to get to selenizing molybdenum-carbon nano tube compound material;
(7) selenizing being prepared molybdenum-carbon nano tube compound material deionized water and ethyl alcohol are respectively washed twice, so
It is dry in 50 DEG C of vacuum drying ovens afterwards, obtain selenizing molybdenum-carbon nano tube compound material powder;
(8) by 50mg selenizings molybdenum-carbon nano tube compound material powder and sublimed sulfur in mass ratio 1:4 grindings make it uniformly
Mixing, 450 DEG C of reaction 2h, obtain sulphur selenizing molybdenum-carbon nano tube compound material under nitrogen gas protection.
Embodiment 2
(1) 3g carbon nanotubes are dispersed in the 100mL concentrated sulfuric acids-concentrated nitric acid (volume ratio 2:1) in mixed solution, at 80 DEG C
At a temperature of be stirred to react 8h, obtain acid processing carbon nanotube mixed acid solution;
(2) it waits for that carbon nanotube mixed acid solution is cooled to room temperature, is centrifuged, respectively washed twice with deionized water and ethyl alcohol,
It is dry in 50 DEG C of vacuum drying ovens, obtain the carbon nanotube powder of acid processing;
(3) carbon nanotube powder that 50mg acid is handled is scattered in 25mL n,N-Dimethylformamide, when one section ultrasonic
Between, obtain the organic dispersions of carbon nanotube;
(4) 50mg selenium powders are dissolved in 25mL hydrazine hydrates, stirring a period of time, are allowed to be uniformly dispersed;
(5) 76.61mg sodium molybdates are dissolved in 0.2mL water, ultrasound is allowed to fully dissolve, and is allowed to be uniformly dispersed;
(6) mixed liquor containing carbon nanotube, molybdate, selenium and hydrazine hydrate is poured into 100mL water heating kettles, at 180 DEG C
Lower solvent thermal reaction 12h is to get to selenizing molybdenum-carbon nano tube compound material;
(7) selenizing being prepared molybdenum-carbon nano tube compound material deionized water and ethyl alcohol are respectively washed twice, so
It is dry in 50 DEG C of vacuum drying ovens afterwards, obtain selenizing molybdenum-carbon nano tube compound material powder;
(8) by 50mg selenizings molybdenum-carbon nano tube compound material powder and sublimed sulfur in mass ratio 1:2 grindings make it uniformly
Mixing, 450 DEG C of reaction 2h, obtain sulphur selenizing molybdenum-carbon nano tube compound material under nitrogen gas protection.
Embodiment 3
(1) 3g carbon nanotubes are dispersed in the 100mL concentrated sulfuric acids-concentrated nitric acid (volume ratio 2:1) in mixed solution, at 80 DEG C
At a temperature of be stirred to react 8h, obtain acid processing carbon nanotube mixed acid solution;
(2) it waits for that carbon nanotube mixed acid solution is cooled to room temperature, is centrifuged, respectively washed twice with deionized water and ethyl alcohol,
It is dry in 50 DEG C of vacuum drying ovens, obtain the carbon nanotube powder of acid processing;
(3) carbon nanotube powder that 50mg acid is handled is scattered in 25mL n,N-Dimethylformamide, when one section ultrasonic
Between, obtain the organic dispersions of carbon nanotube;
(4) 50mg selenium powders are dissolved in 25mL hydrazine hydrates, stirring a period of time, are allowed to be uniformly dispersed;
(5) 76.61mg sodium molybdates are dissolved in 0.2mL water, ultrasound is allowed to fully dissolve, and is allowed to be uniformly dispersed;
(6) mixed liquor containing carbon nanotube, molybdate, selenium and hydrazine hydrate is poured into 100mL water heating kettles, at 180 DEG C
Lower solvent thermal reaction 12h is to get to selenizing molybdenum-carbon nano tube compound material;
(7) selenizing being prepared molybdenum-carbon nano tube compound material deionized water and ethyl alcohol are respectively washed twice, so
It is dry in 50 DEG C of vacuum drying ovens afterwards, obtain selenizing molybdenum-carbon nano tube compound material powder;
(8) by 50mg selenizings molybdenum-carbon nano tube compound material powder and sublimed sulfur in mass ratio 1:6 grindings make it uniformly
Mixing, 450 DEG C of reaction 2h, obtain sulphur selenizing molybdenum-carbon nano tube compound material under nitrogen gas protection.
Claims (9)
1. a kind of preparation method of sulphur selenizing molybdenum/carbon nano tube compound material, including:
(1) carbon nanotube is dispersed in acid solution, is stirred, centrifuge washing, it is dry, obtain the carbon nanotube of acid processing;
(2) in organic solvent by the carbon nanotube dispersion of above-mentioned acid processing, ultrasound obtains carbon nano tube dispersion liquid;
(3) selenium powder is dissolved in hydrazine hydrate, stirs, obtains selenium-hydrazine hydrate mixed liquor;
(4) molybdate is soluble in water, ultrasonic disperse obtains molybdate dispersion liquid;
(5) by above-mentioned carbon nano tube dispersion liquid, selenium-hydrazine hydrate mixed liquor, molybdate dispersion liquid, mixing carries out solvent thermal reaction,
Reaction temperature is 160-220 DEG C, and reaction time 10-48h is washed out, dry, obtains selenizing molybdenum/carbon nanotube composite
Material;
(6) it is 1 by mass ratio:2-1:6 selenizing molybdenum/carbon nanotube is ground with sulphur powder, then under inert gas conditions,
250-650 DEG C of reaction 0.5-4h is to get sulphur selenizing molybdenum/carbon nano tube compound material.
2. a kind of preparation method of sulphur selenizing molybdenum/carbon nano tube compound material according to claim 1, it is characterised in that:
It is 4 that acid solution, which is volume ratio, in the step (1):1-1:10 concentrated sulfuric acid and the mixed liquor of concentrated nitric acid;Carbon nanotube is dispersed in acid
A concentration of 10-100mg/mL in liquid.
3. a kind of preparation method of sulphur selenizing molybdenum/carbon nano tube compound material according to claim 1, it is characterised in that:
Under the conditions of stirring is 60-120 DEG C in the step (1), it is stirred to react 1-24h.
4. a kind of preparation method of sulphur selenizing molybdenum/carbon nano tube compound material according to claim 1, it is characterised in that:
Organic solvent is one in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone in the step (2)
Kind;The volume of a concentration of 0.1-5mg/mL of carbon nano tube dispersion liquid, carbon nano tube dispersion liquid are 10-50mL.
5. a kind of preparation method of sulphur selenizing molybdenum/carbon nano tube compound material according to claim 1, it is characterised in that:
In the step (3) in selenium-hydrazine hydrate mixed liquor, the volume of a concentration of 0.5-6mg/mL of selenium, hydrazine hydrate are 10-30mL.
6. a kind of preparation method of sulphur selenizing molybdenum/carbon nano tube compound material according to claim 1, it is characterised in that:
The mass ratio of carbon nanotube and selenium powder is 1 in step (5):1-1:3, the molar ratio of molybdate and selenium powder is 1:2.
7. a kind of preparation method of sulphur selenizing molybdenum/carbon nano tube compound material according to claim 1, it is characterised in that:
Solvent thermal reaction is in the step (5):It carries out in a kettle, reaction temperature is 180-200 DEG C, reaction time 12-
24h。
8. a kind of preparation method of sulphur selenizing molybdenum/carbon nano tube compound material according to claim 1, it is characterised in that:
Inert gas is high-purity argon gas or high pure nitrogen in the step (6);Reaction temperature is 350-550 DEG C, time 1-3h.
9. a kind of application of sulphur selenizing molybdenum/carbon nano tube compound material as described in claim 1, it is characterised in that:Sulphur selenizing
Application of the molybdenum-carbon nano tube compound material in electro-catalysis water decomposition device, lithium ion battery, ultracapacitor.
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