CN109273726A - A kind of carbon coated air electrode material and its preparation method and application - Google Patents
A kind of carbon coated air electrode material and its preparation method and application Download PDFInfo
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- CN109273726A CN109273726A CN201810972331.XA CN201810972331A CN109273726A CN 109273726 A CN109273726 A CN 109273726A CN 201810972331 A CN201810972331 A CN 201810972331A CN 109273726 A CN109273726 A CN 109273726A
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- carbon
- electrode material
- air electrode
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- carbon nanotube
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 84
- 239000007772 electrode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 131
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 74
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 238000012545 processing Methods 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 20
- 238000006557 surface reaction Methods 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 11
- 239000011609 ammonium molybdate Substances 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 13
- 229910052961 molybdenite Inorganic materials 0.000 abstract description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000010148 water-pollination Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001323 Li2O2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- -1 carbon nano tube compound Chemical class 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- 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
- Y02E60/50—Fuel cells
Abstract
The present invention relates to electrode fields, in particular to a kind of carbon coated air electrode material and its preparation method and application.By using MoS2Enveloped carbon nanometer tube not only can be improved the chemical stability of CNTs, but also show good catalytic activity to ORR and OER, will not reduce the high conductivity of CNTs.The MS-CNTs cathode shows high specific capacity and low charging potential and excellent cyclicity.This clad structure also preferably inhibits the contact between CNTs and electrolyte and discharging product.Such a unique structure provides high discharge capacity, good cyclical stability for actual industrial manufacture, and simply, the preparation and design of inexpensive and other similar clad structure provide scheme.
Description
Technical field
The present invention relates to electrode field, in particular to a kind of carbon coated air electrode material and preparation method thereof and
Using.
Background technique
Energy crisis and environmental pollution are the two big challenges that modern society faces.From the perspective of sustainable development, the world
It is badly in need of stepping up to explore environmentally protective renewable new energy in various countries.But since these renewable energy cannot continuously and steadily
Applied in daily life, so needing to design and developing corresponding energy storage system, so that it is become available for people and continue benefit
The energy.In a variety of different electric storage systems, secondary cell is considered as a kind of most effective, simple, reliable system,
It can be directly realized by the mutual conversion of electric energy and chemical energy.Most widely used at present is lithium ion battery, but low energy
Metric density (theoretical value about 400Wh/kg) limits its application in next-generation high-performance energy-storage system.And metal-air is electric
Pond have open architecture, participate in anode reaction active material --- oxygen can continue to obtain from the air of surrounding, not need to store up
It deposits in the battery, thus there is very high theoretical energy density.
Wherein, the theoretical energy density of lithium-air battery is up to 3505Wh/kg and (is based on ), it is
More than 10 times of commercial lithium-ion batteries energy density at present, it is considered to be one of most potential energy storage system,
The extensive concern of basic research and application field is attracted.
Although having carried out a large amount of research work around lithium-air battery, many critical issues do not obtain thoroughly yet
It solves.In lithium-air battery electric discharge and charging process, positive hydrogen reduction and the high overpotential of oxygen evolution reaction are substantially reduced
The energy efficiency and cycle performance of battery causes it to be not met by the demand of commercialization energy storage system.Largely grind
Study carefully the result shows that, the addition of catalyst can be effectively reduced air electrode reaction overpotential, and then improve battery performance.Cause
This, the exploitation of efficient, stable, cheap catalyst has vital effect to the development of lithium-air battery.
The catalyst being most widely used in LABs at present is carbon-based material (such as carbon nanotube CNTs), but its is unstable
Property, to Li2O2The problems such as catalytic activity and promotion electrolyte of difference are decomposed causes the cycle performance of LABs to significantly reduce, this makes
Carbon-based material is not the selection of the ideal cathodes of LABs.Therefore, the stable and reversible carbon cathode of building or searching substitution cathode
It is top priority to avoid the side reaction for being related to carbon-based material.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of carbon coated air electrode material and preparation method thereof and answering
With.
To achieve the goals above, technical solution used in the embodiment of the present invention is as follows:
A kind of preparation method of carbon coated air electrode material, by surface functionalized carbon nanotube/detergent alkylate
After sodium sulfonate solution ultrasonic treatment, hydro-thermal reaction is carried out with ammonium molybdate, thiocarbamide, controls 200 DEG C of hydrothermal temperature, heating reaction
The carbon coated air electrode material of molybdenum sulfide enveloped carbon nanometer tube is made in 24~36h of time, filtration washing, vacuum drying, wherein
The surface functionalization of carbon nanotube is the inert gas environment annealing at 550~600 DEG C, then is handled in the nitric acid of 70%w/w,
It is dried in vacuum overnight.
A kind of preparation method of carbon coated air electrode material, comprising the following steps: by the carbon of surface functionalized processing
After nanotube and dispersant are uniform, be used to prepare the sulphur source material of molybdenum sulfide 180~220 DEG C of hydro-thermal reactions 24~
After 36h, washing, vacuum drying；Wherein, functionalization processing is that carbon nanotube is annealed in inert gas environment and/or receives carbon
Mitron carries out acidic treatment.
A kind of carbon coated air electrode material is made using the preparation method of such as above-mentioned carbon coated air electrode material.
A kind of such as application of the above-mentioned carbon coated air electrode material in lithium-air battery.
The beneficial effects of the present invention are:
The preparation method of a kind of carbon coated air electrode material provided by the invention, by carrying out surface official to carbon nanotube
Energyization processing effectively improves the fault of construction on the surface of carbon nanotube, reduces the inhomogeneities of its structure, improves carbon nanometer
The hydrophily of pipe, to provide advantageous guarantee for subsequent acquisition carbon coated air electrode material of good performance.Pass through control
The reaction raw materials of hydro-thermal reaction carry out ultrasonic mixing to each reaction raw materials before hydro-thermal reaction, and control hydro-thermal reaction
The carbon coated air electrode material with excellent chemical property has been made in reaction temperature and reaction time.
A kind of carbon coated air electrode material provided by the invention, MoS2The chemical stability of CNTs not only can be improved,
Good catalytic activity is shown to ORR and OER, and the high conductivity of CNTs will not be reduced.MS-CNTs cathode shows height
Specific capacity and low charging potential and excellent cyclicity (in 100mAg-1Current density under recycle 50 times or more).This
This clad structure of invention preparation also preferably inhibits the contact between CNTs and electrolyte and discharging product.It is such a
Unique structure for actual industrial manufacture provide high discharge capacity, good cyclical stability, simply, low cost and other
The preparation and design of similar clad structure provide scheme.
It is provided by the invention a kind of such as application of the above-mentioned carbon coated air electrode material in lithium-air battery.Molybdenum sulfide
Enveloped carbon nanometer tube has high specific capacity and low charging potential, Yi Jiyou on the cathode material for be applied to lithium-air battery
The cycle performance of benefit.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is that the BET of carbon coated air electrode material provided in an embodiment of the present invention schemes；
Fig. 2 is that the SEM of carbon coated air electrode material provided in an embodiment of the present invention schemes；
Fig. 3 is that the TEM of carbon coated air electrode material provided in an embodiment of the present invention schemes；
Fig. 4 is the XRD diagram of carbon coated air electrode material provided in an embodiment of the present invention；
Fig. 5 is the first charge-discharge figure of carbon coated air electrode material provided in an embodiment of the present invention；
Fig. 6 is the cycle charge discharge electrograph of carbon coated air electrode material provided in an embodiment of the present invention.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
In the description of the present invention, it should be noted that term " first ", " second " etc. are only used for distinguishing description, without
It can be interpreted as indication or suggestion relative importance.
A kind of carbon coated air electrode material of the embodiment of the present invention and its preparation method and application is carried out below specific
Explanation.
A kind of preparation method of carbon coated air electrode material provided in an embodiment of the present invention, comprising:
S1, processing is functionalized to the surface of carbon nanotube.
Carbon atom is in carbon nanotube with sp2Based on hydridization, while there are a degree of bending, shapes for hexangle type network
At Space expanding, wherein certain sp can be formed3Hybrid bond, that is, the chemical bond formed while having sp2And sp3It mixes miscellaneous
Change state, and these p tracks overlap each other and form the delocalized big pi bond of height outside carbon nanotube graphene sheet layer, carbon nanometer
The big pi bond of tube outer surface is carbon nanotube and some chemical fundamentals for having the macromolecular for being conjugated performance compound with non-covalent bond.
Its surface, which is all combined with certain functional group, to be shown to the photoelectron spectroscopy result of study of carbon nanotube, especially
It is that multi-wall carbon nano-tube pipe surface vivaciously much will be combined with a large amount of surface group, such as carboxyl.This leads to carbon nano tube surface
Defect and chemical reactivity enhancing, surface chemical structure tend to complicate.The chemical structure of internal layer carbon atom is relatively simple, outside
The chemical composition of layer carbon atom is more complicated, and a large amount of amorphous carbon is often deposited on outer layer carbon atom.Due to having
The inhomogeneities of physical structure and chemical structure, a large amount of surface carbon atom has different surface microenvironments in carbon nanotube,
Therefore also with the inhomogeneity of energy.
It therefore,, can be effectively after being functionalized processing by the surface to above-mentioned carbon nanotube in the present embodiment
The fault of construction for improving the surface of carbon nanotube, reduces the inhomogeneities of its structure, and then can effectively improve carbon nanotube
Hydrophily, to obtain carbon coated air electrode material of good performance to be subsequent and provide advantageous guarantee.
Further, in the present embodiment, being functionalized processing to the surface of carbon nanotube is by carbon nanotube lazy
Property gaseous environment annealing and/or carbon nanotube is subjected to acidic treatment.
Specifically, processing is functionalized by the way of annealing to the surface of carbon nanotube, is in inert gas environment
Lower annealing.
It is functionalized processing in such a way that the surface to carbon nanotube is using annealing, carbon nanometer can be effectively removed
The surface of pipe metal impurities that may be present.And by annealing, so that the amorphous carbon on the surface of carbon nanotube is changed into crystalline state
Carbon to achieve the effect that crystallization, and then can effectively improve the hydrophily of carbon nanotube, thus good for subsequent acquisition performance
Good carbon coated air electrode material provides advantageous guarantee.
Still optionally further, it anneals in Ar environment.
It should be understood that in other of the invention optional embodiments, also can choose other inertia applicatory of this field its
He makes annealing treatment the surface of carbon nanotube.
Further, when annealing in an inert atmosphere, annealing time selects 1.8~2h.
Further, when annealing in an inert atmosphere, annealing temperature selects 550~600 DEG C.
In other optional embodiments, the above-mentioned surface to carbon nanotube, which is functionalized processing, be can choose to carbon
Nanotube carries out acidic treatment.
Further, in the present embodiment, by carbon nanotube progress acidic treatment be in concentrated nitric acid ultrasonic treatment 1~
1.5 hour.
It should be understood that carbon nanotube progress acidic treatment can choose this field in the embodiment of other choosings of the present invention
Other common acid with strong oxidizing property are handled.
Optionally, the selection concentrated sulfuric acid carries out acidic treatment to carbon nanotube.
Acidic treatment, which is carried out, by the surface to carbon nanotube enables to carbon using the strong oxidizing property of acid with strong oxidizing property
The amorphous carbon of nanotube surface is changed into crystalline state carbon, to improve the crystallization degree of carbon nanotube, and then can effectively mention
The hydrophily of high carbon nanotube, to provide advantageous guarantee for subsequent acquisition carbon coated air electrode material of good performance.
Still optionally further, the concentration of above-mentioned concentrated nitric acid is selected as 70%w/w.
Further, in other optional embodiments of the invention, processing is functionalized to the surface of carbon nanotube,
It can choose and carry out acidic treatment combination processing using in inert gas environment annealing and by carbon nanotube.
Specifically, first carbon nanotube is made annealing treatment, then the carbon nanotube by annealing is carried out at acidity
Reason.
Still optionally further, the surface functionalization of carbon nanotube is the inert gas environment annealing at 550~600 DEG C, then
It is handled in acid with strong oxidizing property.
Further alternative, above-mentioned inert gas selects argon gas, and above-mentioned acid with strong oxidizing property selects concentrated nitric acid, specifically
Ground, concentration 70%w/w.
Further, the surface functionalization processing of carbon nanotube is also dried in vacuo.Vacuum drying temperature be 55~
60℃。
Specifically, when selecting to handle the surface functionalization of carbon nanotube by the way of annealing, after annealing, also
Washing drying is carried out, the impurity on surface is further removed.
Further, when selection is handled the surface functionalization of carbon nanotube by the way of acidic treatment, at acidity
After reason, washing drying is also carried out, further removes the impurity on surface.
Since using after acidic treatment, the surface of carbon nanotube can remain acid solution, residual acid solution can be removed by washing.
Further, the remaining excessive moisture of carbon nano tube surface can be removed by vacuum drying, and then guarantees the parent of carbon nanotube
It is aqueous, to provide advantageous guarantee for subsequent acquisition carbon coated air electrode material of good performance.
Further alternative, the above-mentioned vacuum drying time can choose overnight.Processing can be to carbon nanotube overnight
Surface functionalization processing has facilitation.Extra moisture and a small amount of remaining nitre that do not wash off can be further removed overnight
Acid.
Further, it when selecting to handle by the way of annealing and acidic treatment superposition, after annealing, carries out acid
Processing, then washed, vacuum drying treatment, to remove the remaining excessive moisture of carbon nano tube surface, and then guarantee that carbon is received
The hydrophily of mitron, to provide advantageous guarantee for subsequent acquisition carbon coated air electrode material of good performance.
It is S2, the carbon nanotube of surface functionalized processing and dispersant is uniform.
By the way that the carbon nanotube of above-mentioned surface functionalized processing and dispersant is uniform, can be effectively prevented from
The problem of carbon nanotube is reunited, to effectively guarantee that subsequent acquisition carbon coated air electrode material of good performance provides
Advantageous guarantee.
Further, dispersing agent is selected from neopelex solution or cetyl trimethylammonium bromide solution.
Further, the carbon nanotube of surface functionalized processing and dispersant are uniformly used to the side of ultrasonic disperse
Formula is dispersed.
Still optionally further, the carbon nanotube of surface functionalized processing and dispersant are uniformly used into ultrasonic disperse
Mode when being dispersed, sonication treatment time is 1~1.5h.
By selecting ultrasonic disperse, effectively the mixed solution of carbon nanotube and dispersing agent can be uniformly dispersed.
Still optionally further, the concentration of the mixed solution of above-mentioned carbon nanotube and dispersing agent is 0.2%w/w.
S3, the mixed solution of carbon nanotube and dispersing agent and the sulphur source material of molybdenum sulfide will be used to prepare at 180~220 DEG C
24~36h of hydro-thermal reaction.
Further, before hydro-thermal reaction, also by the mixed solution sonication treatment time of carbon nanotube and dispersing agent be 1~
1.5h。
Further, before hydro-thermal reaction, also by the mixed solution of carbon nanotube and dispersing agent and the sulphur of molybdenum sulfide is prepared
Source material is add to deionized water 30~45min of ultrasonic treatment.
So as to which each raw material of hydro-thermal reaction to be uniformly mixed, and then for follow-up hydrothermal react to obtain comprehensive performance good
Good carbon nano tube compound material provides advantageous guarantee.
Further, sulphur source material includes at least one of ammonium molybdate or sodium molybdate；And it is thiocarbamide, sulphur powder, thio
At least one of acetamide or vulcanized sodium.
Optionally, after surface functionalized carbon nanotube/neopelex solution being ultrasonically treated, with molybdenum
Sour ammonium, thiocarbamide carry out hydro-thermal reaction.Further, the mass ratio between carbon nanotube and ammonium molybdate, thiocarbamide is 5:19:21.
Ultrasonic mixing is carried out by controlling the reaction raw materials of hydro-thermal reaction, before hydro-thermal reaction to each reaction raw materials, with
And reaction temperature and the reaction time of control hydro-thermal reaction, thus be effectively guaranteed follow-up hydrothermal react to obtain comprehensive performance it is good
Good carbon nano tube compound material.
S4, the product that hydro-thermal reaction obtains is washed, is dried in vacuo.
Further, by washing, impurity can be removed.By vacuum drying, the remaining water of surface can be removed
Point, guarantee its good performance.
Further, vacuum drying temperature is 55~60 DEG C.
Some embodiments of the present invention also provide a kind of carbon coated air electrode material, empty using such as above-mentioned carbon coated
The preparation method of gas electrode material is made.In the carbon coated air electrode material, molybdenum sulfide MoS2It not only can be improved CNTs's
Chemical stability shows good catalytic activity to oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and will not drop
The high conductivity of low CNTs.MS-CNTs cathode shows high specific capacity and low charging potential and excellent cyclicity
(in 100mAg-1Current density under recycle 50 times or more).This clad structure also preferably inhibit CNTs and electrolyte and
Contact between discharging product.Such a unique structure provides high discharge capacity for actual industrial manufacture, good follows
Ring stability, simply, the preparation and design of inexpensive and other similar clad structure provide scheme.
Some embodiments of the present invention also provide a kind of if above-mentioned carbon coated air electrode material is in lithium-air battery
In application.Molybdenum sulfide enveloped carbon nanometer tube is on the cathode material for be applied to lithium-air battery with high specific capacity and low
Charging potential and beneficial cycle performance.
Feature and performance of the invention are described in further detail with reference to embodiments:
Embodiment 1
The present embodiment provides a kind of carbon coated air electrode materials, the preparation method is as follows:
1) surface functionalization of carbon nanotube (CNTs):
By a certain amount of CNTs at 550 DEG C (Ar) anneal 2h, then by sample in dense HNO3It is super in 60 DEG C in (70%w/w)
Sonication 1h is to further increase hydrophily.It is washed with deionized for several times, is dried in vacuum overnight at 60 DEG C later.
2) synthesis of MS-CNTs:
The CNTs of 200mg surface functionalization is dispersed in 1000ml neopelex (SDBS) solution (0.2%w/
W) in, it is ultrasonically treated 1h, it is spare as carbon source；
By 0.1mmol ammonium molybdate, 2.8mmol thiocarbamide and 25ml are added to 45ml deionization from the CNTs solution of step 1
In water and it is ultrasonically treated 30 minutes；
Then uniform solution is transferred in reaction kettle, and is heated for 24 hours at 200 DEG C.Simultaneously by black suspension filtering
It is washed with deionized for several times, it is then dry in vacuum drying oven.Finally obtain MS-CNTs.
Embodiment 2
The present embodiment provides a kind of carbon coated air electrode materials, the preparation method is as follows:
1) surface functionalization of carbon nanotube (CNTs):
By a certain amount of CNTs at 550 DEG C (Ar) anneal 2h, then by sample in dense HNO3It is super in 60 DEG C in (70%w/w)
Sonication 1.5h is to further increase hydrophily.It is washed with deionized for several times, is dried in vacuum overnight at 55 DEG C later.
2) synthesis of MS-CNTs:
The CNTs of 200mg surface functionalization is dispersed in 1000ml neopelex (SDBS) solution (0.2%w/
W) in, it is ultrasonically treated 1.5h, it is spare as carbon source.
By 0.1mmol ammonium molybdate, 2.5mmol thiocarbamide and 25ml are added to 45ml deionization from the CNTs solution of step 1
In water and it is ultrasonically treated 30 minutes.
Then uniform solution is transferred in reaction kettle, and is heated for 24 hours at 200 DEG C.Simultaneously by black suspension filtering
It is washed with deionized for several times, it is then dry in vacuum drying oven.Finally obtain MS-CNTs.
Embodiment 3
The present embodiment provides a kind of carbon coated air electrode materials, the preparation method is as follows:
1) surface functionalization of carbon nanotube (CNTs):
By a certain amount of CNTs at 600 DEG C (Ar) anneal 1.8h, then by sample in dense HNO3In 60 DEG C in (70%w/w)
1h is ultrasonically treated to further increase hydrophily.It is washed with deionized for several times, is dried in vacuum overnight at 60 DEG C later.
2) synthesis of MS-CNTs:
The CNTs of 200mg surface functionalization is dispersed in 1000ml neopelex (SDBS) solution (0.2%w/
W) in, it is ultrasonically treated 1h, it is spare as carbon source.
By 0.1mmol ammonium molybdate, 2.8mmol thiocarbamide and 25ml are added to 45ml deionization from the CNTs solution of step 1
In water and it is ultrasonically treated 45 minutes.
Then uniform solution is transferred in reaction kettle, and is heated for 24 hours at 200 DEG C.Simultaneously by black suspension filtering
It is washed with deionized for several times, it is then dry in vacuum drying oven.Finally obtain MS-CNTs.
Embodiment 4
The present embodiment provides a kind of carbon coated air electrode materials, the preparation method is as follows:
1) surface functionalization of carbon nanotube (CNTs):
By a certain amount of CNTs at 560 DEG C (Ar) anneal 1.8h, then by sample in the concentrated sulfuric acid (70%w/w) in 60 DEG C
1h is ultrasonically treated to further increase hydrophily.It is washed with deionized for several times, is dried in vacuum overnight at 60 DEG C later.
2) synthesis of MS-CNTs:
The CNTs of 200mg surface functionalization is dispersed in 1000ml cetyl trimethylammonium bromide (CTAB) solution
In (0.2%w/w), it is ultrasonically treated 1h, it is spare as carbon source.
By 0.1mmol sodium molybdate, 2.8mmol sulphur powder and 25ml are added to 45ml deionization from the CNTs solution of step 1
In water and it is ultrasonically treated 45 minutes.
Then uniform solution is transferred in reaction kettle, and heats 36h at 180 DEG C.Simultaneously by black suspension filtering
It is washed with deionized for several times, it is then dry in vacuum drying oven.Finally obtain MS-CNTs.
Embodiment 5
The present embodiment provides a kind of carbon coated air electrode materials, the preparation method is as follows:
1) surface functionalization of carbon nanotube (CNTs):
By a certain amount of CNTs at 560 DEG C (Ar) anneal 1.8h, then by sample in the concentrated sulfuric acid (70%w/w) in 60 DEG C
1h is ultrasonically treated to further increase hydrophily.It is washed with deionized for several times, is dried in vacuum overnight at 60 DEG C later.
2) synthesis of MS-CNTs:
The CNTs of 200mg surface functionalization is dispersed in 1000ml cetyl trimethylammonium bromide (CTAB) solution
In (0.2%w/w), it is ultrasonically treated 1h, it is spare as carbon source.
By ammonium molybdate and the total 0.1mmol of sodium molybdate, the CNTs solution of 2.8mmol thioacetamide and 25ml from step 1
It is added in 45ml deionized water and is ultrasonically treated 33 minutes.
Then uniform solution is transferred in reaction kettle, and heats 30h at 220 DEG C.Simultaneously by black suspension filtering
It is washed with deionized for several times, it is then dry in vacuum drying oven.Finally obtain MS-CNTs.
Embodiment 6
The present embodiment provides a kind of carbon coated air electrode materials, the preparation method is as follows:
1) surface functionalization of carbon nanotube (CNTs):
By a certain amount of CNTs at 560 DEG C (Ar) anneal 1.8h, then by sample in the concentrated sulfuric acid (70%w/w) in 60 DEG C
1h is ultrasonically treated to further increase hydrophily.It is washed with deionized for several times, is dried in vacuum overnight at 60 DEG C later.
2) synthesis of MS-CNTs:
The CNTs of 200mg surface functionalization is dispersed in 1000ml cetyl trimethylammonium bromide (CTAB) solution
In (0.2%w/w), it is ultrasonically treated 1h, it is spare as carbon source.
By 0.1mmol sodium molybdate, vulcanized sodium and thiocarbamide total 2.8mmol and 25ml are added from the CNTs solution of step 1
Into 45ml deionized water and it is ultrasonically treated 35 minutes.
Then uniform solution is transferred in reaction kettle, and heats 30h at 220 DEG C.Simultaneously by black suspension filtering
It is washed with deionized for several times, it is then dry in vacuum drying oven.Finally obtain MS-CNTs.
Its morphological structure and electrochemistry are investigated to carbon coated air electrode material made from embodiment 1-6 below
Energy.
Experimental example 1:
Carbon coated air electrode material made from embodiment 1-6 is investigated using the characterizing method of specific surface area test (BET)
Morphological structure.
As a result as shown in Figure 1.From figure 1 it appears that MS-CNTs has the IV thermoisopleth of H3 shape hysteresis loop, it was demonstrated that
Made sample has mesoporous property.Show the specific surface area of MS-CNTs by BET calculated result and pore volume is respectively
21.70m2g-1And 0.058cm3g-1).Therefore, obtained MS-CNTs has high-specific surface area and high pore volume, in air electricity
Active site abundant is provided in the reaction process of pole, improves the energy conversion efficiency of battery；And to be put in cyclic process
The formation and decomposition of electric product provide enough spaces, improve the cyclic reversibility of battery.
Experimental example 2:
The shape of carbon coated air electrode material made from embodiment 1-6 is investigated using the characterizing method of scanning electron microscope (SEM)
Looks structure feature.
As a result as shown in Figure 2.From figure 2 it can be seen that MS-CNTs is formed uniformly after adding CNTs in water-heat process
The flower-like nanometer spherical structure of distribution, and flower-like nanometer ball keeps the porous network structure of three-dimensional interconnection.This structure has rich
Rich porosity, can be catalyzed Li2O2Formation and decomposition in surface-active site are Li+And O2Effective transport provide and fill
The space of foot.It is expected that this unique porous spherical structure can keep the structural intergrity of electrode during circulation, lithium is improved
The rate capability and cyclical stability of air cell.
Experimental example 3:
The shape of carbon coated air electrode material made from embodiment 1-6 is investigated using the characterizing method of transmission electron microscope (TEM)
Looks structure feature.
As a result as shown in Figure 3.From figure 3, it can be seen that CNT and flower-shaped MoS as support frame2Nanosphere is mutual
Connection, and the diameter of nanosphere is about 300-400nm, and confirms MoS2It is compound with the success of CNT.It is detected with scanning electron microscope
As a result consistent.
Experimental example 4:
The shape of carbon coated air electrode material made from embodiment 1-6 is investigated using the characterizing method of X-ray diffraction (XRD)
Looks structure feature.
As a result as shown in Figure 4.Figure 4, it is seen that obtained material shows polycrystalline property, all diffraction maximums
(100), (103), (002), (110) and (105) are directed to 2H-MoS2(JCPDS Card No.37-1492), and without coming
From other characteristic diffraction peaks of impurity phase, the surface MoS of pure phase2The formation of product.
Experimental example 5:
The chemical property of the carbon coated air electrode material as made from electrochemistry experiment investigation embodiment 1.
Specifically experimental procedure is as follows: firstly, by the MS-CNTs of above-mentioned acquisition and polyvinylidene fluoride (PVDF) adhesive
It is the mixing of 8:2 to prepare slurry with mass ratio.Then slurry is coated in Ni foam current collector.Before assembled battery,
Cathode is dried in vacuo at 100 DEG C to remove moisture and organic solvent.Battery component includes: the cathode of above-mentioned preparation, electrolysis
Matter 1M LiClO4InDMSO, Li metal anode and fibreglass diaphragm.It is assembled in the glove box of Ar filling and carries out, electrochemistry
It tests in the sealing container filled with high pure oxygen and carries out.Constant current charge and discharge is recorded using LAND CT2001A battery test system
Electrical testing.All fully charged-discharge tests record in the voltage range of 2.0-4.5V.Based on catalyst and polymer-bonded
The gross mass of agent standardizes current density and specific capacity.
Experimental result is as shown in Figure 5 and Figure 6.From figure 5 it can be seen that the lithium-air battery with MS-CNTs cathode exists
Under the current density of 500mA/g, the discharge capacity of 4080mAh/g is provided, overpotential is charged and discharged down to 1.39V, significantly mentions
Rise the energy efficiency of battery.From fig. 6 it can be seen that electric current of the lithium-air battery with MS-CNTs cathode in 100mA/g is close
Degree is lower to stablize circulation 50 times, and cycle performance is good.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of carbon coated air electrode material, which is characterized in that by surface functionalized carbon nanotube/ten
After dialkyl benzene sulfonic acids sodium solution ultrasonic treatment, hydro-thermal reaction is carried out with ammonium molybdate, thiocarbamide, controls 200 DEG C of hydrothermal temperature,
24~36h of reaction time is heated, the carbon coated air electrode material of molybdenum sulfide enveloped carbon nanometer tube is made in filtration washing, vacuum drying
Material, wherein the surface functionalization of carbon nanotube is the inert gas environment annealing at 550~600 DEG C, then in the nitric acid of 70%w/w
Middle processing, is dried in vacuum overnight.
2. the preparation method of carbon coated air electrode material as described in claim 1, which is characterized in that
Mass ratio between the carbon nanotube, the ammonium molybdate and the thiocarbamide is 5:19:21.
3. the preparation method of carbon coated air electrode material as described in claim 1, which is characterized in that
Before hydro-thermal reaction, also the carbon nanotube/neopelex solution, the ammonium molybdate, the thiocarbamide are added
30~45min is ultrasonically treated into deionized water.
4. a kind of preparation method of carbon coated air electrode material, which comprises the following steps:
By the carbon nanotube of surface functionalized processing and dispersant it is uniform after, with the sulphur source material for being used to prepare molybdenum sulfide
After 180~220 DEG C of 24~36h of hydro-thermal reaction, washing, vacuum drying；
Wherein, functionalization processing is the carbon nanotube to be annealed in inert gas environment and/or by the carbon nanotube
Carry out acidic treatment.
5. the preparation method of carbon coated air electrode material as claimed in claim 4, which is characterized in that
The sulphur source material includes at least one of ammonium molybdate or sodium molybdate；And
At least one of thiocarbamide, sulphur powder, thioacetamide or vulcanized sodium.
6. the preparation method of carbon coated air electrode material as claimed in claim 4, which is characterized in that
The dispersing agent is selected from neopelex solution or cetyl trimethylammonium bromide solution.
7. such as the preparation method of carbon coated air electrode material described in claim 5 or 6, which is characterized in that
The carbon nanotube is annealed in inert gas environment is annealed 1.8~2 hours at 550~600 DEG C.
8. the preparation method of carbon coated air electrode material as claimed in claim 7, which is characterized in that
It by carbon nanotube progress acidic treatment is ultrasonically treated 1~1.5 hour in concentrated nitric acid.
9. a kind of carbon coated air electrode material, which is characterized in that using such as the described in any item carbon coateds skies of claim 1-8
The preparation method of gas electrode material is made.
10. a kind of application of carbon coated air electrode material as claimed in claim 9 in lithium-air battery.
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