CN109309235A - A kind of bifunctional electrocatalyst and its application and preparation method - Google Patents
A kind of bifunctional electrocatalyst and its application and preparation method Download PDFInfo
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- CN109309235A CN109309235A CN201710624668.7A CN201710624668A CN109309235A CN 109309235 A CN109309235 A CN 109309235A CN 201710624668 A CN201710624668 A CN 201710624668A CN 109309235 A CN109309235 A CN 109309235A
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- sulfide
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- mesoporous material
- bifunctional electrocatalyst
- air battery
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- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 45
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000013335 mesoporous material Substances 0.000 claims abstract description 34
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 125000000101 thioether group Chemical group 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 130
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007767 bonding agent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 abstract description 46
- 239000001301 oxygen Substances 0.000 abstract description 46
- 238000006722 reduction reaction Methods 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 description 121
- 239000002041 carbon nanotube Substances 0.000 description 121
- 239000010408 film Substances 0.000 description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 238000004502 linear sweep voltammetry Methods 0.000 description 11
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 11
- 229910002451 CoOx Inorganic materials 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- -1 cobalt class compound Chemical class 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000003990 capacitor Substances 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
- H01M4/8867—Vapour deposition
-
- 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
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention discloses a kind of bifunctional electrocatalyst and its application and preparation method.The bifunctional electrocatalyst is sulfide/mesoporous material, and the sulfide/mesoporous material is to coat sulfide film on mesoporous material by Atomic layer deposition method to be prepared.The present invention utilizes technique for atomic layer deposition, and one layer of sulfide film is equably deposited on the mesoporous material of high-specific surface area, and a kind of new efficient difunctional oxygen evolution reaction, oxygen reduction reaction elctro-catalyst sulfide/mesoporous material has been prepared.Sulfide of the present invention/mesoporous material material presents superior catalytic performance and stability.Sulfide/mesoporous material of the present invention is alternatively arranged as the air electrode of chargeable metal-air battery.The metal-air battery of liquid can export very high power density, and have good long-time stable charge/discharge, and solid metal-air battery presents flexible and stability well in the bent state.
Description
Technical field
The present invention relates to elctro-catalyst technical field more particularly to a kind of bifunctional electrocatalyst and its application and preparation sides
Method.
Background technique
For many renewable energy systems, oxygen evolution reaction and oxygen reduction reaction are two kinds of very important electrochemistry
Process, such as fuel cell, photoelectrochemical cell, electrolyzer, metal-air battery etc..However, oxygen evolution reaction and oxidation are former anti-
The dynamic process answered is very slow, needs efficient elctro-catalyst to accelerate reaction process, reduce reaction overpotential.RuO2With
Pt is often used as the elctro-catalyst during oxygen evolution reaction and oxygen reduction reaction, however these materials are very expensive and stablize
Property is poor, largely hinders their large-scale application.Therefore, the relatively high elctro-catalyst of exploitation sexual valence is needed.Separately
Outside, for can charge and discharge metal-air battery, for regenerative fuel cell, the catalyst loaded on electrode needs to have double function
Energy property, that is, be required to reversibly be catalyzed oxygen evolution reaction and oxygen reduction reaction simultaneously.
In recent years, cobalt class compound is widely used in being catalyzed the elctro-catalyst of oxygen evolution reaction and oxygen reduction reaction, passes through
Some traditional synthesizing means, such as the methods of hydro-thermal, solvent heat, pyrolysis, solution precipitating, cobalt class compound is synthesized into various each
The nanostructure of sample, or be combined together with Carbon materials (porous carbon, carbon nanotube, graphene etc.).However, these are synthesized
Means are usually or being extremely difficult to extensive, high duplication produces, or need special safety event, so they are difficult
Industrially it is applied to batch synthetic material.
In recent years, atomic layer deposition causes wide as a kind of common nano material synthetic method of energy technology field
General concern.Atomic layer deposition using saturation, from restrictive surface chemical reaction process, theoretically can be in any complexity
3-D nano, structure on equably, guarantor property, thickness controllable precise ground deposition film.Atomic layer deposition process is height simultaneously
Repeatable, it has been widely used in many industry and has prepared film to Macroscale homogenous.In fact, coming for elctro-catalyst
It says, its catalytic performance is often to be determined by the property of material most surface, equal in substrate surface using technique for atomic layer deposition
One layer of electro catalytic activity material film is covered evenly, so that it may obtain elctro-catalyst.Therefore, technique for atomic layer deposition is for preparation
Elctro-catalyst can be described as highly useful.Importantly, by technique for atomic layer deposition, the performance of the material surface deposited
It can not be influenced by base material shape, so, in the porous structure support substrate of some high-specific surface areas, use atomic layer
Deposition technique coats one layer of active material, can prepare the electrode that catalytic performance significantly improves.
Summary of the invention
The purpose of the present invention is to provide a kind of bifunctional electrocatalyst and its application and preparation method, technology of the invention
Scheme is as follows:
A kind of bifunctional electrocatalyst, wherein the bifunctional electrocatalyst is sulfide/mesoporous material, sulfide/Jie
Porous materials are to coat sulfide film on mesoporous material by Atomic layer deposition method to be prepared.
The bifunctional electrocatalyst, wherein the sulfide is cobalt sulfide, nickel sulfide, iron sulfide, manganese sulfide, sulphur
Change one of copper, molybdenum sulfide, tungsten sulfide or a variety of.
The bifunctional electrocatalyst, wherein the mesoporous material is carbon nanotube (CNT), in nickel foam, porous charcoal
It is one or more.
The bifunctional electrocatalyst, wherein the bifunctional electrocatalyst is Co9S8/CNT。
The bifunctional electrocatalyst, wherein the bifunctional electrocatalyst is Co9S8/CNT/CC；The Co9S8/
CNT/CC is that first CNT is carried on CC, and Co is then coated on CNT by Atomic layer deposition method9S8What film preparation obtained.
The application of a kind of as above any bifunctional electrocatalyst, wherein the sulfide/mesoporous material is as gold
Category-air cell air electrode.
The application of the bifunctional electrocatalyst, wherein the metal-air battery is the metal-air electricity of liquid
Pond or solid metal-air battery.
The application of the bifunctional electrocatalyst, wherein the metal-air battery is zinc-air battery, lithium-sky
One of pneumoelectric pond, aluminium-air cell, magnesium-air cell.
As above a kind of preparation method of any bifunctional electrocatalyst, wherein comprising steps of
It disperses mesoporous material in solvent, and bonding agent is added, then stir evenly, obtain suspension；
Hanging drop is added on electrode, is transferred to after then drying electrode in the reaction chamber of atomic layer deposition apparatus and carries out sulphur
The deposition of compound film obtains the sulfide/mesoporous material.
The preparation method of the bifunctional electrocatalyst, wherein the solvent is ethyl alcohol, and the bonding agent is perfluor sulphur
Acid, the electrode are one of carbon cloth, glass-carbon electrode.
The utility model has the advantages that the present invention utilizes technique for atomic layer deposition, in the mesoporous material such as carbon nanotube of high-specific surface area
(CNT) one layer of sulfide film is equably deposited on, and a kind of new efficient difunctional oxygen evolution reaction, hydrogen reduction has been prepared
React elctro-catalyst sulfide/mesoporous material.As a kind of bifunctional catalyst, in catalysis oxygen evolution reaction and the former reaction of oxidation
On, sulfide/mesoporous material such as Co of the present invention9S8/ CNT material presents superior catalytic performance and stability, and future has
Prestige is applied in more renewable energy systems.
Detailed description of the invention
Fig. 1 a is atomic layer deposition Co on the carbon nanotubes in embodiment 19S8Flow diagram.
Fig. 1 b is that the SEM of uncoated carbon nanotube schemes.
Fig. 1 c is atomic layer deposition Co9S8The SEM of the carbon nanotube of cladding schemes.
Fig. 1 d is Co9S8The EDS spectrogram of/CNT.
Fig. 1 e and 1f are atomic layer deposition Co9S8The TEM of the carbon nanotube of cladding schemes.
Fig. 1 g is atomic layer deposition Co9S8The electron diffraction diagram of the carbon nanotube of cladding.
Fig. 1 h is the XPS spectrum figure of Co 2p.
Fig. 1 i is the XPS spectrum figure of S 2p.
Fig. 1 j is Co9S8The XPS spectrum figure of the C 1s of/CNT and its uncoated CNT.
Fig. 2 a is respectively elctro-catalyst Co9S8/CNT、CoOx/ CNT, film Co9S8、RuO2, CNT speed of sweeping be 5 mV/s
Linear sweep voltammetry curve.
Fig. 2 b is the corresponding tower Fil curve of linear sweep voltammetry curve each in Fig. 2 a.
Fig. 2 c is the linear sweep voltammetry curve comparison figure before and after 2000 Cyclic voltamogram curves.
Fig. 2 d is the electrode Co at 369 mV of overpotential9S8The constant potential curve of/CNT.
Fig. 2 e is respectively elctro-catalyst Co9S8/CNT/CC、Co9S8The linear sweep voltammetry curve of/CNT, blank CC, illustration
For Co9S8The tower Fil curve of/CNT/CC.
Fig. 2 f is the electrode Co in the case where overpotential is 321mV9S8The constant potential curve of/CNT/CC.
Fig. 3 a is respectively Co9S8/ CNT, CoOx/ CNT, Co9S8Film, CNT and Pt/C are in rotating disk electrode (r.d.e) in O2It is full
Linear sweep voltammetry curve in 0.1 mol/L of sum.
Fig. 3 b is respectively Co9S8The mass transfer of/CNT and Pt/C influences the tower Fil curve after deducting.
Fig. 3 c is Co9S8The linear sweep voltammetry characteristic curve of/CNT under different rotating speeds, illustration Koutecky-
Levich curve.
Fig. 3 d is Co9S8Chronoa mperometric plot of/the CNT and Pt/C at 0.52 V vs.RHE, illustration be electric current for
Response diagram after the methanol for the 1mol/L that 4 mL are added in 0.1 mol/L KOH solution.
Fig. 3 e is Co9S8The rotating ring disk electrode (r.r.d.e) curve of/CNT and CNT.
Fig. 3 f is that the electronics transfer quantity being calculated from Fig. 3 e and yields of hydrogen peroxide and the relationship of on-load voltage are bent
Line.
Fig. 4 a is Co9S8The zinc-air battery open-circuit voltage of/CNT as air electrode.
Fig. 4 b is respectively Co9S8/ CNT and Pt/C+RuO2The polarization curve of zinc-air battery as air electrode and
Corresponding power density curve.
Fig. 4 c is respectively Co9S8/ CNT and Pt/C+RuO2Charge and discharge electric polarization curve.
Fig. 4 d is Co9S8The constant current cycle charge-discharge curve of/CNT as the zinc-air battery of air electrode.
Fig. 5 a is the schematic diagram of solid state rechargeable zinc-air battery.
The battery that Fig. 5 b is Fig. 5 a is 1 mA/cm in current density2Under conditions of, 10 hours continuous discharge curves.
Fig. 5 c is the constant current charge-discharge cyclic curve of Fig. 5 a battery in the bent state.
It in current density is 1 mA/cm that Fig. 5 d, which is Fig. 5 a battery,2Constant current discharge under the conditions of, bending state is to output
The influence relational graph of voltage.
Specific embodiment
The present invention provides a kind of bifunctional electrocatalyst and its application and preparation method, to make the purpose of the present invention, technology
Scheme and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that described herein specific
Embodiment is only used to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of bifunctional electrocatalyst, wherein the bifunctional electrocatalyst is sulfide/mesoporous material
Material, the sulfide/mesoporous material is to coat sulfide film on mesoporous material by Atomic layer deposition method to be prepared
's.
Preferably, the sulfide can be cobalt sulfide (such as Co9S8, CoS or Co3S4Deng), nickel sulfide, in iron sulfide etc.
It is one or more.
Preferably, the mesoporous material can be one of CNT, nickel foam, porous charcoal etc. or a variety of.
The present invention also provides the applications of a kind of as above any bifunctional electrocatalyst, wherein sulfide/Jie
Air electrode of the Porous materials as metal-air battery.The metal-air battery can be the metal-air battery of liquid
Or solid metal-air battery.Preferably, the metal-air battery is zinc-air battery, lithium-air battery, aluminium-sky
One of pneumoelectric pond, magnesium-air cell etc..
The present invention also provides the preparation methods of a kind of as above any bifunctional electrocatalyst, wherein comprising steps of
It disperses mesoporous material in solvent (such as ethyl alcohol), and bonding agent (such as perfluorinated sulfonic acid) is added, then stir evenly, obtain
Suspension；
Hanging drop is added on electrode (such as carbon cloth or glass-carbon electrode), is transferred to atomic layer deposition after then drying electrode
The deposition that sulfide film is carried out in the reaction chamber of equipment, obtains the sulfide/mesoporous material.
As a preferred specific embodiment, the sulfide/mesoporous material is Co9S8/CNT.The present invention utilizes atomic layer
Deposition technique equably deposits one layer of Co on the CNT of high-specific surface area9S8Film has synthesized a kind of new efficient difunctional
Oxygen evolution reaction, oxygen reduction reaction elctro-catalyst Co9S8/CNT.As a kind of bifunctional catalyst, in catalysis oxygen evolution reaction and oxidation
The Co former to react, that the present invention synthesizes9S8/ CNT material presents superior catalytic performance and stability.Meanwhile the present invention
The Co for also further synthesizing this technique for atomic layer deposition9S8/ CNT bifunctional catalyst is as chargeable metallic zinc-air electricity
The air cell in pond.The chargeable zinc-air battery of liquid can export very high power density, and have long well
Time stable charge/discharge, it is solid can charge and discharge zinc-air battery present flexible well and stability in the bent state
Energy.These are the result shows that the present invention utilizes the Co of technique for atomic layer deposition synthesis9S8/ CNT catalyst can not only be efficiently catalyzed
Oxygen evolution reaction and oxygen reduction reaction, and future is expected to be applied in more renewable energy systems.
Below by embodiment, the present invention is described in detail.
Embodiment
1, Co is prepared on glass-carbon electrode9S8/ CNT prepares Co on the glass-carbon electrode9S8The method of/CNT is as follows:
1), firstly, dispersing the carbon nanotube of commercialization in ethanol solution, and bonding agent is added, wherein perfluorinated sulfonic acid conduct
Binder.
2), then, the good suspension of ultrasonic disperse is dripped respectively on various glass-carbon electrodes, including plane electricity
Pole, rotating disk electrode (r.d.e), rotating ring disk electrode (r.r.d.e), load capacity are 0.2 mg/cm2。
3), finally, being transferred to the reaction of atomic layer deposition apparatus after the glass-carbon electrode of above-mentioned load carbon nanotube is dried
Co is carried out in room9S8Film deposition.The heating temperature for controlling reaction chamber is 120 DEG C, wherein the presoma of cobalt element can be N,
The alkyl-substituted amidino groups cobalt class compound of N'-, for example, two (N, N'- diisopropylacetamidinate base) cobalt [Co (amd)2].In addition, institute
State Co (amd)2In isopropyl also could alternatively be the alkyl such as ethyl, tert-butyl, sec-butyl, tertiary pentyl or sec-amyl, wherein
Ethanamidine base could alternatively be the groups such as carbonamidine base, isopropyl amidino groups or normal-butyl.The presoma of element sulphur can be H2S。
2、Co9S8The characterization and electrocatalysis characteristic of/CNT material are tested
1), the Co of atomic layer deposition preparation9S8/ CNT material characterization result is as follows:
As shown in Figure 1a, by Atomic layer deposition method, can in carbon nanotube substrate guarantor property, equably coat one layer
Co9S8Film；And by the cycle-index for changing atomic layer deposition, Co in carbon nanotube can be accurately controlled9S8The thickness of layer
Degree.In the present embodiment, 200 Co of cyclic deposition9S8, the Co of available about 7 nm9S8Film.
SEM is for observing carbon nanotube in atomic layer deposition Co9S8Shape characteristic before and after film.Such as Fig. 1 b, shown in 1c,
In deposition Co9S8After film, the integrality of its network structure is can still be maintained in carbon nanotube, deposits Co9S8Carbon after film is received
Mitron thickness has increased slightly.
EDS in Fig. 1 d is the result shows that atomic layer deposition Co9S8There is the presence of Co, S element in carbon nanotube after film.
TEM is equally used for the carbon nanotube of characterization atomic layer deposition thin film cladding.
Such as Fig. 1 e, shown in f, about 7 nm Co9S8Film is uniformly coated in entire carbon nanotube, this shows atomic layer deposition
Product clad is high uniformity and guarantor property.
Electron diffraction diagram in Fig. 1 g presents clearly diffraction ring, the Co with face-centred cubic structure9S8 (a = 9.92
, JCPDS 86-2273) and it matches very much.X-ray photoelectron spectroscopy is for analyzing Co9S8Chemical environment in/CNT around element.
Such as Fig. 1 h, shown in 1i, Co 2p has a pair of of spin orbit splitting peak at 778.3 eV and 793.2 eV, and S 2p exists
There are a pair of of spin orbit splitting peak, Co in the position at these peaks and bibliography at 161.3 eV and 162.4 eV9S8Peak position one
It causes.
In addition, as shown in fig. ij, due to surface C o9S8The intensity of the screen effect of thin layer, C 1s significantly reduces, further
Prove the height conformality and uniformity of atomic layer deposition clad.
2), for oxygen evolution reaction, selection measures catalyst Co in 0.1 mol/L KOH9S8The electrocatalysis characteristic of/CNT.
In order to avoid the influence of mass transfer, the electro-chemical test of Fig. 2 a-2d is executed in the rotating disk electrode (r.d.e) that revolving speed is 1600 rpm
's.
Material C o is characterized with linear sweep voltammetry first9S8The performance of/CNT catalysis oxygen evolution reaction.As a comparison, it also surveys
Pure nano-carbon tube, atomic layer deposition CoO are determinedxEnveloped carbon nanometer tube (CoOx/ CNT), atomic layer deposition Co9S8Film and catalysis
The RuO of the most effective catalyst of oxygen evolution reaction2Linear sweep voltammetry curve, as a result as shown in Figure 2 a.In above-mentioned catalyst,
The Co of atomic layer deposition preparation9S8/ CNT presents best catalytic performance, is 10 mA/cm for reaching current density value2 This
One index, Co9S8It is only necessary to the overpotential of 369 mV by/CNT, are less than RuO2409 mV, CoOx431 mV of/CNT, film
Co9S8511 mV, while overpotential be 500 mV within, the current density of uncoated carbon nanotube can be ignored substantially.
Catalyst can be evaluated for being catalyzed the dynamics of oxygen evolution reaction by the method for tower Fil, wherein from linearly sweeping
It is as shown in Figure 2 b to retouch tower Fil curve obtained in volt-ampere result.RuO2, CoOx/ CNT, film Co9S8Tafel slope value point
Not Wei 110,81,63 mV/ octaves, compared with these catalyst, atomic layer deposition preparation Co9S8The Tafel slope of/CNT
It is worth smaller, only 58 mV/ octaves, this shows Co9S8/ CNT is catalyzed the dynamics of oxygen evolution reaction in these catalyst
It is most fast.
By arriving 1.77V(vs. RHE 0.97) in range, with the continuous cyclic voltammetry scan of the speed of 100mV/s,
Test Co9S8Stability of/the CNT for oxygen evolution reaction.As shown in Figure 2 c, the line before and after 2000 Rapid Circulation voltammetric scans
Property scanning curve substantially without what difference, this illustrates the catalyst Co of the present embodiment atomic layer deposition preparation9S8The circulation of/CNT
Stability is good.
In addition, the present embodiment also further tests Co by 10 hours constant potentials9S8The stability of/CNT, wherein electricity
It is 369 mV that pressure, which is maintained at overpotential, and corresponding initial current density values are 10 mA/cm2, as shown in Figure 2 d.In the survey of this 10h
It tries in the time, electric current is held essentially constant, and after 10 hours, current density remains as 9.62 mA/cm2, this result is again
Show catalyst Co9S8/ CNT has good stability.
Fig. 2 e is respectively catalyst Co9S8/CNT/CC、Co9S8The linear sweep voltammetry curve of/CNT, blank CC, illustration are
Co9S8The tower Fil curve of/CNT/CC.
Fig. 2 f is the electrode Co in the case where overpotential is 321mV9S8The constant potential curve of/CNT/CC.
Above the result shows that, the present embodiment atomic layer deposition preparation Co9S8/ CNT is a kind of good oxygen evolution reaction electricity
Catalyst can effectively be catalyzed oxygen evolution reaction under very low overpotential.This good catalytic performance largely obtains
Beneficial to technique for atomic layer deposition can guarantor property, equably cover carbon nanotube substrate, catalysis oxygen evolution reaction in can be abundant
Utilize the high surface area of carbon nanotube.Therefore, pass through this method of atomic layer deposition, effective electrochemical surface area of catalyst
It can be seen that its section has increased considerably.The present embodiment tests the electrochemical double-layer capacitor of catalyst, the results showed that atomic layer deposition system
Standby Co9S8The effective surface area of/CNT is film Co9S830 times, therefore, with film Co9S8It compares, in identical overpotential
Under, catalyst Co9S8/ CNT shows as higher current density.Meanwhile the coarse of more carbon nanotubes can be accommodated using one
Or porous structure, such as conductive carbon cloth can be further improved the catalytic performance of catalyst.In order to test Co9S8/
The catalytic performance of CNT/CC, the present embodiment have loaded about 0.5 mg/cm on carbon cloth (CC) electrode2Carbon nanotube, then exist
Co is coated above using technique for atomic layer deposition under the same terms before9S8Layer.As shown in Figure 2 e, Co9S8The certain table of CNT/CC
Better oxygen evolution reaction performance is showed, reaching current density is 10mA/cm2, overpotential reduction, it is only necessary to which 321 mV compare Co9S8/
Small 48 mV of CNT.Co9S8The Tafel slope of/CNT/CC is 58 mV/ octaves (decade), with Co9S8/ CNT is in rotational circle
Value on disc electrode is consistent.In fact, compared with other base metal class catalyst, the catalyst table of atomic layer deposition preparation
Existing overpotential and Tafel slope is more preferable, this shows technique for atomic layer deposition on preparing elctro-catalyst with very big excellent
Gesture.
It is tested by timing constant potential, i.e., it is 10 that maintenance overpotential, which is the corresponding initial current density of 321 mV(, for a long time
mA/cm2), observation electric current changes with time trend to evaluate catalyst Co9S8The stability of/CNT/CC.As shown in figure 2f, 20
After a hour, current density is still 9.63 mA/cm2(less than the reduction of 4 %), this shows catalyst Co9S8/ CNT/CC has very
Good catalytic performance.In addition, several work reported recently are thought: under the test of oxygen evolution reaction condition, transition metal vulcanization
Object can gradually develop into corresponding metal hydroxides, and the metal hydroxides of this differentiation is only really effectively electricity and urges
Agent.Therefore, catalyst Co is analyzed using XPS technology9S8Ingredient and element chemistry ring of/the CNT after oxygen evolution reaction test
Border.The result shows that cobalt sulfide changes really to play the cobalt hydroxide class compound of catalysis oxygen evolution reaction really.Although some machines
Reason is analysis shows cobalt hydroxide is only real catalyst, however, such as Fig. 2 a, shown in b, and the catalyst Co of this differentiation9S8/CNT
The oxygen evolution reaction performance of performance is than CoO prepared by same Atomic layer deposition methodx/ CNT is good very much.It is therefore contemplated that this atom
The catalyst Co of layer deposition preparation9S8/ CNT is a kind of good base metal class oxygen evolution reaction elctro-catalyst, while atomic layer deposition
Product technology plays a very important role for synthesizing this high performance elctro-catalyst.
3), on the other hand, it is also tested for the catalyst Co of the present embodiment technique for atomic layer deposition preparation9S8/ CNT is for oxygen
The electrocatalysis characteristic of reduction reaction.
Catalyst Co is tested using linear sweep voltammetry in rotating disk electrode (r.d.e)9S8The hydrogen reduction performance of/CNT,
In sweep speed be 10 mV/s, rotating disk electrode (r.d.e) revolving speed be 1600 rpm.Similarly, as a comparison, it is also tested for pure carbon nanometer
Pipe, atomic layer deposition CoOxEnveloped carbon nanometer tube (CoOx/ CNT), atomic layer deposition Co9S8Film and oxygen reduction reaction are most effective
Catalyst Pt/C linear sweep voltammetry curve.As a result as shown in Figure 3a, the catalyst of technique for atomic layer deposition synthesis
Co9S8/ CNT presents good hydrogen reduction performance, and wherein take-off potential is 0.94 V, and half wave potential is 0.82 V(vs.
RHE).Meanwhile Co9S8/ CNT catalytic oxidation-reduction reacts active considerably beyond pure nano-carbon tube, atomic layer deposition CoOxCladding
Carbon nanotube (CoOx/ CNT), only active weaker (take-off potential: 1.04 V, 0.89 V of half wave potential) than Pt/C.
Fig. 3 b is that mass transfer influences the tower Fil curve graph after deducting, catalyst Co9S8The Tafel slope of/CNT is 59 mV/
Octave, the 70 mV/ octaves less than Pt/C, shows Co9S8/ CNT has faster dynamics for oxygen reduction reaction.
Using rotating disk electrode (r.d.e), it is investigated influence of the revolving speed for catalyst performance, curve is as shown in Figure 3c.From song
Koutecky-Levich curve obtained in line 3c is as shown in the illustration in the upper left corner, in 0.35 to 0.65 V(vs. RHE) model
In enclosing, j-1 presents good linear relationship relative to ω -1/2.Meanwhile from Koutecky-Levich slope, it can calculate
The electronics transfer quantity of oxygen reduction reaction is 3.83 out, and close to 4, this shows the catalyst Co of technique for atomic layer deposition preparation9S8/
CNT occur in catalytic oxidation-reduction reaction process one preferably close to the transfer process of 4 electronics (wherein also with method of the same race
The electronics transfer quantity in Pt/C catalytic oxidation-reduction reaction process is obtained, for 3.98).
In addition, catalyst Co9S8/ CNT presents good stability, keeps carrying out not under the bias of 0.52V vs. RHE
Disconnected oxygen reduction reaction, after 7200 s, electric current has only been decayed 5 % or so, under identical condition, for Pt/C, electric current
Attenuation percentage is 21%.Catalyst Co9S8/ CNT also presents the performance of good methanol tolerance cross contamination, and future is expected to firing
It is applied in material battery.
Rotating ring disk electrode (r.r.d.e) is for further accurately confirming the yield and electron transfer number of intermediate product hydrogen peroxide
Amount, wherein ring electrode current potential is maintained at 1.4 Vvs. RHE, for collecting the intermediate product hydrogen peroxide during hydrogen reduction.Such as
Shown in Fig. 3 e and 3f, catalyst Co9S8The circular current very little of/CNT calculates in 0.3 ~ 0.7 V vs. RHE voltage range
The percentage yield of the intermediate product hydrogen peroxide arrived less than 10%, corresponding electronics transfer quantity between 3.94 ~ 3.90, this
A result further demonstrates that catalyst Co9S8/ CNT is close to ideal 4 electronic transfer process.From result above, it may infer that
The Co of atomic layer deposition preparation9S8/ CNT is a kind of good oxygen reduction electro-catalyst.
The above result shows that the Co of atomic layer deposition preparation9S8/ CNT is a kind of good oxygen evolution reaction and oxygen reduction reaction
Elctro-catalyst.Then, be further prepared for liquid and solid zinc-air battery, wherein bifunctional catalyst Co9S8/
CNT is as air electrode, and metal zinc metal sheet is as cathode, and 6 mol/L KOH and 0.2 mol/L zinc acetate are as electrolyte.Such as figure
Shown in 4a, the zinc-air battery of liquid can be to be maintained for more than 24 hours at ~ 1.43 V in open-circuit voltage.
The polarization curve that discharges is as shown in Figure 4 b, uses Co9S8/ CNT is put as the zinc-air battery of air electrode very high
Still there is very high output voltage under electric current, be greater than 150 mA/cm in current density2Under, output voltage has been even more than use
Mixture Pt/C+RuO2Zinc-air battery as air electrode.According to zinc-air battery current density and power in Fig. 4 b
The relation curve of density, uses Co9S8/ CNT is up to 200 mW/ as the maximum power density of the zinc-air battery of air electrode
cm2, get a good chance of being applied in the device that high power needs.
Fig. 4 c is compared respectively with catalyst Co9S8/ CNT and Pt/C+RuO2Zinc-air battery as air electrode fills
Discharge polarization curve, wherein Co9S8/ CNT presents better performance as the zinc-air battery of air electrode, is being greater than 10
mA/cm2Charging current under, its required voltage ratio Pt/C+RuO2Small 60 ~ 90 mV of zinc-air battery as air electrode.
It is 10 mA/cm in current density2Under, the long-time stable charge/discharge of battery is tested, as a result such as Fig. 4 d institute
Show, within the loop test time more than 96 hours, change substantially without charging/discharging voltage, this shows to utilize Co9S8/ CNT makees
Superior cyclical stability is able to maintain that for the zinc-air battery of air electrode.In addition, as zinc-air battery practical application
Example, Co9S8/ CNT can replace button cell or AAA battery for driving as the zinc-air battery of air electrode
Temperature/humidity detection meter or remote controler.
In addition, as shown in Figure 5 a, encapsulation is prepared for solid zinc-air battery, wherein catalyst Co9S8/ CNT is as empty
Pneumoelectric pole, PVA/KOH gel is as electrolyte.
As shown in Figure 5 b, the solid-state zinc-air battery of preparation can export relatively high and stable voltage, be in discharge current
2 mA/cm2Under conditions of, by the continuous discharge of 10 hours, the output voltage of battery from initial 0.89 V to 0.81 V,
Only about 9% decaying.
Meanwhile 3 solid-state zinc-air batteries are cascaded, the blue LED lamp of 3 V can be lighted.It is prior
It is that the solid-state zinc-air battery of assembling can be bent, as shown in Fig. 5 c-d, when battery is bent under a different angle,
Its charging and discharging curve does not change substantially, in addition, battery, under the conditions of constant current discharge, bending also has no its output voltage
It influences.These results indicate that with catalyst Co9S8The solid-state zinc-air battery that/CNT is encapsulated as air cell is in bending state
Under still present preferable stability, future is expected to be applied in flexible energy device.
In conclusion a kind of bifunctional electrocatalyst provided by the invention and its application and preparation method, the present invention is utilized
Technique for atomic layer deposition equably deposits one layer of sulfide film on the mesoporous material of bigger serface, is a kind of new analysis oxygen
Reaction and oxygen reduction reaction bifunctional electrocatalyst.Have benefited from mesoporous material high surface area and technique for atomic layer deposition it is conformal
The advantage of property deposition film, this sulfide/catalyst of mesoporous material presents very high in oxygen evolution reaction and oxygen reduction reaction
Activity and stability.Meanwhile using this bifunctional catalyst as air electrode, it has also been probed into can charge and discharge zinc-
A possibility that being applied on air cell.The result shows that the zinc-air battery of liquid can export very high power density and holding
Superior long-time stability in the bent state can in addition, solid zinc-air battery presents good flex capability
Enough maintain good stability.In view of oxygen conversion process is the core status in many energy conversion systems, it is believed that this
Bifunctional electrocatalyst sulfide/mesoporous material of technique for atomic layer deposition synthesis gets a good chance of depositing in following renewable energy
It is applied in storage switching device.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of bifunctional electrocatalyst, which is characterized in that the bifunctional electrocatalyst is sulfide/mesoporous material, described
Sulfide/mesoporous material is to coat sulfide film on mesoporous material by Atomic layer deposition method to be prepared.
2. bifunctional electrocatalyst according to claim 1, which is characterized in that the sulfide be cobalt sulfide, nickel sulfide,
One of iron sulfide, manganese sulfide, copper sulfide, molybdenum sulfide, tungsten sulfide are a variety of.
3. bifunctional electrocatalyst according to claim 1, which is characterized in that the mesoporous material be CNT, nickel foam,
One of porous charcoal is a variety of.
4. bifunctional electrocatalyst according to claim 1, which is characterized in that the bifunctional electrocatalyst is Co9S8/
CNT。
5. bifunctional electrocatalyst according to claim 4, which is characterized in that the bifunctional electrocatalyst is Co9S8/
CNT/CC；The Co9S8/ CNT/CC is that first CNT is carried on CC, is then coated on CNT by Atomic layer deposition method
Co9S8What film preparation obtained.
6. a kind of application of bifunctional electrocatalyst a method as claimed in any one of claims 1 to 5, which is characterized in that the sulfide/
Air electrode of the mesoporous material as metal-air battery.
7. the application of bifunctional electrocatalyst according to claim 6, which is characterized in that the metal-air battery is
The metal-air battery of liquid or solid metal-air battery.
8. the application of bifunctional electrocatalyst according to claim 6, which is characterized in that the metal-air battery is
One of zinc-air battery, lithium-air battery, aluminium-air cell, magnesium-air cell.
9. a kind of preparation method of bifunctional electrocatalyst a method as claimed in any one of claims 1 to 5, which is characterized in that including step
It is rapid:
It disperses mesoporous material in solvent, and bonding agent is added, then stir evenly, obtain suspension；
Hanging drop is added on electrode, is transferred to after then drying electrode in the reaction chamber of atomic layer deposition apparatus and carries out sulphur
The deposition of compound film obtains the sulfide/mesoporous material.
10. the preparation method of bifunctional electrocatalyst according to claim 9, which is characterized in that the solvent is ethyl alcohol,
The bonding agent is perfluorinated sulfonic acid, and the electrode is one of carbon cloth, glass-carbon electrode.
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