CN109530714A - A kind of combination electrode material and its preparation method and application - Google Patents
A kind of combination electrode material and its preparation method and application Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 75
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 81
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 abstract description 34
- 239000000463 material Substances 0.000 abstract description 25
- 239000002041 carbon nanotube Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229910002555 FeNi Inorganic materials 0.000 description 21
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000956 alloy Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910017356 Fe2C Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明公开了一种复合电极材料及其制备方法和应用，涉及能源转换与储存材料技术领域。本发明所述复合电极材料为氮原子掺杂的石墨化碳纳米管包覆镍铁合金纳米颗粒的核壳纳米管状复合材料，所述氮原子掺杂在石墨化碳纳米管的碳层中，所述镍铁合金纳米颗粒中Fe与Ni的摩尔比为3:1～1:3。所述复合电极材料具有优异的HER、OER和ORR三功能催化性能，具有良好的稳定性，且原料成本较低，制备方法简单有效，合成过程绿色、可控，十分有利于该材料的大量生产，在全水裂解以及锌‑空气电池中有相当大的实际应用前景。
The invention discloses a composite electrode material, a preparation method and application thereof, and relates to the technical field of energy conversion and storage materials. The composite electrode material of the present invention is a core-shell nano-tubular composite material in which the graphitized carbon nanotubes doped with nitrogen atoms are coated with nickel-iron alloy nanoparticles, and the nitrogen atoms are doped in the carbon layer of the graphitized carbon nanotubes, so The molar ratio of Fe to Ni in the nickel-iron alloy nanoparticles is 3:1 to 1:3. The composite electrode material has excellent three-functional catalytic performance of HER, OER and ORR, good stability, low cost of raw materials, simple and effective preparation method, green and controllable synthesis process, and is very beneficial to mass production of the material , has considerable practical application prospects in total water splitting and zinc-air batteries.
Description
Technical field
The present invention relates to energy conversions and storage material technical field, and in particular to a kind of combination electrode material and its system
Preparation Method and application.
Background technique
In recent years, due to the large-scale use of petroleum resources, a series of Global Environmental Problems are caused.And develop cleaning
Energy technology is considered as alleviating Global climate change, the method for improving people's quality of life.In various researchs, the energy turns
Change technology has attracted the extensive concern from academia and industry.In Energy Conversion Technology, about electrolysis water evolving hydrogen reaction
(HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) become the focus studied at present.It can be with by HER and OER
Water is resolved into hydrogen and oxygen, wherein be a kind of very excellent clean fuel by the hydrogen that cathode HER is generated, and it is positive
The oxygen that pole OER is generated can also be widely used in life production.ORR then may be implemented chemically arrive electric energy
Conversion, this direct energy conversion have quite high efficient energy conversion and nontoxicity, thus are considered a kind of
Very potential and environmental-friendly energy conversion apparatus.However being limited due to slow dynamics on oxygen electrode, it leads
Cause the efficiency of OER and ORR still lower.Commercially the application of HER and ORR relies primarily on Pt base catalyst at present.Its price
It is sufficiently expensive and poor in alkaline stability inferior, and to the gas sensitizations such as CO, methanol, easy " poisoning ".For OER, currently
The main oxide composite for using Ir base or Ru base.These materials equally exist expensive, stable under alkaline conditions
Property difference and catalytic activity it is single the disadvantages of.Presence based on these defects is unfavorable for being electrolysed aquatic products hydrogen and zinc-air
The practical application of battery is promoted.
In order to solve these problems, to the even nonmetallic research of base metal so that the type of elctro-catalyst obtains
Greatly expand.In numerous materials, carbon nanotube (CNTs) has high-specific surface area as a kind of, and high conductivity is high mechanical
Intensity and good flexible material make it become a kind of very potential catalyst.Although carbon nanotube has many excellent
Point, but its latent active is poor, typically just serves as the carrier of other catalyst.
Summary of the invention
It is an object of the invention to a kind of combination electrode material and its preparation are provided in place of overcome the deficiencies in the prior art
Methods and applications, the combination electrode material have the function of excellent tri- catalytic performance of HER, OER and ORR, have good steady
It is qualitative, and cost of material is lower, preparation method is simple and effective, and entire synthesis process is green, controllable, is advantageous to the material
Mass production.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of combination electrode material, the combination electrode material are the graphitized carbon nano pipe (N- of nitrogen atom doping
GCNTs the core-shell nano tubular composite material (N-GCNTs/NiFe) of dilval nano particle) is coated, the nitrogen-atoms is mixed
It is miscellaneous in the carbon-coating of graphitized carbon nano pipe, the molar ratio of Fe and Ni is in the dilval nano particle (NiFe NPs)
3:1~1:3.
Combination electrode material of the invention be N-GCNTs/NiFe, by NiFe NPs construct and to CNTs into
Row nitrogen atom doping forms various carboritrides using the special electronic structure of nitrogen-atoms, wherein the activity of pyridine nitrogen
It is most strong.In addition, making the N-GCNTs surface-active site outside total layer by metallic atom and the interatomic interaction of carbon-coating
It also can be by inner layer metal-carrier stress, so that the electronic structure of surface atom is also accurately regulated and controled.
This newly-established electronic structure be different from common pyridine N structure, although its chemical structure there is no variation, due to
The influence of interior ply stress is received, so that the electronic structure of part is changed.The variation of this electronic structure can be effective
Ground reduces the energy barrier in HER, OER and ORR catalytic reaction process, and can by the metal alloy particle of excellent electric conductivity
Further to improve the electric conductivity of material, accelerate the electron transfer rate in HER, OER and ORR reaction process, to have
Improve reactivity in effect ground.In addition, research shows that transition metal particles have stronger catalytic growth carbon nanotube ability, energy
Catalysis polyphosphazene polymer meeting object transforms into carbon nanotube, and the N-GCNTs/ of nanoscale can be obtained using simple heat treatment
NiFe, while present invention also reduces the pollution level of Industrial Catalysis synthesizing carbon nanotubes and degrees of danger.
Preferably, the molar ratio of Fe and Ni is 3:1 in the dilval nano particle.
N-GCNTs/Fe prepared by the present invention3Most, high price when active site of the Ni when Fe and Ni ratio is 3:1
The Ni ion and Fe ion of state can further enhance the stress to carbon layer on surface, and this effect also promotes table
The activity of face active site further enhances.
The present invention also provides the preparation methods of above-mentioned combination electrode material, comprising the following steps:
(1) using metal soluble-salt, organic carbon source and nitrogen source as presoma, uniformly mixed precursor solution is prepared, is steamed
After hair drying, the compound precursor object of metallic Yu the uniform mixed ligand of organic precursor is obtained；
(2) compound precursor object is placed in nitrogen or inert atmosphere and is heat-treated, obtain combination electrode material.
The present invention can be closed successfully using metal soluble-salt, organic carbon source and nitrogen source as presoma using one-step calcination method
At the N-GCNTs/NiFe material with fine nanostructur, and entire synthesis process is green, controllable, is advantageous to this
The mass production of material, and then strong popularization is played for the further commercialization of zinc-air battery.
Present invention growth in situ surface richness active site on metal nanoparticle by simple and effective one-step calcination method
N-GCNT, and mixed by what the electron interaction of the NiFe NPs and N-GCNTs of internal layer and Ni atom pair Fe were carried out
Miscellaneous, realization optimizes the electronic structure of material activity component, thus further such that HER, OER and ORR of the material
Reach optimum performance；The encapsulation carried out by N-GCNTs to NiFe NPs, also enhances the stabilization of the combination electrode material
Property.
Preferably, the metal soluble-salt is nickel nitrate and ferric nitrate, and the organic carbon source is glucose, the nitrogen
Source is melamine.Using common, cheap nickel nitrate and ferric nitrate as metal soluble-salt, glucose is as carbon source, and three
Poly cyanamid reduces cost of material as nitrogen source.
Further, the precursor solution includes 0.145~0.435g Nickelous nitrate hexahydrate, 0.202~0.606g
Fe(NO3)39H2O, 0.05g glucose, 4g melamine and 20mL distilled water.
Further, the precursor solution include 0.145g Nickelous nitrate hexahydrate, 0.606g Fe(NO3)39H2O,
0.05g glucose, 4g melamine and 20mL distilled water.The dosage of glucose and melamine is fixed by the present invention
0.05g and 4g has studied different iron nickel ratios, has obtained the Fe of different component2C and FeNi alloy, after contrast properties, really
High performance tri- function catalyst of HER, ORR, OER has been obtained when being scheduled on Fe:Ni=3:1, can be used for full water-splitting and zinc-sky
In pneumoelectric pond.
Preferably, in the step (1), the temperature of evaporation is 40 DEG C.
Preferably, in the step (2), the inert atmosphere includes argon gas, the process of thermal treatment parameter setting
Are as follows: first stage calcination temperature is 500 DEG C, calcination time 120min, and the heating-up time is 500 min；Second stage calcining temperature
Degree is 800 DEG C, calcination time 120min, heating-up time 150min.
By various reaction conditions in above-mentioned technical proposal, regulate and control NiFe alloy component and carbon nanotube growth and
The doping level of nitrogen-atoms, obtain possess tri- function catalytic performance of HER, OER and ORR N-GCNTs/NiFe nanometer it is multiple
Condensation material.
The present invention also provides application of the above-mentioned combination electrode material in full water-splitting and zinc-air battery.
N-GCNTs/NiFe material of the invention has the function of excellent tri- catalytic performance of HER, OER and ORR, and has
Good stability has a wide range of applications in full water-splitting and zinc-air battery.
Compared with prior art, the invention has the benefit that
The present invention utilizes nitrogen former by constructing and carry out nitrogen atom doping to CNTs to NiFe alloy nano particle
The special electronic structure of son, forms various carboritrides, and wherein the activity of pyridine nitrogen is most strong.In addition, relying on metallic atom
With the interatomic interaction of carbon-coating, make the N-GCNTs surface-active site outside total layer also can be by inner layer metal-carrier
Stress so that the electronic structure of surface atom is also accurately regulated and controled.This newly-established electronic structure is not
It is same as common pyridine N structure, although there is no variations for its chemical structure, due to receiving the influence of interior ply stress,
So that the electronic structure of part is changed.The variation of this electronic structure can be effectively reduced HER, OER and ORR
Energy barrier in catalytic reaction process, and material can further be improved by the metal alloy particle of excellent electric conductivity
Electric conductivity accelerates the electron transfer rate in HER, OER and ORR reaction process, to effectively improve reactivity.This
Outside, research shows that transition metal particles have stronger catalytic growth carbon nanotube ability, can be catalyzed polyphosphazene polymer can object conversion
As carbon nanotube, the N-GCNTs/NiFe of nanoscale can be obtained using simple heat treatment, while the present invention also reduces
The pollution level and degree of danger of Industrial Catalysis synthesizing carbon nanotubes.
For the present invention by controlling various reaction conditions, growth and the nitrogen for regulating and controlling NiFe alloy component and carbon nanotube are former
The doping level of son, obtains the nano combined material of N-GCNTs/NiFe for possessing tri- function catalytic performance of HER, OER and ORR
Material.
Detailed description of the invention
The synthesis mechanism schematic diagram of Fig. 1, (a) N-GCNTs/NiFe.N-GCNTs/Fe3(b) XRD map of Ni, (c) sweeps
Retouch Electronic Speculum (SEM) picture, transmission electron microscope (TEM) picture under (d-e) different multiplying；(f) in HR-TEM NiFe alloy lattice
Striped and (g) corresponding SAED image；(h) lattice fringe of the graphitized carbon in HR-TEM and (i) to deserved SAED scheme
Picture；(i) Mapping image.
Fig. 2, N-GCNTs/Fe3Ni and Pt/C ∥ RuO2(a) polarization curve of HER and OER and corresponding (b-c) tower are luxuriant and rich with fragrance
That slope figure；(d) polarization curve under two electrode systems；(e) the configuration picture of two electrode assemblies.
Fig. 3, N-GCNTs/Fe3Ni and Pt/C ∥ RuO2(a) OER and ORR polarization curve, (b-c) corresponding tower is luxuriant and rich with fragrance
That slope figure；(d) charging and discharging curve figure；(h) two use N-GCNTs/Fe3Ni is used as zinc-sky that anode and cathode is assembled into simultaneously
Pneumoelectric pond lightening LED lamp.
Fig. 4, N-GCNTs/Fe3The N of Ni2Adsorption desorption isothermal curve map.
Fig. 5, N-GCNTs/Fe3Ni, N-GCNTs/Fe2Ni, N-GCNTs/FeNi, N-GCNTs/FeNi2, N-GCNTs/
FeNi3, the XRD spectrum of N-GCNTs/Fe.
Fig. 6, N-GCNTs/Fe3The SEM picture of Ni different multiplying.
Fig. 7, N-GCNTs/Fe2The SEM picture of Ni different multiplying.
The SEM picture of Fig. 8, N-GCNTs/FeNi different multiplying.
Fig. 9, N-GCNTs/FeNi2The SEM picture of different multiplying.
Figure 10, N-GCNTs/FeNi3The SEM picture of different multiplying.
The SEM picture of Figure 11, N-GCNTs/Fe different multiplying.
Figure 12, (a) N-GCNTs/Fe3Ni, N-GCNTs/Fe2The OER polarization curve of Ni and N-GCNTs/FeNi, and
Corresponding (c) Tafel slope figure.N-GCNTs/FeNi, N-GCNTs/FeNi2And N-GCNTs/FeNi3OER polarization curve
Figure and corresponding (d) Tafel slope figure.
Figure 13, (a) N-GCNTs/Fe3Ni, N-GCNTs/Fe2The HER polarization curve of Ni and N-GCNTs/FeNi, and
Corresponding (c) Tafel slope figure.N-GCNTs/FeNi, N-GCNTs/FeNi2And N-GCNTs/FeNi3HER polarization curve
Figure and corresponding (d) Tafel slope figure.
Figure 14, N-GCNTs/Fe3Ni, N-GCNTs/Fe2The pole of (a) of Ni and N-GCNTs/FeNi all-hydrolytic HER and OER
Change curve graph；And corresponding XPS (b) Ni 2p map and (c) Fe 2p map.
Figure 15, N-GCNTs/FeNi, N-GCNTs/FeNi2And N-GCNTs/FeNi3All-hydrolytic HER and OER polarization
Curve graph.
Specific embodiment
Purposes, technical schemes and advantages in order to better illustrate the present invention, below in conjunction with specific embodiment to the present invention
It further illustrates.It will be appreciated by those skilled in the art that described herein, specific examples are only used to explain the present invention, and
It is not used in the restriction present invention.
If the ratio is molar percentage without certain illustrated, the NiFe refers to that sensu lato ferronickel closes
Gold, N-GCNTs/NiFe are the N-GCNTs/Fe including but not limited to prepared using this method3Ni, N-GCNTs/Fe2Ni, N-
GCNTs/FeNi, N-GCNTs/FeNi2, N-GCNTs/FeNi3, the general name of N-GCNTs/Fe.
In embodiment, used experimental method is conventional method unless otherwise specified, material used, reagent
Deng being commercially available unless otherwise specified.
Embodiment 1
N-GCNTs/Fe3The preparation method of Ni nanocomposite the following steps are included:
(1) 0.145g Nickelous nitrate hexahydrate, 0.606g Fe(NO3)39H2O, 4g melamine and 0.05g glucose are mixed
Conjunction is dissolved in 20mL distilled water, 60min is stirred, so that three kinds of material mixings are uniform；It is ground after evaporation drying at 40 DEG C
Mill, obtains compound precursor object；
(2) resulting predecessor is placed in tube furnace, calcines 120min in 500 DEG C of nitrogen atmospheres, the heating-up time is
500min；800 DEG C are continuously heating to, 120min, heating-up time 150min are calcined.
By research, we describe the synthesis step of this method and mechanism (Fig. 1 a) are as follows: pass through organic carbon source first
Metal ion is coordinated with nitrogen source, is then calcined at 500 DEG C, forms C3N4/ metallic particles intermediate, further
It is calcined at 800 DEG C, the available N-GCNTs/Fe being catalyzed by metal nanoparticle3Ni。
Further the SEM of N-GCNTs/NiFe and TEM is tested, observes its pattern (Fig. 1 c-e, Fig. 6).It is surveyed by SEM
Attempt it is found that N-GCNTs/Fe3Ni pattern is nano tubular structure, and diameter is about 100nm.It can be seen that by TEM figure
N-GCNTs/Fe3Ni is wrapped up by few layer of N-GCNTs.In XRD spectra it can be seen that resulting materials be mainly graphitized carbon and
NiFe alloy composition.Wherein, for the XRD diffraction peak of graphitized carbon in 26.4 °, correspondence crystal face is (002) crystal face；And NiFe
The XRD diffraction maximum of alloy is then located at 43.6 ° and 50.8 °, and corresponding crystal face is respectively (111) and (200) crystal face.While from
The lattice fringe for belonging to NiFe NPs can be clearly seen in HR-TEM image.Mapping image then illustrates that Ni and Fe are uniform
Distribution, Ni realize uniform doping to Fe.N-GCNTs/Fe is obtained from BET test (Fig. 4)3The specific surface area of Ni is
124m2g-1。
Further it is carried out XPS characterization (Figure 14), it can be seen that N-GCNTs/Fe3Ni and Fe in Ni is mainly by list
Matter and ion composition.Wherein N-GCNTs/Fe3The Ni and Fe of elemental in Ni are accounted for always than at least, illustrating in Fe and Ni ratio
It is most when active site when for 3:1.The Ni ion and Fe ion of high-valence state can further enhance to carbon layer on surface
Stress, this act on also promote the activity in surface-active site and further enhance.
By N-GCNTs/Fe3Ni carries out electrocatalysis characteristic test as liberation of hydrogen and oxygen-separating catalyst under three-electrode system,
It is graphite electrode to electrode, reference electrode is saturated calomel electrode (Fig. 2).Pass through N-GCNTs/Fe3Ni and business Pt/C and
RuO2Catalyst is compared, and is had smaller Tafel slope on HER and OER and is reached 10mA cm-2Current density
Overpotential illustrates N-GCNTs/Fe3Ni is more than business Pt/C and RuO on HER and OER respectively2Catalyst.Same condition
Lower test N-GCNTs/Fe3The ORR performance (Fig. 3) of Ni, N-GCNTs/Fe3Ni is in the performances such as carrying current and Tafel slope
Already close to the Pt/C catalyst of noble metal base, and as anode performance it is then remote super noble metal RuO2。
Further by N-GCNTs/Fe3Ni is used as cathode and anode assembling in zinc-air battery simultaneously.It is clear that
N-GCNTs/Fe3Ni has higher open circuit potential and power density, and wherein open circuit potential is up to 1.24V, energy density
For 872.2mA h g-1, power density is up to 653.2W h kg-1It can be with the Pt/C ∥ RuO of noble metal base2Catalyst group is mutually equal to
(energy density is 782.2mA h g to beauty-1, power density is 717.0W h kg-1).And wider source and cheaper valence
Lattice make N-GCNTs/Fe3Ni catalyst has more wide application prospect.
Embodiment 2
N-GCNTs/Fe2The preparation method of Ni nanocomposite the following steps are included:
(1) 0.193g Nickelous nitrate hexahydrate, 0.539g Fe(NO3)39H2O, 4g melamine and 0.05g glucose are mixed
Conjunction is dissolved in 20mL distilled water, 60min is stirred, so that three kinds of material mixings are uniform；It is ground after 40 DEG C of evaporations are dried
Mill, obtains compound precursor object.
(2) resulting predecessor is placed in tube furnace, calcines 120min in 500 DEG C of nitrogen atmospheres, the heating-up time is
500min；800 DEG C are continuously heating to, 120min, heating-up time 150min are calcined.
As can be seen that N-GCNTs/Fe from XRD spectrum (Fig. 5)2N-GCNTs/Fe of the crystal form of Ni compared with embodiment 13Ni
It is similar, illustrate its structure proximate.SEM (Fig. 7) then illustrates that its pattern is also and N-GCNTs/Fe3Ni is approximate, but also occurs
It is apparent to reunite.It can be seen that N-GCNTs/Fe in HER and OER performance test (Figure 12-13)2The catalytic activity of Ni is obvious
Than the N-GCNTs/Fe of optimization3Ni wants poor, it was demonstrated that the dilval ratio after optimization plays electronics in N-GCNTs
The effect of regulation.It is in 50mA cm-2Under voltage obviously compared with the N-GCNTs/Fe of embodiment 13Ni is big, illustrates embodiment 1
N-GCNTs/Fe3Ni is more preferably to form.
Embodiment 3
The preparation method of N-GCNTs/FeNi nanocomposite the following steps are included:
(1) 0.290g Nickelous nitrate hexahydrate, 0.404g Fe(NO3)39H2O, 4g melamine and 0.05g glucose are mixed
Conjunction is dissolved in 20mL distilled water, 60min is stirred, so that three kinds of material mixings are uniform.It is ground after 40 DEG C of evaporations are dried
Mill, obtains compound precursor object.
(2) resulting predecessor is placed in tube furnace, calcines 120min in 500 DEG C of nitrogen atmospheres, the heating-up time is
500min；800 DEG C are continuously heating to, 120min, heating-up time 150min are calcined.
It can be seen that N-GCNTs/Fe of the crystal form compared with embodiment 1 of N-GCNTs/FeNi from XRD spectrum (Fig. 5)3Ni
Fe is lacked2The peak of C and simple substance Fe illustrate that its structure is can to regulate and control by the variation of component.And SEM (Fig. 8) then illustrates
Its substantially pattern and N-GCNTs/Fe3Ni is approximate, but comparatively compared with N-GCNTs/Fe3Ni caliber is inhomogenous.In HER and
It can be seen that the catalytic activity of N-GCNTs/FeNi is obviously than the N-GCNTs/ of optimization in OER performance test (Figure 12-13)
Fe3Ni wants poor, also illustrates Fe2C plays a major role in whole system, and the addition of a small amount of Ni can further regulate and control it is whole
Body performance, but performance will be obviously than the N-GCNTs/Fe in embodiment 13Ni wants poor.
Embodiment 4
N-GCNTs/FeNi2The preparation method of nanocomposite the following steps are included:
(1) 0.387g Nickelous nitrate hexahydrate, 0.269g Fe(NO3)39H2O, 4g melamine and 0.05 g glucose are mixed
Conjunction is dissolved in 20mL distilled water, 60min is stirred, so that three kinds of material mixings are uniform.It is ground after 40 DEG C of evaporations are dried
Mill, obtains compound precursor object.
(2) resulting predecessor is placed in tube furnace, calcines 120min in 500 DEG C of nitrogen atmospheres, the heating-up time is
500min；800 DEG C are continuously heating to, 120min, heating-up time 150min are calcined.
As can be seen that N-GCNTs/FeNi from XRD spectrum (Fig. 5)2Crystal form compared with embodiment 3 N-GCNTs/FeNi
It is similar, but the peak of NiFe alloy occur it is a small amount of shuffle, illustrate that the spacing of lattice of NiFe alloy occurs for more Ni
Reduce.And SEM (Fig. 9) then illustrates its substantially pattern and N-GCNTs/Fe3Ni is approximate, and caliber is more uniform, but also occurs
Some short grained agglomerations.It can be seen that N-GCNTs/FeNi in HER and OER performance test (Figure 12-13)2Urge
Change activity and compared with the N-GCNTs/FeNi in embodiment 3 also wants poor, also NiFe alloy of the side illustration based on Fe is also
There is catalytic action, the Ni content further increased destroys the NiFe alloy structure based on Fe, so as to cause performance
Reduction.
Embodiment 5
N-GCNTs/FeNi3The preparation method of nanocomposite the following steps are included:
(1) 0.435g Nickelous nitrate hexahydrate, 0.202g Fe(NO3)39H2O, 4g melamine and 0.05 g glucose are mixed
Conjunction is dissolved in 20mL distilled water, 60min is stirred, so that three kinds of material mixings are uniform.It is ground after 40 DEG C of evaporations are dried
Mill, obtains compound precursor object.
(2) resulting predecessor is placed in tube furnace, calcines 120min in 500 DEG C of nitrogen atmospheres, the heating-up time is
500min；800 DEG C are continuously heating to, 120min, heating-up time 150min are calcined.
As can be seen that N-GCNTs/FeNi from XRD spectrum (Fig. 5)3Crystal form compared with embodiment 3 N-GCNTs/FeNi
It is similar, but further shuffling occurs in the peak of NiFe alloy, illustrate more Ni make the spacing of lattice of NiFe alloy into
One step reduces, and Ni becomes the main body of alloy instead of Fe.And SEM (Figure 10) then illustrates its substantially pattern and N-GCNTs/Fe3Ni
Approximation, caliber is more uniform, but its caliber is also obviously compared with the N-GCNTs/Fe in embodiment 13Ni is big.In HER and OER
It can be seen that N-GCNTs/FeNi in test (Figure 12-13)2Catalytic activity it is poor compared with the N-GCNTs/FeNi in embodiment 3,
Also NiFe alloy of the side illustration based on Fe has catalytic action, replaces Fe, the NiFe alloy based on Ni
Catalytic activity is poor.
Embodiment 6
The preparation method of N-GCNTs/Fe nanocomposite the following steps are included:
(1) by 0.808g Fe (NO3)3·9H2O, 4g melamine and 0.05g glucose mixed dissolution are distilled in 20mL
In water, 60min is stirred, so that three kinds of material mixings are uniform.It is ground after 40 DEG C of evaporations are dried, obtains compound precursor object.
(2) resulting predecessor is placed in tube furnace, calcines 120min in 500 DEG C of nitrogen atmospheres, the heating-up time is
500min；800 DEG C are continuously heating to, 120min, heating-up time 150min are calcined.
By XRD spectrum (Fig. 5) it can be seen that the N-GCNTs/Fe main component that single Fe salt is raw material is simple substance
Fe, the N-GCNTs/Fe in comparative example 13Ni, it can be found that a small amount of Ni can promote the Fe of catalytic activity2C and essence
The NiFe alloy of fine tuning control.Further confirmation, the doping of a small amount of Ni just can maximumlly promote this nitrogen-doped carbon nanometer
The optimization of tri- functional performance of dilval HER, OER and ORR of pipe package.Similarly (Figure 11) can also be seen in SEM figure
This N-GCNTs/Fe has the N-GCNTs/Fe with embodiment 1 out3The similar structure of Ni.Also illustrate that this method has very
Wide applicability can be used for preparing the metal nanoparticle of the nitrogen-doped carbon nanometer pipe package of various ingredients.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than to the present invention
The limitation of protection scope, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art are answered
Work as understanding, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the reality of technical solution of the present invention
Matter and range.
Claims (9)
1. a kind of combination electrode material, which is characterized in that the combination electrode material is the graphitized carbon nano of nitrogen atom doping
Pipe coats the core-shell nano tubular composite material of dilval nano particle, and the nitrogen atom doping is in graphitized carbon nano pipe
In carbon-coating, the molar ratio of Fe and Ni is 3:1~1:3 in the dilval nano particle.
2. combination electrode material according to claim 1, which is characterized in that Fe and Ni in the dilval nano particle
Molar ratio is 3:1.
3. the preparation method of combination electrode material according to claim 1 or claim 2, which comprises the following steps:
(1) using metal soluble-salt, organic carbon source and nitrogen source as presoma, uniformly mixed precursor solution is prepared, evaporation is dried
After dry, the compound precursor object of metallic Yu the uniform mixed ligand of organic precursor is obtained；
(2) compound precursor object is placed in nitrogen or inert atmosphere and is heat-treated, obtain combination electrode material.
4. the preparation method of combination electrode material according to claim 3, which is characterized in that the metal soluble-salt is nitre
Sour nickel and ferric nitrate, the organic carbon source are glucose, and the nitrogen source is melamine.
5. the preparation method of combination electrode material according to claim 4, which is characterized in that the precursor solution includes
0.145~0.435g Nickelous nitrate hexahydrate, 0.202~0.606g Fe(NO3)39H2O, 0.05g glucose, 4g melamine and
20mL distilled water.
6. the preparation method of combination electrode material according to claim 5, which is characterized in that the precursor solution includes
0.145g Nickelous nitrate hexahydrate, 0.606g Fe(NO3)39H2O, 0.05g glucose, 4g melamine and 20mL distilled water.
7. according to the preparation method of any one of claim 3~6 combination electrode material, which is characterized in that the step (1)
In, the temperature of evaporation is 40 DEG C.
8. the preparation method of combination electrode material according to claim 7, which is characterized in that described lazy in the step (2)
Property atmosphere include argon gas, the process of thermal treatment parameter setting are as follows: first stage calcination temperature is 500 DEG C, and calcination time is
120min, heating-up time 500min；Second stage calcination temperature is 800 DEG C, calcination time 120min, and the heating-up time is
150min。
9. application of the combination electrode material according to claim 1 or 2 in full water-splitting or zinc-air battery.
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