CN110783582A - Nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 110
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 103
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 229910000531 Co alloy Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 36
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 35
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 239000013110 organic ligand Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000001301 oxygen Substances 0.000 claims abstract description 7
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 105
- 239000000243 solution Substances 0.000 claims description 33
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- 239000000956 alloy Substances 0.000 claims description 4
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- 230000000630 rising effect Effects 0.000 claims description 2
- 229910017061 Fe Co Inorganic materials 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
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- 238000011161 development Methods 0.000 description 7
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- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002546 FeCo Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000001420 photoelectron spectroscopy Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
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- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
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- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- CYXIENZYTDFIFC-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Fe].[Co] CYXIENZYTDFIFC-UHFFFAOYSA-N 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-M thiophene-2-carboxylate Chemical compound [O-]C(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-M 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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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
-
- 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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- 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
- H01M4/9075—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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst, and a preparation method and application thereof.A structural unit of the catalyst takes nitrogen-doped carbon nanotubes (NCNTs) as a conductive network, and iron-cobalt alloy nanoparticles coated by a nitrogen-doped ultrathin carbon layer are loaded on the carbon nanotubes; the preparation method comprises the following steps: pretreatment of the carbon nanotubes: cleaning to remove impurities on the surface of the carbon nano tube, and generating a large amount of defects and oxygen-containing surface functional groups on the surface of the carbon nano tube through acid treatment; carrying out a grafting reaction of an iron-cobalt organic ligand and melamine on the surface of the functionalized carbon nanotube; and calcining the iron-cobalt organic ligand and the melamine grafted functionalized carbon nano tube at high temperature to obtain the nitrogen-doped carbon nano tube loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation of new energy materials, namely zinc-air battery electrode materials, and particularly relates to a high-efficiency and stable zinc-air battery air electrode bifunctional catalyst, and a preparation method and application thereof.
Background
With the development of social economy and technology, people's lives become more and more intelligent, and many wearable devices are used to provide convenience for people's lives, and play an important role in aspects such as measuring physical conditions, recording physiological parameters or notifying medication time for people's health protection and driving and navigation, for example, sports bracelets and wearable devices used as medical technology carriers. Many battery products are also beginning to enter human lives widely with the advent of these devices, however, many of these batteries are environmentally hazardous and represent a significant inefficiency in practical applications.
The development of cities is closely connected with traffic, energy sources and the like, and the rapid urbanization development leads to a series of ecological environment problems in the cities. In recent years, ecological environment protection is gradually a topic which is increasingly concerned by the current society, and the damage of urban ecological environment directly influences the sustainable development of the whole ecological system and the improvement of the living quality of residents, and simultaneously poses certain threats to the physical health of the residents. China has a large population and huge resource consumption, and the problem of energy shortage is increasingly prominent at present when the industry is developed at a high speed. The sustainable development of cities and the construction of healthy cities urgently require our society to shift from fossil energy economy to clean energy economy. Therefore, in recent years, research on the acquisition, conversion, and storage of sustainable energy is actively conducted globally, and batteries have long been considered as an effective energy conversion and storage device. Taking a sports bracelet as an example, a lithium ion battery is always a power supply device of the sports bracelet. However, the common heavy metal elements such as cobalt and nickel in the lithium ion battery material are not only rare in resources and expensive, but also have adverse effects on the environment. Particularly, the synthesis of the positive electrode material requires a considerable proportion of lithium-containing precursors, and the storage capacity of lithium is very limited, so that the situation of lithium salt short supply inevitably occurs along with the rapid expansion of the application range and the demand of the lithium ion battery. In the later stage of 2015, the output of the lithium ion battery is increased due to the rapid increase of the output of electric vehicles in China, so that the price of lithium carbonate rises dramatically. Therefore, the lithium ion battery has the defects of high cost, insufficient energy density and the like, and the waste lithium ion battery contains various toxic substances and has strong corrosivity and pollution.
Zinc-air batteries have attracted considerable attention as one of the replacement technologies for lithium ion batteries. Zinc-air batteries have a very high theoretical energy density, about 5 times that of current lithium ion batteries. The price of zinc is also much lower than that of lithium, so that the cost of zinc-air batteries is much lower than that of lithium ion batteries.
The zinc-air battery eliminates toxic substances such as lead, mercury, cadmium and the like in the traditional battery, and solves the pollution problem of the traditional battery. In addition, the main reaction product after the battery is used is zinc oxide, and the recycling is convenient. Zinc-air batteries provide high energy densities for many applications. Although the battery has the advantages of early start and great potential, the current zinc-air battery has the following defects:
(1) the slow kinetics of Oxygen Evolution (OER) and oxygen reduction (ORR) reactions during the charging and discharging process are hindered, and the development of zinc-air batteries is hindered;
(2) since catalysts with higher catalytic activity towards ORR are generally detrimental to OER and vice versa. Therefore, the development of the high-efficiency and stable ORR/OER dual-function catalyst can obviously improve the efficiency of the zinc-air battery;
(3) among the non-noble metal ORR/OER dual function electrocatalysts, metals such as iron, cobalt, nickel have been widely used as catalysts for ORR and OER in alkaline environments. However, the alloyed metal nanoparticles have the problems of poor stability and significant self-aggregation (especially in harsh electrochemical environments) when subjected to the ORR and OER processes.
Disclosure of Invention
The invention aims to provide an efficient and stable ORR/OER bifunctional electrocatalyst material for a rechargeable zinc-air battery, which overcomes the defects of the zinc-air battery and effectively improves the electrochemical performance of the rechargeable zinc-air battery.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the efficient and stable ORR/OER bifunctional electrocatalyst material for the rechargeable zinc-air battery is characterized in that a structural unit of the material is a conductive network made of nitrogen-doped carbon nanotubes (NCNTs), and iron-cobalt alloy nanoparticles wrapped by a nitrogen-doped ultrathin carbon layer are loaded on the conductive network.
In order to achieve the above object, the present invention provides a method for preparing the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst supported by the nitrogen-doped carbon nanotube, which specifically comprises the following steps:
firstly, pretreatment of carbon nanotubes: cleaning to remove impurities on the surface of the carbon nano tube, and generating a large amount of defects and oxygen-containing surface functional groups on the surface of the carbon nano tube through acid treatment;
secondly, carrying out a grafting reaction of an iron-cobalt organic ligand and melamine on the surface of the functionalized carbon nanotube;
and thirdly, calcining the iron-cobalt organic ligand and the melamine grafted functional carbon nano tube at high temperature to obtain the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nano tube.
Step one, the pretreatment of the carbon nano tube is specifically as follows:
dissolving 50mg-200mg of Carbon Nanotubes (CNTs) in 5mL-10mL of acetone, stirring for 3-5h at normal temperature, washing and drying; adding the dried CNTs into a flask, and then adding 50-100mL of HNO
3And H
2O
2Mixing the above materials, heating to 60-80 deg.C, refluxing, stirring for 3-5 hr, cooling, vacuum filtering, washing the filter cake with deionized water to neutrality, and drying in a vacuum oven at 50-80 deg.CAnd (3) grinding the dried functionalized CNTs sample for later use under constant weight.
The grafting reaction of the organic ligand of di-iron-cobalt and melamine on the surface of the functionalized carbon nano tube specifically comprises the following steps: under the condition of stirring, 30-100mg of FePc (phthalocyaniron) and 30-100mg of CoPc (phthalocyancobalt) material are ultrasonically dispersed in N, N Dimethylformamide (DMF) to obtain 0.2-1mg of mL
-1The FePc-CoPc/DMF mixture is added into 200-300mL of the mixture with the concentration of 0.2-1mg mL
-1The obtained mixed solution is stirred and reacted for 3 to 6 hours at room temperature in the CNTs/DMF solution. And then adding 1-3g of melamine, continuing ultrasonic dispersion treatment for 1-3h, carrying out suction filtration and purification on the obtained product, removing a DMF solution, and finally drying in a vacuum oven at 60-80 ℃ to constant weight, wherein FePc and CoPc are adsorbed on the surface of CNTs through pi-pi bonds, and hydrogen bonds and amino bonds in melamine molecules interact with oxygen-containing functional groups in the CNTs to form protonated amine and carboxyl ionic bonds which are adsorbed on the surface of the CNTs.
Calcining the functionalized carbon nano tube grafted by the ferroferric oxide-cobalt organic ligand and the melamine at high temperature to obtain the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nano tube, which comprises the following steps: putting the obtained solid powder material into a quartz boat, and calcining in a tube furnace in two sections under the calcining conditions: heating from room temperature to 400-450 ℃ in an inert gas or reducing gas atmosphere at a heating rate of 1-3 ℃ for min
-1Keeping the temperature for 2-4h, and then keeping the temperature for 5-10 min
-1The temperature rising rate is up to 700-850 ℃, the temperature is kept for 1-3h, and finally the temperature is reduced to the room temperature to obtain black solid powder which is 0.5-1M H
2SO
4Soaking in the solution for 24-36h to remove the surface unreacted FePc, CoPc and melamine.
Preferably, in the first step, the mass percent of the hydrogen peroxide is 10-35%, the mass percent of the nitric acid is 5-10%, and the volume ratio of the 5-10% nitric acid to the 10-35% hydrogen peroxide is 2-3: 1;
preferably, in the second step, the mass ratio of phthalocyanferric to phthalocyancobalt is 1-3.5: 1-3.5;
preferably, in the third step, the inert gas or the reducing gasThe body atmosphere is N
2、Ar、N
2And H
2Mixed gases or Ar and H
2And (4) mixing the gases.
The nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nano tube takes the nitrogen-doped CNTs as a conductive framework, has a stable structure, avoids the agglomeration of iron-cobalt alloy nano particles, is beneficial to the transmission of electrons, is wrapped by the nitrogen-doped ultrathin carbon layer, does not influence the electron transmission, provides more catalytic active sites, enables the electrocatalytic performance of the iron-cobalt alloy to be exerted to the maximum extent, and has good ORR and OER bifunctional catalytic performance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nanotube has a large specific surface area, a hierarchical pore structure, abundant active sites and strong oxygen adsorption capacity on the surface;
(2) in the nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst loaded by the nitrogen-doped carbon nanotube, the iron-cobalt alloy nanoparticles are coated by the ultrathin nitrogen-doped graphitized carbon layer, so that the alloy nanoparticles are prevented from being directly corroded by electrolyte, the efficient ORR circulation stability of the alloy nanoparticles is kept, and the methanol interference resistance and CO toxicity resistance of the alloy nanoparticles are improved;
(3) the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nanotube has high-efficiency and stable ORR/OER electrocatalytic performance. And the zinc-air battery formed by the electrode material has good discharge performance when being bent, and shows good application prospect in flexible wearable electronic equipment.
Drawings
FIG. 1 shows Fe in example 1
1.2Scanning electron microscope images of Co @ NC/NCNTs;
FIG. 2 shows Fe in example 1
1.2Transmission electron microscopy images of Co @ NC/NCNTs;
FIG. 3 shows Fe in example 1
1.2A high resolution transmission electron micrograph of Co @ NC/NCNTs;
FIG. 4 is a graph of ORR LSV of the samples of example 1 and comparative examples 1, 2;
FIG. 5 is a graph of OER LSV for the samples of example 1 and comparative examples 1, 2.
Detailed Description
In order to make the objects, technical schemes and beneficial technical effects of the present invention clearer, the principle of the rechargeable zinc-air battery, the preparation method of the dual-function catalyst and the beneficial effects thereof according to the present invention are described in detail below with reference to the accompanying drawings and the specific embodiments. It should be understood that the embodiments described in this specification are only for the purpose of illustrating the invention and are not to be construed as limiting the invention, and the parameters, proportions and the like of the embodiments may be suitably selected without materially affecting the results.
Example 1: nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst (Fe) loaded by nitrogen-doped carbon nano tube
1.2Co @ NC/NCNTs) synthesis:
(1) pretreatment of the carbon nanotubes:
dissolving 100mg of Carbon Nanotubes (CNTs) in 10mL of acetone, stirring for 3h at normal temperature, washing and drying; the dried CNTs were added to a flask, followed by 100mL of 2:1 by volume 10% HNO
3And 10% of H
2O
2And (3) mixing the solution, starting stirring, heating to 60 ℃, refluxing and stirring for 5h, cooling, performing suction filtration, washing a filter cake to be neutral by using deionized water, drying in a vacuum oven at 50 ℃ to constant weight, and grinding the dried functionalized CNTs sample for later use.
(2) The grafting reaction of the iron-cobalt organic ligand and melamine on the surface of the functionalized carbon nanotube:
under stirring, 50mg of FePc (phthalocyaniron) and 50mg of CoPc (phthalocyancobalt) material were ultrasonically dispersed in N, N Dimethylformamide (DMF) to obtain 0.4mg mL
-1The mixture of FePc-CoPc/DMF was added to 250mL of a 0.4 mg/mL solution
-1The obtained mixture is stirred and reacted for 6 hours at room temperature in the CNTs/DMF solution. Then adding 3g of melamine, continuing ultrasonic dispersion treatment for 1h, carrying out suction filtration and purification on the obtained product, removing DMF solution, and finallyThen dried in a vacuum oven at 80 ℃ to constant weight.
(3) Calcining the iron-cobalt organic ligand and the melamine grafted functionalized carbon nanotube at high temperature to obtain the nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst:
putting the obtained solid powder material into a quartz boat, and calcining in a tube furnace in two sections under the calcining conditions: in N
2Heating to 420 deg.C from room temperature in gas atmosphere at a heating rate of 3 deg.C for min
-1Keeping the temperature for 2h, and then keeping the temperature for 5 ℃ for min
-1Heating to 750 deg.C, maintaining for 1 hr, and cooling to room temperature to obtain black solid powder at 0.5M H
2SO
4Soaking in the solution for 24h to remove the surface unreacted FePc, CoPc and melamine.
The detection of photoelectron spectroscopy results in that the Fe of the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nanotube in example 1: the atomic ratio of Co is 1.2: 1.
the morphology of the Fe1.2Co @ NC/NCNTs material obtained in example 1 was analyzed by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and as a result, the CNTs surface was rough and the nanoparticles were supported on the CNTs surface as shown in FIG. 1. FIG. 2 is a TEM image of Fe1.2Co @ NC/NCNTs material, which fully demonstrates that the nano-particles are loaded on the surface of CNTs, and the result of enlarging TEM is shown in FIG. 3, and clearly shows that the ultra-thin carbon layer wraps the metal nano-particles and is loaded on the surface of CNTs.
Evaluation of bifunctional catalytic Performance:
all electrochemical tests were performed using an electrochemical workstation model CHI 760E equipped with a PINE rotating disk electrode test system and were performed at room temperature.
Preparation of a working electrode: before using a Rotating Disk Electrode (RDE), i.e. a glassy carbon electrode (GCE, d ═ 0.5cm), Al was first used
2O
3Grinding the surface of the electrode on polishing cloth to a mirror surface by using powder, then washing the electrode with distilled water for several times, ultrasonically oscillating for 10s, and drying the electrode at room temperature for later use. Accurately weighed catalyst powder (4.0mg) was dispersed in a mixed solution comprising 13 μ L of an Afion solutionLiquid (5 wt.%), 705 μ L of ultrapure water and 282 μ L of isopropanol solution, followed by ultrasonic dispersion for 60min to form a homogeneous mixture. Finally, 10 mu L of the prepared ink is uniformly dripped on the surface of GCE and naturally dried, so that the working electrode used for testing is obtained. The loading of the catalyst on the surface of the electrode is about 0.2mg cm
-2. As a control experiment, a commercial 20 wt.% Pt/C catalyst was also prepared and tested using the same electrode preparation method.
And (3) electrochemical performance testing: a standard three-electrode electrochemical test system was used in the test procedure, where the counter electrode was Pt mesh and the reference electrode was Saturated Calomel Electrode (SCE) and the working electrode prepared above.
The LSV curve of the Fe1.2Co @ NC/NCNTs sample with a commercial 20 wt.% Pt/C catalyst in a 0.1M KOH solution saturated with O2 at 1600rpm was tested using a Rotating Disk Electrode (RDE) and the results are shown in FIG. 4. The Fe1.2Co @ NC/NCNTs sample exhibited very high ORR electrocatalytic activity at 0.842 and 0.82Vvs. RHE starting and half-wave potentials, respectively, which was close to that of the commercial Pt/C catalyst tested under the same conditions (0.964 and 0.858V vs. RHE starting and half-wave potentials, respectively). At potentials below 0.8V, the Fe1.2Co @ NC/NCNTs sample showed the highest limiting current density, even higher than the commercial Pt/C catalyst, indicating that the material has faster reaction kinetics during ORR electrocatalysis.
It is well known that air electrode catalysts for rechargeable Zn-air cells require dual function ORR/OER catalytic performance. Thus, different samples prepared were further evaluated for OER catalytic activity in O2 saturated 0.1M KOH electrolyte, with a commercial 20 wt.% Ir/C catalyst tested under the same conditions as a comparative reference. As shown in FIG. 5, which is an LSV curve of OER catalytic performance for various samples, the Fe1.2Co @ NC/NCNTs sample exhibited the lowest OER onset overpotential (1.43V). At a current density of 10mAcm
-2The OER overpotential was only 355 mV. The overpotential was 20mV lower than that of the commercial Ir/C catalyst under the same test conditions, which means that the Fe1.2Co @ NC/NCNTs sample had excellent OER electrocatalytic activity.
Comparative example 1: synthesizing a nitrogen-doped carbon-coated iron bifunctional catalyst (Fe @ NC/NCNTs) loaded by a nitrogen-doped carbon nanotube:
(1) pretreatment of the carbon nanotubes:
dissolving 100mg of Carbon Nanotubes (CNTs) in 10mL of acetone, stirring for 3h at normal temperature, washing and drying; the dried CNTs were added to a flask, followed by 100mL of 2:1 by volume 10% HNO
3And 10% of H
2O
2And (3) mixing the solution, starting stirring, heating to 60 ℃, refluxing and stirring for 5h, cooling, performing suction filtration, washing a filter cake to be neutral by using deionized water, drying in a vacuum oven at 50 ℃ to constant weight, and grinding the dried functionalized CNTs sample for later use.
(2) Grafting reaction of the iron organic ligand and melamine on the surface of the functionalized carbon nanotube:
under stirring, 100mg of FePc (phthalocyaniron) material was ultrasonically dispersed in N, N Dimethylformamide (DMF) to obtain 0.4mg mL
-1The mixture was added to 250mL of a 0.4 mg/mL FePc/DMF mixture
-1The obtained mixture is stirred and reacted for 6 hours at room temperature in the CNTs/DMF solution. Then adding 3g of melamine, continuing ultrasonic dispersion treatment for 1h, carrying out suction filtration and purification on the obtained product, removing DMF solution, and finally drying in a vacuum oven at 80 ℃ to constant weight.
(3) Calcining the functionalized carbon nano tube grafted by the iron organic ligand and the melamine at high temperature to obtain the nitrogen-doped carbon nano tube loaded nitrogen-doped carbon-coated iron bifunctional catalyst:
putting the obtained solid powder material into a quartz boat, and calcining in a tube furnace in two sections under the calcining conditions: in N
2Heating to 420 deg.C from room temperature in gas atmosphere at a heating rate of 3 deg.C for min
-1Keeping the temperature for 2h, and then keeping the temperature for 5 ℃ for min
-1Heating to 750 deg.C, maintaining for 1 hr, and cooling to room temperature to obtain black solid powder at 0.5M H
2SO
4And soaking in the solution for 24 hours to remove the unreacted FePc and melamine on the surface.
The ORR performance of the Fe @ NC/NCNTs obtained in comparative example 1 is shown in FIG. 4, curve 2, and is inferior to that of the Fe1.2Co @ NC/NCNTs sample obtained in example 1, and the OER performance of the Fe @ NC/NCNTs obtained in comparative example 1 is shown in FIG. 5, curve 2, and is also inferior to that of the Fe1.2Co @ NC/NCNTs sample obtained in example 1.
Comparative example 2: synthesizing a nitrogen-doped carbon-coated cobalt bifunctional catalyst (Co @ NC/NCNTs) loaded by a nitrogen-doped carbon nanotube:
(1) pretreatment of the carbon nanotubes:
dissolving 100mg of Carbon Nanotubes (CNTs) in 10mL of acetone, stirring for 3h at normal temperature, washing and drying; the dried CNTs were added to a flask, followed by 100mL of 2:1 by volume 10% HNO
3And 10% of H
2O
2And (3) mixing the solution, starting stirring, heating to 60 ℃, refluxing and stirring for 5h, cooling, performing suction filtration, washing a filter cake to be neutral by using deionized water, drying in a vacuum oven at 50 ℃ to constant weight, and grinding the dried functionalized CNTs sample for later use.
(2) The grafting reaction of the cobalt organic ligand and melamine on the surface of the functionalized carbon nanotube:
100mg of CoPc (cobalt phthalocyanine) material was ultrasonically dispersed in N, N Dimethylformamide (DMF) with stirring to obtain 0.4mg mL
-1The mixture of CoPc and DMF was added to 250mL of a 0.4 mg/mL solution
-1The obtained mixture is stirred and reacted for 6 hours at room temperature in the CNTs/DMF solution. Then adding 3g of melamine, continuing ultrasonic dispersion treatment for 1h, carrying out suction filtration and purification on the obtained product, removing DMF solution, and finally drying in a vacuum oven at 80 ℃ to constant weight.
(3) Calcining the functionalized carbon nano tube grafted by the cobalt organic ligand and the melamine at high temperature to obtain the nitrogen-doped carbon nano tube loaded nitrogen-doped carbon-coated cobalt bifunctional catalyst:
putting the obtained solid powder material into a quartz boat, and calcining in a tube furnace in two sections under the calcining conditions: in N
2Heating to 420 deg.C from room temperature in gas atmosphere at a heating rate of 3 deg.C for min
-1Keeping the temperature for 2h, and then keeping the temperature for 5 ℃ for min
-1Heating to 750 deg.C, maintaining for 1 hr, and cooling to room temperature to obtain black solid powder at 0.5M H
2SO
4And soaking in the solution for 24h to remove unreacted CoPc and melamine on the surface.
The ORR performance of the Co @ NC/NCNTs obtained in comparative example 1 is shown in FIG. 4, Curve 1, and is inferior to that of the Fe1.2Co @ NC/NCNTs sample obtained in example 1, and the OER performance of the Co @ NC/NCNTs obtained in comparative example 1 is shown in FIG. 5, Curve 1, and is also inferior to that of the Fe1.2Co @ NC/NCNTs sample obtained in example 1.
Example 2: nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst (Fe) loaded by nitrogen-doped carbon nano tube
2.8Co @ NC/NCNTs) synthesis:
(1) pretreatment of the carbon nanotubes:
dissolving 200mg of Carbon Nanotubes (CNTs) in 10mL of acetone, stirring for 5h at normal temperature, washing and drying; the dried CNTs were added to a flask, followed by 100mL of 10% HNO at a 3:1 volume ratio
3And 35% H
2O
2And (3) mixing the solution, starting stirring, heating to 80 ℃, refluxing and stirring for 5h, cooling, performing suction filtration, washing a filter cake to be neutral by using deionized water, drying in a vacuum oven at 80 ℃ to constant weight, and grinding the dried functionalized CNTs sample for later use.
(2) The grafting reaction of the iron-cobalt organic ligand and melamine on the surface of the functionalized carbon nanotube:
under stirring, 100mg of FePc (phthalocyaniron) and 30mg of CoPc (phthalocyancobalt) material were ultrasonically dispersed in N, N Dimethylformamide (DMF) to obtain 1mg mL
-1The mixture of FePc-CoPc/DMF was added to 300mL of a 0.2 mg/mL solution
-1The obtained mixture is stirred and reacted for 6 hours at room temperature in the CNTs/DMF solution. Then adding 3g of melamine, continuing ultrasonic dispersion treatment for 3h, carrying out suction filtration and purification on the obtained product, removing DMF solution, and finally drying in a vacuum oven at 80 ℃ to constant weight.
(3) Calcining the iron-cobalt organic ligand and the melamine grafted functionalized carbon nanotube at high temperature to obtain the nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst:
putting the obtained solid powder material into a quartz boat, and calcining in a tube furnace in two sections under the calcining conditions: heating to 450 deg.C from room temperature in Ar gas atmosphere at a heating rate of 3 deg.C for min
-1Keeping the temperature for 4 hours, and thenAt 10 ℃ for min
-1Heating to 850 deg.C, maintaining for 3 hr, cooling to room temperature to obtain black solid powder, and heating to 1M H deg.C
2SO
4And soaking in the solution for 36h to remove the unreacted FePc, CoPc and melamine on the surface.
The detection of photoelectron spectroscopy results in that the Fe of the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nanotube in example 2: the atomic ratio of Co is 2.8: 1.
the Fe2.8Co @ NC/NCNTs sample exhibited very high ORR electrocatalytic activity at an onset potential and a half-wave potential of 0.839 and 0.818V vs. RHE, respectively, which was close to that of a commercial Pt/C catalyst tested under the same conditions (onset potential and half-wave potential of 0.964 and 0.858V vs. RHE, respectively). The Fe1.2Co @ NC/NCNTs sample exhibited a low OER onset overpotential (1.429V). At a current density of 10mA cm
-2The OER overpotential is only 357 mV.
Example 3: nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst (FeCo) loaded by nitrogen-doped carbon nano tube
2.5@ NC/NCNTs) synthesis:
(1) pretreatment of the carbon nanotubes:
dissolving 50mg of Carbon Nanotubes (CNTs) in 5mL of acetone, stirring for 3h at normal temperature, washing and drying; the dried CNTs were added to a flask followed by 50mL of 2:1 by volume 5% HNO
3And 10% of H
2O
2And (3) mixing the solution, starting stirring, heating to 60 ℃, refluxing and stirring for 3h, cooling, performing suction filtration, washing a filter cake to be neutral by using deionized water, drying in a vacuum oven at 50 ℃ to constant weight, and grinding the dried functionalized CNTs sample for later use.
(2) The grafting reaction of the iron-cobalt organic ligand and melamine on the surface of the functionalized carbon nanotube:
under stirring, 30mg of FePc (phthalocyaniron) and 100mg of CoPc (phthalocyancobalt) material were ultrasonically dispersed in N, N Dimethylformamide (DMF) to obtain 0.2mg mL
-1The mixture of FePc-CoPc/DMF was added to 200mL of a 0.25 mg/mL solution
-1The obtained mixture is stirred and reacted for 3 hours at room temperature in the CNTs/DMF solution. 1g of melamine was then added and the ultrasonic separation was continuedDispersing for 1h, filtering and purifying the obtained product, removing DMF solution, and finally drying in a vacuum oven at 80 ℃ to constant weight.
(3) Calcining the iron-cobalt organic ligand and the melamine grafted functionalized carbon nanotube at high temperature to obtain the nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst:
putting the obtained solid powder material into a quartz boat, and calcining in a tube furnace in two sections under the calcining conditions: in N
2And H
2Heating to 400 deg.C from room temperature in mixed gas atmosphere at a heating rate of 1 deg.C for min
-1Keeping the temperature for 2h, and then keeping the temperature for 5 ℃ for min
-1Heating to 850 deg.C, keeping the temperature for 1h, and cooling to room temperature to obtain black solid powder at 0.5MH
2SO
4Soaking in the solution for 24h to remove the surface unreacted FePc, CoPc and melamine.
The detection of photoelectron spectroscopy results in that the Fe of the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nanotube in example 3: the atomic ratio of Co is 1: 2.5.
FeCo
2.5the @ NC/NCNTs sample exhibited very high ORR electrocatalytic activity at 0.837 and 0.815V vs. RHE for the onset and half-wave potentials, respectively, which was close to that of the commercial Pt/C catalyst tested under the same conditions (0.964 and 0.858V vs. RHE for the onset and half-wave potentials, respectively). FeCo
2.5The @ NC/NCNTs sample exhibited a low OER onset overpotential (1.428V). At a current density of 10mA cm
-2The OER overpotential is only 359 mV.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by a nitrogen-doped carbon nanotube is characterized in that a structural unit of the catalyst is that nitrogen-doped carbon nanotubes (NCNTs) are used as a conductive network, and iron-cobalt alloy nanoparticles coated by a nitrogen-doped ultrathin carbon layer are loaded on the catalyst.
2. The preparation method of the nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst of claim 1, which is characterized by comprising the following steps:
firstly, pretreatment of carbon nanotubes: cleaning to remove impurities on the surface of the carbon nano tube, and generating a large amount of defects and oxygen-containing surface functional groups on the surface of the carbon nano tube through acid treatment;
secondly, carrying out a grafting reaction of an iron-cobalt organic ligand and melamine on the surface of the functionalized carbon nanotube;
and thirdly, calcining the iron-cobalt organic ligand and the melamine grafted functional carbon nano tube at high temperature to obtain the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nano tube.
3. The preparation method of the nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst according to claim 2, which is characterized in that: the pretreatment of the carbon nanotubes in the first step is specifically as follows: dissolving 50mg-200mg of Carbon Nanotubes (CNTs) in 5mL-10mL of acetone, stirring for 3-5h at normal temperature, washing and drying; adding the dried CNTs into a flask, and then adding 50-100mL of HNO
3And H
2O
2And (3) mixing the solution, starting stirring, heating to 60-80 ℃, refluxing and stirring for 3-5h, cooling, performing suction filtration, washing a filter cake to be neutral by using deionized water, drying in a vacuum oven at 50-80 ℃ to constant weight, and grinding the dried functionalized CNTs sample for later use.
4. The preparation method of the nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst according to claim 2, which is characterized in that: the iron-cobalt organic ligand and the melamine in the second stepThe grafting reaction on the surface of the functionalized carbon nanotube specifically comprises the following steps: under the condition of stirring, 30-100mg of FePc (phthalocyaniron) and 30-100mg of CoPc (phthalocyancobalt) material are ultrasonically dispersed in N, N Dimethylformamide (DMF) to obtain 0.2-1mg of mL
-1The FePc-CoPc/DMF mixture is added into 200-300mL of the mixture with the concentration of 0.2-1mg mL
-1The obtained mixed solution is stirred and reacted for 3 to 6 hours at room temperature in the CNTs/DMF solution. Then adding 1-3g of melamine, continuing ultrasonic dispersion treatment for 1-3h, carrying out suction filtration and purification on the obtained product, removing DMF solution, and finally drying in a vacuum oven at 60-80 ℃ to constant weight.
5. The preparation method of the nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst according to claim 2, which is characterized in that: the method comprises the following steps of calcining the iron-cobalt organic ligand and the melamine grafted functionalized carbon nanotube at high temperature to obtain the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst loaded by the nitrogen-doped carbon nanotube, wherein the nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst comprises the following specific steps: putting the obtained solid powder material into a quartz boat, and calcining in a tube furnace in two sections under the calcining conditions: heating from room temperature to 400-450 ℃ in an inert gas or reducing gas atmosphere at a heating rate of 1-3 ℃ for min
-1Keeping the temperature for 2-4h, and then keeping the temperature for 5-10 min
-1The temperature rising rate is up to 700-850 ℃, the temperature is kept for 1-3h, and finally the temperature is reduced to the room temperature to obtain black solid powder which is 0.5-1M H
2SO
4Soaking in the solution for 24-36h to remove the surface unreacted FePc, CoPc and melamine.
6. The preparation method of the nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst according to claim 3, wherein in the first step, the mass percent of hydrogen peroxide is 10-35%, the mass percent of nitric acid is 5-10%, and the volume ratio of 5-10% nitric acid to 10-35% hydrogen peroxide is 2-3%.
7. The method for preparing the nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst according to claim 3, wherein in the second step, the mass ratio of phthalocyaniron to phthalocyancobalt is 1-3.5: 1-3.5.
8. The method for preparing the N-doped carbon nanotube supported N-doped carbon coated Fe-Co alloy bifunctional catalyst as claimed in claim 3, wherein preferably, in the third step, the inert gas or reducing gas atmosphere is N
2、Ar、N
2And H
2Mixed gases or Ar and H
2And (4) mixing the gases.
9. The application of the nitrogen-doped carbon nanotube-supported nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst of claim 1 as an air electrode catalyst of a zinc-air battery.
10. The use of a rechargeable zinc-air battery assembled with the nitrogen-doped carbon nanotube-supported nitrogen-doped carbon-coated iron-cobalt alloy bifunctional catalyst of claim 1 as a wearable device.
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