CN108511766B - Bifunctional electrocatalyst and preparation method thereof - Google Patents

Bifunctional electrocatalyst and preparation method thereof Download PDF

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CN108511766B
CN108511766B CN201810371766.9A CN201810371766A CN108511766B CN 108511766 B CN108511766 B CN 108511766B CN 201810371766 A CN201810371766 A CN 201810371766A CN 108511766 B CN108511766 B CN 108511766B
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stirring
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bifunctional electrocatalyst
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CN108511766A (en
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何传新
裴蕾
李国栋
柴晓燕
范梁栋
张黔玲
刘剑洪
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Shenzhen University
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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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a bifunctional electrocatalyst, a preparation method and a preparation method thereofThe method comprises the following steps: adding an acrylonitrile oligomer into a solvent, then adding a hydroxylated multi-walled carbon nanotube, and stirring for 1-2 hours to obtain a pasty suspension; adding a metal salt solution into the pasty turbid liquid while stirring, transferring the turbid liquid into an oil bath after stirring for 0.5 to 1.5 hours, and performing stirring for 30 to 50 hoursoStirring for 2-5 hours under the atmosphere of C; removing the solvent in the mixture obtained in the step to obtain a solid mixture; under the protection of inert atmosphere, the solid mixture is subjected to reaction at 800-1000 DEG CoAnd calcining for 0.5-1.5 hours under the condition of C to obtain a calcined product, and grinding the calcined product to obtain the bifunctional electrocatalyst. The invention synthesizes the high-performance ORR and OER bifunctional electrocatalyst by using the carbon nano tube and the acrylonitrile oligomer as raw materials. The synthesis method is simple, environment-friendly and low in cost.

Description

Bifunctional electrocatalyst and preparation method thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a bifunctional electrocatalyst and a preparation method thereof.
Background
The slow and complex oxygen electrodes of the fuel cell cathode Oxygen Reduction Reaction (ORR) and the water electrolysis device anode Oxygen Evolution Reaction (OER) have limited their commercial application in fuel cells and water electrolysis devices. On the other hand, the cathode reaction of a metal-air battery is mainly an oxygen reaction, including an oxygen reduction reaction at the time of battery discharge and an oxygen evolution reaction at the time of battery charge. Due to the kinetically slow nature of the oxygen reaction process, the use of a catalyst greatly enhances the efficiency of the oxygen reaction.
The current researchers are not limited to research a single catalyst, and finding out the cheap and excellent ORR and OER bifunctional catalyst has important significance for realizing the long-term development of the metal-air battery. The existing noble metal Pt catalyst can catalyze the oxygen reduction reaction with high efficiency, but has weak catalytic capability in the oxygen precipitation reaction, and cannot be applied to a metal-air battery as a bifunctional catalyst.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a bifunctional electrocatalyst and a preparation method thereof, which aims to solve the problem that the existing catalyst cannot be applied to a metal-air battery as an ORR and OER bifunctional catalyst.
The technical scheme of the invention is as follows:
a method of preparing a bifunctional electrocatalyst, comprising:
step A, adding an acrylonitrile oligomer into a solvent, then adding a hydroxylated multi-walled carbon nanotube, and stirring for 1-2 hours to obtain a pasty suspension;
and step B, adding a metal salt solution into the pasty turbid liquid while stirring, transferring the turbid liquid into an oil bath for 30-50 hours after stirring for 0.5-1.5 hoursoStirring for 2-5 hours under the atmosphere of C;
step C, removing the solvent in the mixture obtained in the step B to obtain a solid mixture;
step D, under the protection of inert atmosphere, enabling the solid mixture to be at 800-1000 DEGoAnd calcining for 0.5-1.5 hours under the condition of C to obtain a calcined product, and grinding the calcined product to obtain the bifunctional electrocatalyst.
The preparation method of the bifunctional electrocatalyst is characterized in that in the step A, the molecular weight of the acrylonitrile oligomer is 200-700.
The preparation method of the bifunctional electrocatalyst comprises the step A, wherein the mass ratio of the acrylonitrile oligomer to the hydroxylated multi-walled carbon nanotube is 1-10.
In the step B, the metal salt is one or two of ferric chloride and cobalt chloride.
In the step B, the mass ratio of the hydroxylated multi-walled carbon nanotube to the metal ions in the metal salt is 0.3-0.4.
The preparation method of the bifunctional electrocatalyst, wherein the step C comprises: placing the mixture obtained in the step B in a temperature range of 70-90 DEG CoC, removing most of solvent by magnetic rotary evaporation in an oil bath atmosphere; then transferring the mixture into a vacuum drying oven at 60-80 DEG CoAnd (C) evaporating the residual solvent to dryness to obtain a solid mixture.
The preparation method of the bifunctional electrocatalyst comprises the steps of carrying out magnetic rotary evaporation for 3-5 hours, and carrying out vacuum drying for 6-8 hours.
In the step D, the calcination process is performed by adopting a programmed temperature rise method: the first stage heating rate is 5oC·min~1To 300oC is kept warm for 20 minutes, and the second-stage heating rate is 2oC·min~1To 800 to 1000oCalcining the C for 0.5 to 1.5 hours.
The preparation method of the bifunctional electrocatalyst is characterized in that in the step D, the temperature is 900 DEGoAnd C, calcining for 1 hour to obtain the calcined product.
The invention relates to a bifunctional electrocatalyst, which is prepared by the preparation method of the bifunctional electrocatalyst.
Has the advantages that: the invention synthesizes the high-performance ORR and OER bifunctional electrocatalyst by using hydroxylated multi-wall carbon nanotubes and acrylonitrile oligomer as raw materials. The synthesis method is simple, environment-friendly and low in cost. The catalyst synthesized by the method has ORR activity comparable to that of a commercial Pt/C catalyst under alkaline conditions, and OER activity superior to that of commercial IrO2Has good application prospect.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst obtained in example 1 of the present invention.
FIG. 2 is a graph showing the L SV test results of the oxygen reduction reaction of the catalyst obtained in example 1 and a commercial Pt/C catalyst in a 0.1M KOH solution.
FIG. 3 is a L SV test chart of the oxygen evolution reaction of the catalyst obtained in example 1 and the commercial Pt/C catalyst in 0.1M KOH solution in accordance with the present invention.
FIG. 4 shows the results of the catalytic conversion of the catalyst obtained in example 1 in the present invention in O2Test plots of the oxygen reduction reaction L SV in saturated 0.1M KOH solution at various speeds.
FIG. 5 shows the results of the catalytic conversion of the catalyst obtained in example 1 in the present invention in O2K-L plot of oxygen reduction reaction in saturated 0.1M KOH solution at different rotation speeds.
Fig. 6 is a graph showing oxygen reduction reaction and oxygen evolution performance tests of ANT-CNT-Fe catalysts and ANT-CNT-Co catalysts prepared in examples 2 and 3 of the present invention, compared to a commercial Pt/C catalyst.
Detailed Description
The invention provides a bifunctional electrocatalyst and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a bifunctional electrocatalyst, which comprises the following steps:
step A, adding an acrylonitrile oligomer into a solvent, then adding a hydroxylated multi-walled carbon nanotube, and stirring for 1-2 hours to obtain a pasty suspension;
and step B, adding a metal salt solution into the pasty turbid liquid while stirring, transferring the turbid liquid into an oil bath for 30-50 hours after stirring for 0.5-1.5 hoursoStirring for 2-5 hours under the atmosphere of C;
step C, removing the solvent in the mixture obtained in the step B to obtain a solid mixture;
step D, keeping the solid mixture in inert atmosphereUnder protection, the temperature is in the range of 800-1000oAnd calcining for 0.5-1.5 hours under the condition of C to obtain a calcined product, and grinding the calcined product to obtain the bifunctional electrocatalyst.
The invention synthesizes the high-performance ORR and OER bifunctional catalyst by using the hydroxylated multi-wall carbon nano-tube and the acrylonitrile oligomer as raw materials. The synthesis method is simple, environment-friendly and low in cost. The dual-function catalyst synthesized by the method has the advantages that the ORR activity is comparable to that of a commercial Pt/C catalyst under the alkaline condition, and the OER activity is superior to that of commercial IrO2Has good application prospect.
The step A specifically comprises the following steps: firstly, dissolving acrylonitrile oligomer into a solvent (such as absolute ethyl alcohol), then adding a hydroxylated multi-walled carbon nanotube, and stirring for 1-2 hours to obtain a black pasty suspension. In order to ensure a better stirring effect, a magnetic stirring device is adopted for stirring, the stirring speed is not too fast or too slow, 200-500 rpm is preferred, and the preferred rotating speed is 300 rpm.
The acrylonitrile oligomer (ANT, Chinese patent CN 102212965A) is a polymer, is a light yellow liquid at room temperature, is prepared by a free radical telomerization method, and has the advantages of simple preparation method and environmental friendliness. The acrylonitrile oligomer has better ORR catalytic performance after high-temperature sintering, and the ANT is used as a doping agent and a liquid carbon precursor, so that the N, S double-doped catalyst can be prepared in one step, and the specific liquid property of the catalyst can be in close contact with the hydroxylated multi-wall carbon nanotube and the metal salt. Furthermore, the high nitrogen content and graphitization ability of ANT is also one of the reasons why ANT after calcination has better ORR catalytic performance. The liquid polymer is therefore an excellent carbon precursor. Preferably, the molecular weight of the acrylonitrile oligomer is between 200 and 700.
The carbon nanotube has less surface defects, which is not favorable for attaching other particles. After acidification, a part of hydroxyl groups and other groups can be generated, and the surface groups are favorable for other species to react with the carbon nanotubes or directly serve as a reaction substrate. Therefore, the invention synthesizes the bifunctional electrocatalyst by using the hydroxylated multi-wall carbon nano-tube as a raw material. Preferably, the hydroxylated multi-wall carbon nanotube has the model of XFM05, the CAS number of 1333-86-4, the purity of more than 95%, the length of 0.5-2 microns and the hydroxylation content of 5.58 wt%.
Preferably, the mass ratio of the acrylonitrile oligomer to the hydroxylated multi-wall carbon nanotube is 1-10, more preferably 1, and the performance of the target product prepared under the ratio is optimal.
The step B specifically comprises the following steps: dropwise adding a metal salt solution (such as a metal salt ethanol solution) into the pasty suspension while stirring, ultrasonically stirring for 0.5-1.5 hours (such as 1 hour), transferring into an oil bath, and keeping the temperature for 30-50 hoursoC (e.g. 40)oC) Stirring for 2-5 hours in the atmosphere.
Preferably, the mass ratio of the hydroxylated multi-wall carbon nanotube to the metal ions in the metal salt is 0.3-0.4. This is because hydroxylated multi-walled carbon nanotubes are, on the one hand, carriers for the active components, encapsulated by polymers (i.e. acrylonitrile oligomers) and embedded with metal particles, and, on the other hand, increase the conductivity of the catalyst. And adding metallic iron or cobalt into the pasty suspension in the form of ferric chloride and cobalt chloride metal salt solution, wherein when the paste is calcined at high temperature, the introduced chlorine element can be volatilized in the form of gas micromolecules, and a pore structure is formed on the surface of the carbonized polymer to play a role in pore forming so as to expose more active sites. Meanwhile, the added metal salt is not too much as an active ingredient, the mass ratio of the hydroxylated multi-wall carbon nanotube to the metal ions in the metal salt is 0.3-0.4, and preferably, when the mass ratio of the hydroxylated multi-wall carbon nanotube to the metal ions in the metal salt is 0.33, the metal dispersion degree is good, and the high-efficiency exertion of the catalytic activity is facilitated.
In order to ensure that the coating effect of the polymer and the hydroxylated multi-walled carbon nanotube is good, the polymer is transferred into an oil bath for 30-50 percentoStirring for 2-5 hours under the atmosphere of C. The thickness of the polymer-coated carbon nanotube is directly influenced by the length of stirring time in the oil bath, and preferably, the polymer-coated carbon nanotube has uniform thickness and stable property after being stirred for 5 hours.
The step C specifically comprises the following steps: placing the mixture obtained in the step B in a temperature range of 70-90 DEG CoC (e.g. 80)oC) Under the oil bath atmosphere, removing most of solvent by magnetic rotary evaporation; then transferring the mixture into a vacuum drying oven at 60-80 DEG CoC (e.g. 80)oC) The remaining solvent was evaporated to dryness at temperature to give a solid mixture. Preferably, the magnetic rotary evaporation time is 3-5 hours, and the vacuum drying time is 6-8 hours.
The step D specifically comprises the following steps: transferring the solid mixture of the evaporated solvent into a clean porcelain boat, placing the porcelain boat into a tubular heating furnace, and calcining under an inert atmosphere at the calcining temperature of 800-1000 DEG CoC (e.g. 900)oC) The calcination time is 0.5 to 1.5 hours (e.g., 1 hour). The inert shielding gas is argon gas, so that side reactions such as oxidation and the like of the solid mixture in the high-temperature calcination process are avoided. Before the calcination is started, the tubular heating furnace needs to be vacuumized until the reading of a vacuum meter is about-0.1 MPa, inert protective gas is supplemented to 0 MPa, and the steps are repeated for three times. An inert protective gas atmosphere is formed to prevent the solid mixture from being oxidized during the temperature rising process. After high-temperature calcining and sintering, naturally cooling, and when the temperature of the tubular heating furnace is lower than 50 DEG CoAnd C, taking out the porcelain boat, cooling to room temperature, grinding and sieving to obtain the bifunctional electrocatalyst.
Preferably, the calcination process is performed by adopting a temperature programming mode: the first stage heating rate is 5oC·min-1To 300oC is kept warm for 20 minutes, and the second-stage heating rate is 2oC·min-1To 800 to 1000 (e.g., 900)oC) Calcining for 0.5-1.5 hours (e.g., 1 hour). The solid mixture can further remove the water combined in the molecules at a low temperature section by adopting a temperature programming method, and the damage to the activity of the catalyst caused by rapidly increasing to a higher temperature is avoided. In the process of continuously raising the temperature to a higher temperature, the adopted temperature raising speed is lower, which on one hand prevents the active components of the catalyst from volatilizing due to the sudden temperature rise, and on the other hand provides sufficient time for the mixture to carry out chemical reaction, thereby obtaining the dual-function electrocatalyst with more uniform structure and composition.
The invention also provides a bifunctional electrocatalyst, which is prepared by the preparation method of the bifunctional electrocatalyst.
The present invention is illustrated in detail below by means of several examples.
Example 1
Firstly, 25M L absolute ethyl alcohol is measured in a beaker, 0.1 g acrylonitrile oligomer (molecular weight is 500) is dripped, 0.1 g hydroxylated multi-wall carbon nano tube (model is XFM 05) is weighed after the polymer is dissolved and added in the same beaker, magnetic stirring is carried out for 1 hour to ensure that the mixture is uniformly mixed, then 330 u L0.5M ferric chloride ethanol solution and 440 u L0.375M cobalt chloride ethanol solution are dripped while stirring, the beaker is transferred to an ultrasonic machine, the metal salt solution is uniformly dispersed by ultrasonic treatment for 1 hour, then the beaker is transferred to an oil bath, 40M absolute ethyl alcohol is added in the oil bathoStirring for 5 hours under the atmosphere of C, and heating to 80 DEGoC, evaporating the solvent, wherein the solvent takes about 3 hours to evaporate. The resulting black solid mixture was then transferred to a porcelain boat and placed in a vacuum oven 80oC, drying overnight. Finally, the boat was placed in a tube furnace at 900 deg.CoAnd C, sintering at high temperature for 1 hour in an argon atmosphere, and grinding to obtain the ANT-CNT-FeCo catalyst.
The ANT-CNT-FeCo catalyst prepared in this example was characterized by scanning electron microscopy, and the results are shown in FIG. 1. It can be seen that the diameter of the carbon nanotubes coated well is 32.3nm, which is about 3 times that of the bare carbon nanotubes (diameter about 8-10 nm). It can also be seen that the coating is not very uniform, and there is a portion of the carbon nanotubes that are not coated by the polymer.
The ANT-CNT-FeCo catalyst prepared in the example is subjected to electrochemical test in an electrolytic cell in which 0.1M KOH solution is used as electrolyte and a glassy carbon electrode, a Pt sheet and Ag/AgCl are respectively used as a working electrode, a counter electrode and a reference electrode. The test was performed using a potentiostat and a rotating disk electrode set. All electrode potentials are directed to the Reversible Hydrogen Electrode (RHE). The test conditions were: catalyst loading was 0.5 mg cm-2(ii) a The sweep rate was 10 mV. s-1. Prior to RDE testing, the catalyst was first subjected to 0-1V, 50 mV. multidot.s-120 cycles of cyclic voltammetry toRemoving surface contaminants. The RDE linear volt-ampere ORR test condition is 0.1-1.1V, and the positive sweep is 5 mV-1(ii) a OER test conditions are 1.0-1.8V. The electrode preparation to RDE test was repeated 3 times until the data stabilized to ensure reproducibility. The results are shown in FIGS. 2 and 3. As can be seen from FIG. 2, the ANT-CNT-FeCo catalyst prepared in this example has an initial potential about 30 mV lower than that of the Pt/C catalyst, and a half-wave potential equivalent to a limiting current comparable to that of the Pt/C catalyst. As is apparent from FIG. 3, the current density was 10 mA cm-2The overpotential was 0.34V. This data is better than the common commercial IrO2Catalyst (0.39V). It can be said that the bifunctional catalyst has better performance.
Another important parameter characterizing ORR performance is the four-electron selectivity of the catalyst, since oxygen is directly reduced to water or OH by a four-electron process-The ANT-CNT-FeCo catalyst prepared in this example was electrochemically tested in an electrolytic cell using 0.1M KOH solution as electrolyte, glassy carbon electrode, Pt sheet and Ag/AgCl as working electrode, counter electrode and reference electrode, respectively.A four-electron selectivity of ANT-CNT-FeCo was obtained by testing ORR polarization curves (see FIG. 4) at different rotation speeds and fitting K-L equation.As can be seen from FIG. 5, the K-L plot of ANT-CNT-FeCo shows good linear relationship at all potentials, indicating that the reaction is a first order reaction, the rate is proportional to the oxygen concentration.the electron transfer number n is 3.8 to 4.0 even at high potentials, indicating that the ORR reaction on ANT-CNT-FeCo proceeds according to a four-electron pathway.
Example 2
Firstly, 25M L absolute ethyl alcohol is measured in a beaker, 0.1 g acrylonitrile oligomer (molecular weight is 700) is dripped in, after the polymer is dissolved, 0.1 g hydroxylated multi-wall carbon nano tube (model is XFM 05) is weighed in the same beaker, magnetic stirring is carried out for 1 hour to ensure that the mixture is evenly mixed, then 595 u L0.5M ferric chloride ethanol solution is dripped in while stirring, the beaker is transferred to an ultrasonic machine, the metal salt solution is evenly dispersed by ultrasonic treatment for 1 hour, then the beaker is transferred to an oil bath, and 40M ethanol solution is added inoStirring for 2 hours under the atmosphere of C, and heating to 80 DEGoC evaporating the solventIt took about 3 hours to evaporate the solvent. The resulting black solid mixture was then transferred to a porcelain boat and placed in a vacuum oven 80oC, drying overnight. Finally, the boat was placed in a tube furnace at 900 deg.CoAnd C, sintering at high temperature for 1 hour in an argon atmosphere, and grinding to obtain the ANT-CNT-Fe catalyst.
Example 3
Firstly, 25M L absolute ethyl alcohol is measured in a beaker, 0.1 g acrylonitrile oligomer (molecular weight is 200) is dripped in, after the polymer is dissolved, 0.1 g hydroxylated multi-walled carbon nano tube (model is XFM 05) is weighed in the same beaker, magnetic stirring is carried out for 1 hour to ensure that the mixture is evenly mixed, then 750 u L0.375.375M cobalt chloride ethanol solution is dripped in while stirring, the beaker is transferred to an ultrasonic machine, the metal salt solution is evenly dispersed by ultrasonic treatment for 1 hour, then the beaker is transferred to an oil bath, and 40M of oil bath is carried out for 40 hoursoStirring for 2 hours under the atmosphere of C, and heating to 80 DEGoCThe solvent was evaporated, taking about 3 hours to evaporate the solvent. The resulting black solid mixture was then transferred to a porcelain boat and placed in a vacuum oven 80oC, drying overnight. Finally, the boat was placed in a tube furnace at 900 deg.CoAnd C, sintering at high temperature for 1 hour in an argon atmosphere, and grinding to obtain the ANT-CNT-Co catalyst.
Fig. 6 is a graph showing oxygen reduction reaction and oxygen evolution performance test of the ANT-CNT-Fe catalyst and the ANT-CNT-Co catalyst prepared in the above examples 2 and 3, compared to a commercial Pt/C catalyst.
In summary, the present invention provides a bifunctional electrocatalyst and a method for preparing the same. The invention synthesizes the high-performance ORR and OER bifunctional electrocatalyst by using the carbon nano tube and the acrylonitrile oligomer as raw materials. The synthesis method is simple, environment-friendly and low in cost. The catalyst synthesized by the method has ORR activity comparable to that of a commercial Pt/C catalyst under alkaline conditions, and OER activity superior to that of commercial IrO2Has good application prospect.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (6)

1. A method of making a bifunctional electrocatalyst, comprising:
step A, adding an acrylonitrile oligomer into a solvent, then adding a hydroxylated multi-walled carbon nanotube, and stirring for 1-2 hours to obtain a pasty suspension;
b, adding a metal salt solution into the pasty turbid liquid while stirring, transferring the turbid liquid into an oil bath after stirring for 0.5 to 1.5 hours, and stirring the turbid liquid for 2 to 5 hours at the temperature of between 30 and 50 ℃;
step C, removing the solvent in the mixture obtained in the step B to obtain a solid mixture;
d, calcining the solid mixture for 0.5-1.5 hours at 800-1000 ℃ under the protection of inert atmosphere to obtain a calcined product, and grinding the calcined product to obtain the ORR and OER dual-function electrocatalyst; in the step A, the molecular weight of the acrylonitrile oligomer is 200-700;
in the step B, the metal salt is one or two of ferric chloride and cobalt chloride;
in the step B, the mass ratio of the hydroxylated multi-wall carbon nano tube to the metal ions in the metal salt is 0.3-0.4;
the catalyst is ANT-CNT-FeCo catalyst, ANT-CNT-Fe catalyst or ANT-CNT-Co catalyst.
2. The preparation method of the bifunctional electrocatalyst according to claim 1, wherein in the step a, the mass ratio of the acrylonitrile oligomer to the hydroxylated multi-walled carbon nanotubes is 1 to 10.
3. The method of preparing a bifunctional electrocatalyst according to claim 1, wherein step C comprises: placing the mixture obtained in the step B in an oil bath atmosphere at 70-90 ℃, and removing most of the solvent through magnetic rotary evaporation; and then transferring the mixture to a vacuum drying oven, and evaporating the residual solvent to dryness at the temperature of 60-80 ℃ to obtain a solid mixture.
4. The method for preparing a bifunctional electrocatalyst according to claim 3, wherein the time for the magnetic rotary evaporation is 3-5 hours and the time for vacuum drying is 6-8 hours.
5. The method for preparing a bifunctional electrocatalyst according to claim 1, wherein in step D, calcination is performed at 900 ℃ for 1 hour to obtain the calcined product.
6. A bifunctional electrocatalyst, characterized in that it is prepared by the method of any one of claims 1 to 5.
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CN101116817A (en) * 2007-05-10 2008-02-06 南京大学 Carbon nitride nanotubes load platinum ruthenium nanometer particle electrode catalyst and method for preparing the same
CN103170371A (en) * 2011-12-21 2013-06-26 冯良荣 Catalyst for preparing chloroethylene by acetylene hydrochlorination
CN103545536A (en) * 2013-10-22 2014-01-29 上海交通大学 Carbon fiber supported metal catalyst as well as preparation method and application thereof

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CN101116817A (en) * 2007-05-10 2008-02-06 南京大学 Carbon nitride nanotubes load platinum ruthenium nanometer particle electrode catalyst and method for preparing the same
CN103170371A (en) * 2011-12-21 2013-06-26 冯良荣 Catalyst for preparing chloroethylene by acetylene hydrochlorination
CN103545536A (en) * 2013-10-22 2014-01-29 上海交通大学 Carbon fiber supported metal catalyst as well as preparation method and application thereof

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