CN115395031A - High-entropy alloy ORR and OER catalytic material and preparation method thereof - Google Patents

High-entropy alloy ORR and OER catalytic material and preparation method thereof Download PDF

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CN115395031A
CN115395031A CN202211143042.1A CN202211143042A CN115395031A CN 115395031 A CN115395031 A CN 115395031A CN 202211143042 A CN202211143042 A CN 202211143042A CN 115395031 A CN115395031 A CN 115395031A
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卜云飞
芮畅
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Nanjing University of Information Science and Technology
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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
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
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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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite

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Abstract

The invention discloses a high-entropy alloy ORR and OER catalytic material and a preparation method thereof, wherein the material is Mn a Co b Ru c Fe d Ni e -NC, wherein a: b: c: d: e = 1: 1-2: 1, and the preparation method comprises the following steps: (1) Dissolving zinc acetate, cobalt salt, ferric salt, nickel salt, ruthenium salt and manganese salt in water to form a uniform solution; (2) Dissolving 2-methylimidazole in water, adding the solution obtained in the step (1), stirring for reaction, and separatingPerforming core washing and drying to obtain a multi-metal organic framework material ZIF- (MnCoRuFeNi); (3) Calcining ZIF- (MnCoRuFeNi) in an inert atmosphere to obtain a MnCoRuFeNi-NC high-entropy alloy catalytic material; the catalytic material has excellent oxygen precipitation and oxygen reduction functions by introducing high-entropy alloy and nitrogen doping.

Description

High-entropy alloy ORR and OER catalytic material and preparation method thereof
Technical Field
The invention relates to a catalytic material and a preparation method thereof, in particular to a high-entropy alloy ORR and OER catalytic material and a preparation method thereof.
Background
Environmental problems caused by excessive use of fossil fuel resources are increasingly prominent, and development of sustainable and efficient energy conversion equipment is urgently required in order to alleviate the problems. Metal-air cells are a group of electrochemical cells that produce electrical energy from metal oxidation and oxygen reduction, and belong to a type of semi-fuel cell. The energy density is higher than that of commercial lead-acid batteries, nickel-metal hydride batteries and lithium ion batteries.
Among them, zinc-air batteries using metal zinc as a cathode fuel and oxygen as an anode fuel are widely concerned by people due to the advantages of low cost, environmental friendliness, high safety performance and the like. The zinc-air battery is a semi-fuel battery which uses oxygen in the air as anode fuel and metal zinc as cathode. Zinc-air batteries, because the anode directly uses oxygen from air as the active material, are mostly determined by the anode metal zinc plate, similar to the fuel electrode of a fuel cell, and are often also referred to as semi-fuel cells. At present, for rechargeable zinc-air batteries, the research focus is to develop a high-efficiency bifunctional catalyst to solve the slow kinetics of oxygen in the processes of oxygen reduction (ORR) and Oxygen Evolution Reaction (OER), so as to improve the charge-discharge efficiency of the battery and reduce the energy loss; in addition, there have been efforts to find noble metal alternatives to reduce the cost of zinc-air cell catalysts.
High-entropy alloys (HEA), are alloys formed from five or more metals in equal or approximately equal amounts. The zinc-air battery anode material can be used as a zinc-air battery anode material due to unique catalytic activity. In patent CN202210252099.9, high-entropy prealloyed ingot FeCoNiMX is cast into a high-entropy alloy target, and then a high-entropy alloy nanoparticle Fe is generated on carbon cloth by magnetron sputtering by using an ultrahigh vacuum nanocluster deposition system 19 Co 16 Ni 25 Mn 20 Cr 20 The catalyst shows ultrahigh-efficiency oxygen evolution performance, but does not have the function of oxygen reduction.
Disclosure of Invention
The invention aims to: the first purpose of the invention is to provide a high-entropy alloy ORR and OER catalytic material with better oxygen precipitation and oxygen reduction performance; the second purpose of the invention is to provide a preparation method of the material.
The technical scheme is as follows: the high-entropy alloy ORR and OER catalytic material is Mn a Co b Ru c Fe d Ni e -NC, wherein a: b: c: d: e = 1: 1-2: 1.
Preferably, the matrix of the catalytic material is a ZIF-8 metal organic framework composed of zinc acetate and 2-methylimidazole.
The preparation method of the high-entropy alloy ORR and OER catalytic material comprises the following steps:
(1) Dissolving zinc acetate, cobalt salt, iron salt, nickel salt, ruthenium salt and manganese salt in water to form a uniform solution;
(2) Dissolving 2-methylimidazole in water, adding the solution obtained in the step (1), stirring for reaction, centrifuging, washing and drying to obtain the polymetallic organic framework material ZIF- (Mn) a Co b Ru c Fe d Ni e )；
(3) Calcining ZIF- (MnCoRuFeNi) in inert atmosphere to obtain Mn a Co b Ru c Fe d Ni e -NC high entropy alloy catalytic material.
Preferably, in the step (1), the molar ratio of the zinc acetate to the manganese, cobalt, ruthenium, iron and nickel is 30-60: 1-2: 1.
Preferably, the cobalt salt, iron salt, nickel salt, ruthenium salt and manganese salt are cobalt nitrate, iron nitrate, nickel nitrate, ruthenium chloride and manganese nitrate, respectively.
In the step (2), the 2-methylimidazole is in an excessive amount, zinc acetate and the 2-methylimidazole form ZIF-8 as a matrix of the catalytic material, the ZIF-8 has large specific surface area and chemical stability, and rich pore channels provide places for loading various metal ions, so that exposure of oxygen catalytic active sites is facilitated.
In the step (3), the high-entropy alloy is generated in the calcining process, nitrogen doping is introduced into the alloy through carbonization, a plurality of high-entropy alloy-N-C active sites are formed in the catalytic material, the combination mode of the alloy and the heteroatom (N) is improved, the loss of metal active sites in oxygen reduction and oxygen precipitation reactions is reduced, and therefore the stability of the material is greatly improved.
Preferably, the calcining temperature is 700-900 ℃, and the heating rate is 3-7 ℃/min.
Preferably, the washing solvent is a mixture of ethanol and water.
Preferably, the drying is carried out at 50-90 ℃ for 12-24 hours under vacuum.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) The catalytic material is formed by introducing high-entropy alloy and doping nitrogen, and because of the composition of different metal elements such as iron, nickel, ruthenium and manganese and the difference of electronegativity of each metal, electrons are rearranged under the strong electron interaction, and the catalytic material has excellent oxygen precipitation and oxygen reduction functions; (2) A metal organic framework ZIF-8 is adopted as a matrix of the catalytic material, wherein the ZIF-8 has large specific surface area and chemical stability, and rich pore channels provide places for loading various metal ions, thereby being beneficial to the exposure of oxygen catalytic active sites; (3) The MnCoRuFeNi-NC catalytic material has the oxygen reduction half-wave potential of 0.88V vs. RHE and the current density of 10mA cm -2 The corresponding oxygen evolution potential is 1.56V vs. RHE; (4) The zinc-air battery assembled by the catalytic material can stably charge and discharge for more than 120 hours; and (5) the preparation method is simple.
Drawings
FIG. 1 is an X-ray crystal diffraction pattern of a MnCoRuFeNi-NC catalytic material prepared in example 1;
FIG. 2 is a scanning electron microscope image of a MnCoRuFeNi-NC catalytic material prepared in example 1;
FIG. 3 is a transmission electron micrograph of a MnCoRuFeNi-NC catalytic material prepared in example 1;
FIG. 4 is an element distribution diagram of a MnCoRuFeNi-NC catalytic material prepared in example 1;
FIG. 5 is a graph of the oxygen reduction polarization curve and stability under three electrodes of the MnCoRuFeNi-NC catalytic material prepared in example 1;
FIG. 6 is a three-electrode oxygen evolution polarization curve and stability diagram of the MnCoRuFeNi-NC catalytic material prepared in example 1;
fig. 7 is a power density diagram and a cyclic charge-discharge diagram of a mncooruneni-NC catalytic material assembled zinc-air battery prepared in example 1;
fig. 8 is a graph showing the effect of practical application of the mncooruneni-NC catalytic material assembled zinc-air battery prepared in example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The preparation method of the high-entropy alloy ORR and OER catalytic material comprises the following steps:
(1) Dissolving 3mmol of zinc acetate dihydrate, 0.1mmol of cobalt nitrate hexahydrate, 0.1mmol of ferric nitrate nonahydrate, 0.1mmol of nickel nitrate hexahydrate, 0.1mmol of ruthenium trichloride and 0.1mmol of manganese nitrate hexahydrate in 40 ml of water, and stirring to fully dissolve the components to form a uniform solution;
(2) Dissolving 24mmol 2-methylimidazole in 40 ml distilled water, adding the solution obtained in the step (1), performing ultrasonic treatment for 30 minutes at room temperature, continuing to perform magnetic stirring at room temperature for 12 hours, centrifuging the solution at the rotating speed of 7000rpm/min, washing for three times, wherein a washing liquid is a mixed liquid formed by ethanol and water in a volume ratio of 1:1, and then drying for 12 hours in a vacuum oven at 60 ℃ to obtain a multi-metal organic framework material ZIF- (MnCoRuFeNi);
(3) And (3) transferring the ZIF- (MnCoRuFeNi) crystal obtained in the step (2) into a tube furnace, setting the temperature at 800 ℃, heating at the speed of 3 ℃/min, and calcining for 3 hours in an argon atmosphere to finally obtain the MnCoRuFeNi-NC high-entropy alloy catalytic material.
Example 2
The preparation method of the high-entropy alloy ORR and OER catalytic material comprises the following steps:
(1) Dissolving 6mmol of zinc acetate dihydrate, 0.1mmol of cobalt nitrate hexahydrate, 0.1mmol of ferric nitrate nonahydrate, 0.1mmol of nickel nitrate hexahydrate, 0.2mmol of ruthenium trichloride and 0.1mmol of manganese nitrate hexahydrate in 40 ml of water, and stirring to fully dissolve the components to form a uniform solution;
(2) Dissolving 24mmol 2-methylimidazole in 40 ml distilled water, addingAdding the mixture into the solution obtained in the step (1), performing ultrasonic treatment for 30 minutes at room temperature, continuing to magnetically stir at room temperature for 12 hours, centrifuging the solution at the rotating speed of 7000rpm/min, washing for three times, wherein the washing solution is a mixed solution of ethanol and water in a volume ratio of 1:1, and then drying in a vacuum oven at 60 ℃ for 12 hours to obtain the multi-metal organic framework material ZIF- (MnCoRu) 2 FeNi)；
(3) ZIF- (MnCoRu) obtained in the step (2) 2 FeNi) crystal is transferred into a tube furnace, the temperature is set to be 800 ℃, the temperature rise speed is 3 ℃/min, and the crystal is calcined for 3 hours in the argon atmosphere to finally obtain MnCoRu 2 FeNi-NC high-entropy alloy catalytic material.
Comparative example 1
(1) Dissolving 3mmol of zinc acetate dihydrate and 0.1mmol of cobalt nitrate hexahydrate in 40 ml of water, and stirring to fully dissolve the zinc acetate dihydrate and the cobalt nitrate hexahydrate to form a uniform solution;
(2) Dissolving 24mmol 2-methylimidazole in 40 ml distilled water, adding the solution obtained in the step (1), performing ultrasonic treatment at room temperature for 30 minutes, continuing to perform magnetic stirring at room temperature for 12 hours, centrifuging and washing the solution at the rotating speed of 7000rpm/min for three times, wherein the washing liquid is a mixed liquid formed by ethanol and water in a volume ratio of 1:1, and drying the mixed liquid in a vacuum oven at 60 ℃ for 12 hours to obtain a multi-metal organic framework material ZIF- (Co);
(3) And (3) transferring the ZIF- (Co) crystal obtained in the step (2) to a tubular furnace, setting the temperature to be 800 ℃, heating up at the speed of 3 ℃/min, and calcining for 3 hours in an argon atmosphere to finally obtain the Co-NC catalytic material.
Comparative example 2
(1) Dissolving 3mmol of zinc acetate dihydrate, 0.1mmol of cobalt nitrate hexahydrate, 0.1mmol of ruthenium trichloride and 0.1mmol of manganese nitrate hexahydrate in 40 ml of water, and stirring to fully dissolve the zinc acetate dihydrate, the cobalt nitrate hexahydrate, the ruthenium trichloride and the manganese nitrate hexahydrate to form a uniform solution;
(2) Dissolving 24mmol 2-methylimidazole in 40 ml distilled water, adding the solution obtained in the step (1), performing ultrasonic treatment at room temperature for 30 minutes, continuing to perform magnetic stirring at room temperature for 12 hours, performing centrifugal washing on the solution at the rotating speed of 7000rpm/min for three times, wherein the washing liquid is a mixed liquid formed by ethanol and water in a volume ratio of 1:1, and then drying in a vacuum oven at 60 ℃ for 12 hours to obtain the polymetallic organic framework material ZIF- (MnCoRu).
(3) And (3) transferring the ZIF- (MnCoRu) crystal obtained in the step (2) into a tube furnace, setting the temperature to be 800 ℃, heating up at the speed of 3 ℃/min, and calcining for three hours in an argon atmosphere to finally obtain the MnCoRu-NC catalytic material.
Comparative example 3
Commercial Pt/C (20 wt%) and RuO were purchased 2 The catalyst was used directly for comparative testing. The following can be specifically classified: in conducting the oxygen reduction test, pt/C (20 wt%) was used as the catalyst used in comparative example 3; in the oxygen evolution test, ruO was used 2 As the catalyst used in comparative example 3; when assembling and testing the zinc-air battery, weighing the components in a ratio of 1: pt/C (20 wt%) of 1 and RuO 2 And mixed well as a catalyst used in comparative example 3.
Structural characterization
And characterizing the prepared MnCoRuFeNi-NC high-entropy alloy catalytic material.
As can be taken from fig. 1, the diffraction peak located in the vicinity of 25 ° corresponds to the (002) crystal plane of carbon, and the three characteristic peaks corresponding to the (111), (200) and (220) crystal planes of the alloy are located at 44.3 °, 51.8 ° and 76.1 °, respectively; only four characteristic peaks appear in the whole graph 1, and with the increase of the metal source, the strength of the alloy peak of the embodiment 1 is more obvious, and no other impurity peak appears, which indicates that the formed high-entropy alloy is formed; the elemental Co standard material card can also prove the formation of the alloy.
As can be taken from fig. 2, the micro-topographic body of example 1 exhibited carbon nanotube structures with irregular sizes.
As can be seen from fig. 3, the high entropy alloy of example 1 was freely supported on carbon nanotubes. By analyzing the high-resolution image, the exposed (111) crystal plane and the (002) characteristic crystal plane of carbon of example 1 can be observed, which corresponds to the XRD pattern analysis result of fig. 1.
As can be seen from FIG. 4, the distribution of Mn, co, ru, fe, ni, C, N and O elements in example 1 was very uniform. The presence of the O element here is due to the slight oxidation of the surface of the high entropy alloy in air. The formation of the high-entropy alloy can also be proved by the uniform distribution of the five metal elements.
Performance test
Modification of electrode material, testing and assembly:
(1) Preparation of working electrode
5mg of MnCoRuFeNi-NC catalytic material is dispersed in 450 microliter of isopropanol, 50 microliter of Nafion solution is added, and uniform slurry is obtained after 1 hour of ultrasonic treatment. 3 microliter of the slurry is dripped on a rotating disk electrode by a pipette gun and dried for standby at room temperature.
(2) Electrochemical test conditions and methods
Electrochemical testing was performed using an Autolab workstation from wanton, switzerland, using a standard three-electrode system: the rotating disc electrode is used as a working electrode, the mercury/mercury oxide electrode is used as a reference electrode, and the graphite rod is used as a counter electrode. Electrochemical tests were carried out in an oxygen-saturated concentration of 0.1M KOH, and all test potentials (vs. hg/HgO) were converted to reversible hydrogen electrode potentials (vs. rhe) according to the nernst equation. Wherein the ORR test potential is-0.8-0.2V vs. Hg/HgO, and the OER test potential is 0.2-1.0V vs. Hg/HgO.
(3) Assembling and testing of zinc-air battery
And (3) taking foamed nickel as a current collector, and hot-pressing the polytetrafluoroethylene-treated waterproof carbon cloth on the foamed nickel. Then adding 1cm of MnCoRuFeNi-NC catalytic material slurry 2 Is dripped on the carbon cloth to ensure that the loading of the catalytic material is 1mg/cm 2 . The carbon cloth loaded by the catalytic material is used as an oxygen anode of the zinc-air battery, a zinc plate with a certain thickness is used as a cathode, and the electrolyte is a mixed solution of 6M KOH and 0.2M zinc acetate. And (3) carrying out primary discharge test and cyclic charge-discharge test on the zinc-air battery by adopting a blue test system.
As can be seen from the analysis of the oxygen reduction curve under three electrodes of the catalytic material of FIG. 5, the MnCoRuFeNi-NC catalytic material prepared in example 1 has a half-wave potential of 0.88V vs. RHE, and has a stability of about 95% after 11 hours, which exceeds that of the commercial Pt/C catalyst of comparative example 3 and other comparative examples.
As can be seen from the analysis of the oxygen evolution curve under the three electrodes of the catalytic material of FIG. 6, the current density of the MnCoRuFeNi-NC catalytic material prepared in example 1 is 10mA cm -2 The corresponding potential is 1.56V vs. RHE, the potential is only attenuated by 12mV after 500 cycles, and the performance and the stability of the composite material exceed those of the commercial RuO of the comparative example 3 2 Catalyst and other comparative examples.
From the analysis of the assembled zinc-air cell test data of the catalytic material of fig. 7, the mncooruneni-NC catalytic material prepared in example 1 at a current density of 220mA cm -2 The peak power density of the position is 161mW cm -2 . The gap between the oxygen reduction potential and the oxygen evolution potential is 0.68V. Assembled zinc-air cell at 5mA cm -2 After 120 hours of charge-discharge cycle under current density, the performance is only attenuated by less than 10 percent, and the performance is superior to that of the commercial Pt/C + RuO of the comparative example 3 2 A catalyst, which shows the advantages of applying a zinc-air battery.
From the analysis of the effect graph of the practical application of the zinc-air battery assembled by the catalytic material in fig. 8, the batteries assembled by the three mncoorunfeni-NC catalytic materials prepared in example 1 are connected in series, and 1 LED display screen with 3V voltage and 2 light emitting diodes with 1.8V voltage can be lighted, which shows the feasibility of the practical application.

Claims (8)

1. A high-entropy alloy ORR and OER catalytic material is characterized in that the material is Mn a Co b Ru c Fe d Ni e -NC, wherein a: b: c: d: e = 1: 1-2: 1.
2. Catalytic material according to claim 1, characterized in that the matrix of the catalytic material is a ZIF-8 metal organic framework made of zinc acetate and 2-methylimidazole.
3. A method of preparing the catalytic material of claim 1, comprising the steps of:
(1) Dissolving zinc acetate, cobalt salt, ferric salt, nickel salt, ruthenium salt and manganese salt in water to form a uniform solution;
(2) Dissolving 2-methylimidazole in water, adding the solution obtained in the step (1), stirring for reaction, centrifuging, washing and drying to obtain the polymetallic organic framework materialZIF-(Mn a Co b Ru c Fe d Ni e )；
(3) Mixing ZIF- (Mn) a Co b Ru c Fe d Ni e ) Calcining under inert atmosphere to obtain Mn a Co b Ru c Fe d Ni e -NC high entropy alloy catalytic material.
4. The method of claim 3, wherein the molar ratio of zinc acetate to manganese, cobalt, ruthenium, iron, and nickel is 30-60: 1-2: 1.
5. The method of claim 3, wherein the cobalt, iron, nickel, ruthenium and manganese salts are cobalt nitrate, iron nitrate, nickel nitrate, ruthenium chloride and manganese nitrate, respectively.
6. The method for preparing the catalytic material of claim 3, wherein the calcination temperature in the step (3) is 700-900 ℃.
7. The method for preparing catalytic material according to claim 3, wherein in the step (3), the temperature increase rate of the calcination is 3-7 ℃/min.
8. The method for preparing catalytic material according to claim 3, wherein in the step (2), the washing solvent is a mixture of ethanol and water.
CN202211143042.1A 2022-09-20 2022-09-20 High-entropy alloy ORR and OER catalytic material and preparation method thereof Pending CN115395031A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116586623A (en) * 2023-03-24 2023-08-15 闽都创新实验室 In-situ co-reduction preparation method of copper-based medium-entropy alloy nano material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116586623A (en) * 2023-03-24 2023-08-15 闽都创新实验室 In-situ co-reduction preparation method of copper-based medium-entropy alloy nano material
CN116586623B (en) * 2023-03-24 2024-04-30 闽都创新实验室 In-situ co-reduction preparation method of copper-based medium-entropy alloy nano material

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