CN111082077B - High-dispersion heterogeneous interface composite nanowire and preparation method and application thereof - Google Patents

High-dispersion heterogeneous interface composite nanowire and preparation method and application thereof Download PDF

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CN111082077B
CN111082077B CN201911394325.1A CN201911394325A CN111082077B CN 111082077 B CN111082077 B CN 111082077B CN 201911394325 A CN201911394325 A CN 201911394325A CN 111082077 B CN111082077 B CN 111082077B
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CN111082077A (en
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唐正华
王凯
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South China University of Technology SCUT
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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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M12/04—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
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts

Abstract

The invention belongs to the technical field of new energy materials, and discloses a high-dispersion heterogeneous interface composite nanowire and a preparation method and application thereof. Dissolving manganese salt and ammonium salt in water to form a uniform solution, and then carrying out heating reaction to obtain a manganese oxide precursor; (2) dispersing the manganese oxide precursor obtained in the step (1) into a transition metal salt solution, and separating a product after stirring; (3) and (3) dispersing the product obtained in the step (2) into a solution containing a sulfur source, uniformly mixing, carrying out heating reaction, and washing and drying after the reaction is finished to obtain the final product. The synthesis method is simple and easy to implement: the invention adopts a two-step hydrothermal synthesis method to construct MnCo with a heterostructure through epitaxial growth2S4/MnSxO2‑xThe preparation conditions are wide, and the method is suitable for industrial production. The obtained composite nanowire has a rich and uniformly dispersed heterogeneous interface structure, the interface is an active site center with catalytic performance, and the composite nanowire has good oxygen production performance.

Description

High-dispersion heterogeneous interface composite nanowire and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new energy materials, and relates to a high-dispersion heterogeneous interface composite nanowire and a preparation method and application thereof.
Background
The development of sustainable and renewable energy and efficient energy storage and conversion technologies is crucial to address environmental and energy challenges. The rechargeable zinc-air battery is a green renewable energy technology conversion device. In the rechargeable zinc-air battery, high voltage conditions are often needed in the charging process, but for the electrode, the high voltage conditions can damage the structure of the electrode material, thereby greatly shortening the service life of the battery. The Oxygen Evolution Reaction (OER) is a reaction generated in the charging process of the rechargeable zinc-air battery, the development of a high-performance oxygen evolution reaction catalyst is adopted, and the reduction of the overpotential of the oxygen evolution reaction is a necessary means for solving the service life problem of the rechargeable zinc-air battery.
In recent years, the development of OER catalysts has focused mainly on layered transition metal hydroxides (LDHs) and heteroatom doping, but improvements in their performance have not been achieved. The heterostructure catalyst composed of electrochemical active materials and various functional dopings shows remarkable electrocatalytic performance to OER, and particularly, the heterostructure of some non-noble metals has activity equivalent to that of a noble metal-based catalyst. However, the heterointerface content of these materials is rare and the distribution is not uniform. Therefore, maximizing the production of uniformly dispersed heterointerfaces is a significant challenge in the production of heterostructure catalysts.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a high-dispersion heterogeneous interface composite nanowire. The heterogeneous interface composite nanowire is MnCo2S4/MnSxO2-x. The hetero-interface consists of MnSxO2-xNanowire and MnCo synthesized by epitaxial growth2S4Is formed, a large number of catalytically active central sites are present at the interface.
The invention also aims to provide a preparation method of the high-dispersion hetero-interface composite nanowire. The material is prepared by a simple two-step hydrothermal method, and the preparation method is simple to operate, high in synthesis yield and good in industrial application prospect.
The invention further aims to provide application of the high-dispersion hetero-interface composite nanowire as a positive electrode material in a rechargeable zinc-air battery. The material has a large number of highly dispersed heterogeneous interface structures, and the structures show excellent performance in an electrocatalytic oxygen evolution reaction. The oxygen evolution reaction is the rate-determining step in the charging process of the rechargeable zinc-air battery, so the excellent catalytic performance of the material can be applied to the electrode material of the rechargeable zinc-air battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a high-dispersion heterogeneous interface composite nanowire comprises the following steps:
(1) dissolving manganese salt and ammonium salt in water to form a uniform solution, and then carrying out heating reaction to obtain a manganese oxide precursor;
(2) dispersing the manganese oxide precursor obtained in the step (1) into a transition metal salt solution, and separating a product after stirring;
(3) and (3) dispersing the product obtained in the step (2) into a solution containing a sulfur source, uniformly mixing, carrying out heating reaction, and washing and drying after the reaction is finished to obtain the final product.
The manganese salt in the step (1) is at least one of potassium permanganate, manganese sulfate, manganese nitrate and manganese acetate, and the ammonium salt is at least one of ammonium nitrate, ammonium chloride and ammonium persulfate;
the quantity concentration ratio of manganese salt to ammonium salt in the uniform solution in the step (1) is 10: 1-1: 10, and the quantity concentration of the manganese salt to the ammonium salt is 0.003-0.03 mol L independently-1；
The heating reaction temperature in the step (1) is 100-180 ℃, and the heating reaction time is 8-48 hours.
The transition metal salt in the step (2) is acetate of transition metal, the transition metal is at least one of iron, cobalt, nickel, copper, zinc and manganese, preferably, the transition metal salt solution is a mixed solution of acetates of two different transition metals, the mass concentration ratio of the mixed solution is 1/3-3/1, and the mass concentration of the mixed solution is 1-4 mmol L independently-1；
The molar ratio of the transition metal salt in the step (2) to the manganese oxide precursor obtained in the step (1) is 1-5: 1-5, and preferably 1: 1.
And (3) stirring at the temperature of 40-100 ℃ for 4-12 hours.
The sulfur source in the step (3) is at least one of thioacetamide, sulfur powder, cysteine and thiourea,
and (4) the solvent in the solution containing the sulfur source in the step (3) is ethanol.
The amount concentration of the sulfur source substance in the solution containing the sulfur source in the step (3) is 0.04-0.1 mol L-1；
The molar ratio of the sulfur source in the step (3) to the product obtained in the step (2) is 1: 1-1: 3.
The step (3) of uniformly mixing is preferably ultrasonic mixing, and the ultrasonic time is 10-60 minutes;
the reaction temperature in the step (3) is 100-180 ℃, and the reaction time is 2-12 hours.
The structural formula of the high-dispersion heterogeneous interface composite nanowire prepared by the methodIs MnCo2S4/MnSxO2-x；
Wherein said x represents MnO2Number of surface moiety O atoms substituted by sulfur atoms, 0<x<2。
The high-dispersion heterogeneous interface composite nanowire is applied to a rechargeable zinc-air battery as a positive electrode material.
Compared with the existing research, the innovation of the invention is as follows:
(1) the preparation method is simple: the invention adopts a two-step hydrothermal synthesis method to construct MnCo with a heterostructure through epitaxial growth2S4/MnSxO2-xAnd thus can be easily commercially produced.
(2) The structure is unique: MnCo of the invention2S4/MnSxO2-xHas rich and uniformly dispersed heterogeneous interface structure, and the interface is the active site center of catalytic performance.
(3) The price is low: the transition metal elements are widely distributed on the earth, and the used sulfur source is a cheap sulfur precursor.
(4) The performance is excellent: the current density reaches 50mA cm in the oxygen production process-2When being MnCo2S4/MnSxO2-xThe required overpotential is 395mV compared with commercial IrO2The (iridium oxide) has 470mV, and the oxygen production performance is superior to that of commercial IrO2。
Drawings
FIGS. 1(a) and (b) are each MnCo in example 12S4/MnSxO2-xScanning Electron Microscopy (SEM) at different resolutions.
FIGS. 2(a) and (b) are MnCo in example 12S4/MnSxO2-xTransmission Electron Microscopy (TEM) at different magnifications, (c) high magnification transmission electron microscopy (HRTEM).
FIG. 3 shows MnCo in example 12S4/MnSxO2-xX-ray powder diffraction (XRD).
FIG. 4 shows MnCo in example 12S4/MnSxO2-xMaterial X-ray photoelectron diffraction spectrum (XPS).
FIG. 5 shows MnCo in example 12S4/MnSxO2-xAnd IrO2At 1mol L-1OER performance in KOH solution (a), corresponding Tafel curve (b) and stability (c) were compared.
FIG. 6 shows MnCo in example 12S4/MnSxO2-xPerformance in rechargeable zinc-air cells, (a) is the charge-discharge curve, (b) the discharge polarization curve and the corresponding power density.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
Example 1
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Analysis of Performance Structure
FIG. 1(a) scanning electron microscope shows MnCo2S4/MnSxO2-xIs a nanowire-like structure, and (b) shows that many small particles are attached to the nanowire wall, and furthermore, the diameter of the nanowire is about 50 nm. Further proving that the nano particles grow on the wall of the nanowire from the low-power transmission electron microscope image (2) a, and the image (2) b shows that a plurality of particles with smaller particle sizes exist on the nanowire, and a heterostructure is formed by preliminary judgment. FIG. 2 (c) clearly shows MnCo2S4/MnSxO2-xHas a large number of heterogeneous interface structures with uniform distribution, and the interface structures have a large number of defects, vacancies and edgesThis is the greatest innovation of the present invention, due to the active sites of electrocatalytic properties.
FIG. 3 shows MnCo2S4/MnSxO2-xIn the presence of manganese oxide and MnCo2S4The existence of the heterostructure is further proved by combining the figure (2) c.
FIG. 4 is MnCo2S4/MnSxO2-xThe characterization reveals that the composition components of the material are Mn, Co, S and O elements, wherein the content of manganese is 13.79%, the content of cobalt is 12.52% and the content of sulfur is 11.20%, which indicates that part of oxygen in manganese oxide and manganese cobaltate is replaced by sulfur, so that a large number of oxygen vacancy points exist at the heterogeneous interface of the material.
FIG. 5(a) is a polarization curve of oxygen evolution, and the catalyst prepared in this example supported thereon has a smaller overpotential than commercial iridium oxide, from which MnCo is known2S4/MnSxO2-xAnd IrO2At a current density of 50mA cm-2The overpotentials of (a) are 395mV and 470mV, respectively. FIG. b shows the Tafel curve, from which MnCo is known2S4/MnSxO2-xThe Tafel slope of (1) is 78mV dec-1And IrO2Is 98mVdec-1From this, MnCo is known2S4/MnSxO2-xHas a specific commercial IrO2More excellent dynamic process. Panel (c) shows MnCo2S4/MnSxO2-xAnd IrO2The stability of (2) was characterized, and it can be seen from the figure that MnCo2S4/MnSxO2-x91% of the initial current is maintained, and IrO2It is only 80%.
FIG. 6(a) is a charge/discharge curve of a zinc-air battery, from which MnCo can be seen2S4/MnSxO2-xThe initial charging and discharging voltage gap of (2) is 0.82V at 10mA cm-2MnCo after 30h of charge-discharge cycle under the condition2S4/MnSxO2-xThe charge-discharge voltage gap of (2) is still 0.84V. And IrO2Of (2) is initiatedThe voltage gaps are respectively 0.90V, and after the continuous cycle charging and discharging for 30h, the voltage gaps are respectively increased to 1.04V. Prove MnCo2S4/MnSxO2-xThe zinc-air battery has more excellent stability when being applied to the zinc-air battery. Panel (b) shows MnCo2S4/MnSxO2-xHas an energy density of 140mW cm-2，IrO2Is 125mW cm-2. Indicating that it has greater power density and superior charge-discharge stability as a rechargeable zinc-air battery positive electrode than commercial iridium oxide.
Example 2
(1) Adding 0.18mmol of potassium permanganate (KMnO)4) And 1.8mmol ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 3
(1) Adding 1.8mmol of potassium permanganate (KMnO)4) And 0.18mmol ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 4
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 120 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 5
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at 180 ℃ to form manganese dioxide nanowires.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 6
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the reaction is carried out for 8h at the temperature of 160 ℃, thus obtaining the manganese dioxide nanowire.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 7
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 48 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 8
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 1mM anhydrous manganese acetate Mn (OAc)2And 3mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 9
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 3mM anhydrous manganese acetate Mn (OAc)2And 1mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) ethanol solution, ultrasonic treating for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and centrifuging。
(3) Dispersing the final product in the step (2) into 40mL of 75mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 10
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 40mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 11
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 100mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 12
(1) 1mmol of manganese sulfate tetrahydrate (MnSO)4·4H2O) and 1mmol ammonium persulfate (NH)4)2S2O8) Dissolving the manganese dioxide nano-wire into 60mL of deionized water, and then reacting for 24h at 160 ℃ to obtain the manganese dioxide nano-wire.
(2) A second step ofManganese oxide nanowires dispersed in 100mL of 2mM manganese acetate anhydrous Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 100mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 13
(1) 1mmol of manganese nitrate hexahydrate (Mn (NO)3)2·6H2O) and 1mmol of ethylenediamine are dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous manganese acetate Mn (OAc)2And 4mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 100mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 14
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM anhydrous zinc acetate (Zn (OAc)2) And 4mM copper acetate monohydrate (Cu (OAc)2·H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 100mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 15
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride(NH4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 2mM nickel acetate tetrahydrate (Ni (OAc)2·4H2O) and 4mM iron acetate tetrahydrate (Fe (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 100mM thioacetamide ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 140 ℃, and washing and drying to obtain a final sample.
Example 16
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 3mM anhydrous manganese acetate Mn (OAc)2And 1mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM sulfur powder ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 160 ℃, and washing and drying to obtain a final sample.
Example 17
(1) Adding 1mmol potassium permanganate (KMnO)4) And 1mmol of ammonium chloride (NH)4Cl) is dissolved in 60mL of deionized water, and then the mixture reacts for 24 hours at the temperature of 160 ℃, so that manganese dioxide nanowires can be formed.
(2) Dispersing the manganese dioxide nanowires into 100mL of 3mM anhydrous manganese acetate Mn (OAc)2And 1mM cobalt acetate tetrahydrate (Co (OAc)2·4H2O) in ethanol solution, performing ultrasonic treatment for 20 minutes, stirring in an oil bath at 80 ℃ for 4 hours, and performing centrifugal separation.
(3) Dispersing the final product in the step (2) into 40mL of 75mM cysteine ethanol solution, reacting for 12 hours in a high-pressure reaction kettle at 160 ℃, and washing and drying to obtain a final sample.
MnCo obtained in examples 2 to 172S4/MnSxO2-xSimilar to example 1.
Comparative example 1
Comparative example 1 is different from example 1 in that the solvent in the solution containing the sulfur source in step (3) is not ethanol but water, methanol, toluene, DMF and the like.
Comparative example 1 the resulting nanowire structure after the reaction was completed was decomposed or the sample could not be vulcanized. The reason is that: when water is used as the solvent, the sulfur source and water will generate sulfuric acid to dissolve the nanowire structure during the hydrothermal process; methanol has similar performance to ethanol, but when methanol is used as a solvent, the methanol is easy to gasify under high temperature conditions due to small molecular weight of the methanol, so that the pressure of a reaction system is increased, thereby causing decomposition of a nanowire structure; toluene and DMF are aprotic solvents, and sulfur ions cannot be decomposed from a sulfur source in the two solvents, so that MnCo cannot be finally formed2S4/MnSxO2-x。
Example 1 has the best application performance, and the structure and the performance are most representative. In structural aspect MnCo2S4/MnSxO2-xHas a large number of uniformly dispersed heterogeneous interface structures which have abundant active sites such as vacancies, edges, defects and the like, and the current density reaches 50mA cm in the oxygen production process-2When being MnCo2S4/MnSxO2-xThe required overpotential is 395mV compared with commercial IrO2470mV, it shows superior catalytic performance in electrocatalytic oxygen evolution reactions compared to commercial OER catalysts. For rechargeable zinc-air batteries, the charging process determines the service life of the battery, MnCo2S4/MnSxO2-xHas excellent OER stability, so that the material has excellent charge and discharge stability as the anode material of the rechargeable zinc-air battery, the charge and discharge voltage gap of the material is only increased by 0.02V after 30h of cycling, and the material has larger power density than commercial iridium oxide.
The above embodiments are preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.

Claims (9)

1. A preparation method of a high-dispersion heterogeneous interface composite nanowire is characterized by comprising the following steps:
(1) dissolving manganese salt and ammonium salt in water to form a uniform solution, and then carrying out heating reaction to obtain a manganese oxide precursor;
(2) dispersing the manganese oxide precursor obtained in the step (1) into a transition metal salt solution, and separating a product after stirring;
(3) dispersing the product obtained in the step (2) into a solution containing a sulfur source, uniformly mixing, carrying out heating reaction, and washing and drying after the reaction is finished to obtain a final product;
the molar ratio of the transition metal salt in the step (2) to the manganese oxide precursor obtained in the step (1) is 1-5: 1-5;
the sulfur source in the step (3) is at least one of thioacetamide, sulfur powder, cysteine and thiourea;
the molar ratio of the solution containing the sulfur source in the step (3) to the product obtained in the step (2) is 1: 1-1: 3.
2. The method for preparing the high-dispersion hetero-interface composite nanowire according to claim 1, wherein:
the manganese salt in the step (1) is at least one of potassium permanganate, manganese sulfate, manganese nitrate and manganese acetate, and the ammonium salt is at least one of ammonium nitrate, ammonium chloride and ammonium persulfate;
the quantity concentration ratio of manganese salt to ammonium salt in the uniform solution in the step (1) is 10: 1-1: 10, and the manganese salt and the ammonium salt
The amount concentration of the ammonium salt is 0.003-0.03 mol L independently-1。
3. The method for preparing the high-dispersion hetero-interface composite nanowire according to claim 1, wherein:
the transition metal salt in the step (2) is acetate of transition metal, and the transition metal is iron, cobalt, nickel, copper and zinc
And manganese.
4. The method for preparing the high-dispersion hetero-interface composite nanowire according to claim 3, wherein:
the transition metal salt solution is a mixed solution of acetates of two different transition metals, the concentration ratio of substances is 1/3-3/1, and the quantity concentration of the substances is 1-4 mmol L-1。
5. The method for preparing the high-dispersion hetero-interface composite nanowire according to claim 1, wherein:
and (4) the solvent in the solution containing the sulfur source in the step (3) is ethanol.
6. The method for preparing the high-dispersion hetero-interface composite nanowire according to claim 1, wherein: the amount concentration of the sulfur source substance in the solution containing the sulfur source in the step (3) is 0.04-0.1 mol L-1。
7. The method for preparing the high-dispersion hetero-interface composite nanowire according to claim 1, wherein:
the heating reaction temperature in the step (1) is 100-180 ℃, and the heating reaction time is 8-48 hours; stirring temperature in the step (2) is 40-100 ℃, and stirring time is 4-12 hours;
the reaction temperature in the step (3) is 100-180 ℃, and the reaction time is 2-12 hours.
8. A high-dispersion hetero-interface composite nanowire prepared by the method of any one of claims 1 to 7
Is prepared byThe structural formula is MnCo2S4/MnSxO2-x；
Wherein said x represents MnO2Number of surface moiety O atoms substituted by sulfur atoms, 0<x<2 。
9. The use of the highly dispersed heterointerface composite nanowires of claim 8 as a positive electrode material in rechargeable zinc-air batteries.
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