CN114899428B - Bifunctional cobalt/cobalt oxide Schottky junction catalyst and preparation method and application thereof - Google Patents
Bifunctional cobalt/cobalt oxide Schottky junction catalyst and preparation method and application thereof Download PDFInfo
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- CN114899428B CN114899428B CN202210630912.1A CN202210630912A CN114899428B CN 114899428 B CN114899428 B CN 114899428B CN 202210630912 A CN202210630912 A CN 202210630912A CN 114899428 B CN114899428 B CN 114899428B
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 127
- 239000010941 cobalt Substances 0.000 title claims abstract description 127
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 73
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 55
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000001301 oxygen Substances 0.000 claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 43
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 92
- 229910052759 nickel Inorganic materials 0.000 claims description 46
- 239000006260 foam Substances 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
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- 239000012535 impurity Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
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- 229910017917 NH4 Cl Inorganic materials 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 9
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- 229910052593 corundum Inorganic materials 0.000 description 14
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000011943 nanocatalyst Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- 229910000510 noble metal Inorganic materials 0.000 description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910017855 NH 4 F Inorganic materials 0.000 description 8
- 238000004502 linear sweep voltammetry Methods 0.000 description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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Classifications
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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
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a bifunctional cobalt/cobalt oxide Schottky junction catalyst and a preparation method and application thereof. The preparation method comprises three main steps of preparation of a homogeneous precursor solution, preparation of a nano needle cobalt-based precursor and preparation of a bifunctional cobalt/cobalt oxide Schottky junction catalyst. The bifunctional cobalt/cobalt oxide Schottky junction catalyst prepared by the hydrothermal method and the in-situ synthesis method has excellent electrocatalytic oxygen evolution and oxygen reduction performances in an alkaline environment; meanwhile, when the bifunctional cobalt/cobalt oxide Schottky junction catalyst prepared by the method is used as an oxygen electrode material of a rechargeable zinc-air battery and a positive electrode material of a flexible solid zinc-air battery, the prepared battery also shows excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to a bifunctional cobalt/cobalt oxide Schottky junction catalyst, and a preparation method and application thereof.
Background
With the increasing demand for energy and the increasing environmental problems worldwide, the exploration of advanced energy conversion and storage devices and technologies such as fuel cells, water electrolysis hydrogen production technology, metal air cells, etc. to reduce the consumption of primary energy and reduce the emission of greenhouse gases has become one of the current trends in sustainable development. Among them, the rechargeable zinc-air battery has been paid attention to because of its remarkable advantages of high theoretical capacity, low cost, high safety, environmental friendliness, and abundant zinc reserves, and in recent years, research reports on the zinc-air battery have been drastically increased, and the zinc-air battery is considered as a sustainable green novel energy conversion device with great development potential. The Oxygen Reduction Reaction (ORR) and the Oxygen Evolution Reaction (OER) occurring on the oxygen electrode thereof play an important role in ensuring the chargeability of the zinc-air battery, however, the synthesis of the optimal ORR and OER bifunctional oxygen electrocatalyst by enhancing the intrinsic kinetic reaction and reducing the cathode overpotential becomes a key to the practical application of the zinc-air battery due to its slow kinetics caused by the high energy barrier of both the ORR and OER reactions. From the standpoint of the electrocatalytic performance of both OER and ORR, the commercial combination of Pt/C-IrO 2 noble metals has been considered as the most advantageous catalyst, but the commercial development and wide application of zinc-air batteries are greatly limited due to the lack of land-based resources, high price, unstable performance and the like. Therefore, there is a need to develop and design a cost-effective, excellent activity and durability dual-function oxygen electrocatalyst to replace noble metal catalysts for high performance rechargeable zinc-air battery applications.
The transition metal-based catalyst has catalytic activity very similar to that of the noble metal-based catalyst, and can be used as a substitute for the noble metal catalyst. The aim of improving the catalytic activity, the conductivity and the reaction kinetics of the transition metal catalyst can be achieved by adopting a nanocrystallization method, a heteroatom doping method and a method for loading a conductive matrix. In the case of bifunctional catalysts, however, the current strategy is to construct a composite catalyst, but the rough interface structure, uneven distribution among various components and poor electronic regulation effect inevitably lead to the reduction of the catalyst activity and stability. Thus, it remains a challenge to design dual active centers with uniform interface structures and to build efficient catalysts with stable interface electron coupling effects. The cobalt-based catalyst has the advantages of rich ground storage resources, low price, adjustable components and the like. In addition, the schottky junction is composed of metal and semiconductor, is one of heterojunctions, and has special electron effect at the interface in order to make the fermi level between the two substances consistent. Cobalt oxide has been reported to have excellent electrocatalytic oxygen reduction properties as a semiconductor catalytic material, with good electrical conductivity and a certain electrocatalytic oxygen evolution activity.
Therefore, the cobalt/cobalt oxide Schottky heterojunction bifunctional nano-catalyst synthesized by a simple method is designed and is effectively applied to rechargeable zinc-air batteries, and has positive significance in enriching design strategies of the bifunctional catalyst and reducing production cost of the zinc-air batteries.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a bifunctional cobalt/cobalt oxide Schottky junction catalyst, and a preparation method and application thereof. The bifunctional cobalt/cobalt oxide schottky junction catalyst shows excellent oxygen reduction and oxygen precipitation reaction activities in an alkaline environment; as an oxygen electrode catalytic material for rechargeable zinc air cells, it exhibits superior cell performance to the Pt/C-IrO 2 noble metal catalyst combination.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The preparation method of the bifunctional cobalt/cobalt oxide Schottky junction catalyst comprises the following steps:
(1) Preparation of a homogeneous precursor solution: dissolving a cobalt source, a surfactant and a precipitator in deionized water, and performing ultrasonic treatment to obtain a homogeneous precursor solution;
(2) Preparing a nano needle cobalt-based precursor: placing the pretreated foam nickel substrate into a polytetrafluoroethylene lining, adding the homogeneous precursor solution obtained in the step (1) into the polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a drying oven for hydrothermal reaction; after the reaction product is cooled to room temperature, washing and drying are sequentially carried out to obtain a nano needle cobalt-based precursor which uniformly grows on the foam nickel substrate;
(3) Preparation of a bifunctional cobalt/cobalt oxide schottky junction catalyst: and (3) pre-reducing the nano needle cobalt-based precursor obtained in the step (2) by preliminary calcination in an argon-ammonia mixed atmosphere, and further heating and calcining to obtain the bifunctional cobalt/cobalt oxide Schottky junction catalyst.
Preferably, in step (1), the cobalt source is one or more of Co(NO3)2·6H2O、CoCl2·6H2O、Co(OAc)2·4H2O、Co(C5H7O2)3.
Preferably, in the step (1), the surfactant is one or more of NH 4 F, NH Cl, polyethylene glycol, glycerol, polyvinylpyrrolidone, and cetyltrimethylammonium bromide.
Preferably, in the step (1), the precipitant is one or more of ammonium hydroxide, urea and cyclohexanetetramine.
Preferably, in step (1), the molar ratio of the cobalt source, the surfactant and the precipitant is 1:1 to 3:3 to 7.
Preferably, in the step (1), the time of the ultrasonic treatment is 0.5 to 1h.
Preferably, in the step (2), the pretreatment method is as follows: the foam nickel substrate is cut into required size and respectively soaked in 1M hydrochloric acid solution, absolute ethanol and deionized water for 10 to 30 minutes for ultrasonic treatment to remove oxide impurities possibly existing on the surface.
Preferably, in the step (2), the temperature of the hydrothermal reaction is 80-120 ℃ and the time is 2-4 hours.
Preferably, in the step (2), the detergent used in the washing is one or more of absolute ethyl alcohol and deionized water.
Preferably, in the step (2), the drying temperature is 80-120 ℃ and the drying time is 8-12 h.
Preferably, in the step (3), in the argon-ammonia mixed atmosphere, the volume flow of the mixed gas is 100-150 sccm, and the volume ratio of the ammonia gas is 5-10%.
Preferably, in the step (3), the temperature rising rate of the preliminary calcination is 1-5 ℃/min, the temperature of the preliminary calcination is 250-350 ℃ and the time is 2-4 h.
Preferably, in the step (3), the temperature rising rate of the temperature rising and calcining is 1-5 ℃/min, the range of the target temperature t 1 is 400 ℃ < t 1 < 500 ℃, and the heat preservation time after reaching the target temperature is 2-4 h.
Meanwhile, the invention claims a bifunctional cobalt/cobalt oxide Schottky junction catalyst prepared by any one of the above methods, and the catalyst is structurally characterized in that a nano needle array uniformly growing on a foam nickel large framework is coated, and the diameter of the nano needle is 50-200 nm.
Meanwhile, the invention claims the application of the prepared bifunctional cobalt/cobalt oxide Schottky junction catalyst as an oxygen electrode catalytic material in a rechargeable zinc-air battery.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the preparation method of the bifunctional cobalt/cobalt oxide Schottky junction catalyst, firstly, a hydrothermal method is adopted, a cheap commercial foam nickel substrate is used as a carrier to directly synthesize a cobalt-based precursor, and then the cobalt-based precursor is subjected to two different high-temperature calcination in an argon-ammonia mixed atmosphere to obtain the bifunctional cobalt/cobalt oxide Schottky junction catalyst; the preparation method is simple, the materials are cheap and easy to obtain, the operation condition is mild, and the reduction process is easy to control and repeat.
2. According to the invention, the cobalt-based precursor synthesized by the hydrothermal method uniformly grows on the 3D foam nickel large framework in a coating manner in a nano needle form, and the nano needle-shaped cobalt-based precursor can expose more active sites of the finally prepared bifunctional cobalt/cobalt oxide Schottky junction catalyst, so that the catalyst has more excellent catalytic activity.
3. According to the invention, the cobalt/cobalt oxide Schottky heterojunction is synthesized in situ by adopting a twice calcining mode, so that the finally prepared bifunctional cobalt/cobalt oxide Schottky junction catalyst has double active centers with uniform interface structures, and thus, an electron coupling effect of a stable interface is generated, and the electrocatalytic activity and the electron conduction capacity are improved.
4. The bifunctional cobalt/cobalt oxide Schottky junction catalyst provided by the invention can drive oxygen evolution reaction with current density of 100mA cm -2 only by low overpotential of 320mV in alkaline environment, and compared with commercial Pt/C, the catalyst has equivalent electrocatalytic oxygen reduction performance and more excellent electrocatalytic oxygen reduction stability, and has oxygen-based bifunctional electrocatalytic activity.
5. When the bifunctional cobalt/cobalt oxide Schottky junction catalyst provided by the invention is used as an oxygen electrode material to be assembled into a chargeable liquid zinc-air battery, the battery has higher peak power density and ultra-long-time constant current charge-discharge cycling stability, and is superior to the battery performance which takes a commercial Pt/C-IrO 2 noble metal combined catalyst as a positive electrode material; when assembled as a positive electrode material into a flexible solid zinc-air battery, the battery exhibits an ultra-high peak power density and excellent cycling stability.
Drawings
FIG. 1 is a flow chart of the preparation of a dual function cobalt/cobalt oxide Schottky junction catalyst in accordance with example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a dual function cobalt/cobalt oxide Schottky junction catalyst prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the bifunctional cobalt/cobalt oxide Schottky junction catalysts (a-c) obtained in example 1, the cobalt oxide nanocatalysts (d-f) obtained in comparative example 1, and the cobalt nanocatalysts (d-f) obtained in comparative example 2 of the present invention;
FIG. 4 is an XRD pattern of three catalysts prepared in example 1 and comparative examples 1-2 according to the present invention;
FIG. 5 is a transmission electron microscope image of a dual function cobalt/cobalt oxide Schottky junction catalyst prepared in example 1 of the present invention;
FIG. 6 is an initial electrocatalytic oxygen LSV (linear sweep voltammetry) curve for three catalysts and commercial nickel foam prepared in example 1 and comparative examples 1-2 of the present invention in 1M KOH electrolyte;
FIG. 7 is an electrocatalytic oxygen-evolving LSV (linear sweep voltammetry) curve after 5000 cycles in 1M KOH electrolyte for three catalysts and commercial nickel foams (available from Taiyuan sources technology Co., ltd., specification: 1.0mm thick by 250mm wide by 1000mm long) prepared in accordance with examples 1 and comparative examples 1-2;
FIG. 8 is an initial LSV curve of three catalysts and commercial Pt/C prepared in inventive example 1 and comparative examples 1-2 in 1M KOH electrolyte;
FIG. 9 is an LSV plot of the dual function cobalt/cobalt oxide Schottky junction catalyst and Pt/C prepared in example 1, initially in 1M KOH electrolyte after 1000 cycles;
FIG. 10 is a Koutecky-Levich graph of the dual function cobalt/cobalt oxide Schottky junction catalyst prepared in example 1 at various voltages;
FIG. 11 is a charge-discharge curve and a power density curve of a zinc-air cell performance test of a dual-function cobalt/cobalt oxide Schottky junction catalyst prepared in example 1 of the present invention as an oxygen electrode catalytic material for a rechargeable liquid zinc-air cell, in comparison to a Pt/C-IrO 2 commercial noble metal catalyst combination;
FIG. 12 is a cycle test chart of performance testing of a zinc air cell using the dual function cobalt/cobalt oxide Schottky junction catalyst prepared in example 1 of the present invention as the oxygen electrode catalytic material for a rechargeable liquid zinc air cell, in contrast to the Pt/C-IrO 2 commercial noble metal catalyst combination;
FIG. 13 is a charge-discharge and power density curve of the dual-function cobalt/cobalt oxide Schottky junction catalyst prepared in example 1 of the present invention as a cathode material for a flexible solid zinc-air battery for performing zinc-air battery performance test;
Fig. 14 is a charge-discharge stability test chart of the performance test of the zinc-air battery by using the dual-function cobalt/cobalt oxide schottky junction catalyst prepared in the invention example 1 as the positive electrode material of the flexible solid zinc-air battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Although the steps of the present invention are arranged by reference numerals, the order of the steps is not limited, and the relative order of the steps may be adjusted unless the order of the steps is explicitly stated or the execution of a step requires other steps as a basis. It is to be understood that the term "and/or" as used herein relates to and encompasses any and all possible combinations of one or more of the associated listed items.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
Example 1
The preparation method of the bifunctional cobalt/cobalt oxide Schottky junction catalyst comprises the following steps:
(1) 1.16g of Co (NO 3)2·6H2 O, 0.30g of NH 4 F and 1.20g of urea are dissolved in 70mL of deionized water at normal temperature and pressure, and the solution is subjected to ultrasonic treatment for 0.5h to obtain a homogeneous cobalt-based precursor solution;
(2) Cutting a commercial foam nickel substrate material with the thickness of 1mm to 3mm multiplied by 4mm, respectively soaking the commercial foam nickel substrate material in a 1M hydrochloric acid solution, absolute ethyl alcohol and deionized water, and ultrasonically cleaning the commercial foam nickel substrate material for 10 minutes to remove oxide impurities possibly existing on the surface; then vertically placing the cleaned foam nickel into a 100mL polytetrafluoroethylene lining, pouring the cobalt-based precursor solution obtained in the step (1), and placing the cobalt-based precursor solution into an electrothermal blowing drying oven to perform heating reaction for 2h at 120 ℃; and after cooling to room temperature, taking out, respectively washing with absolute ethyl alcohol and deionized water for 3 times, then placing in a vacuum drying oven, and drying for 12 hours at 80 ℃ to obtain the nano needle cobalt-based precursor uniformly growing on the 3D foam nickel large framework.
(3) Placing the nano needle cobalt-based precursor obtained in the step (2) in a corundum ark and placing the corundum ark at the center of a tube furnace, heating NH 3/Ar mixed gas (ammonia accounts for 5% of the volume of the mixed gas) to 300 ℃ at a heating rate of 2 ℃/min, calcining for 3 hours at the temperature, further heating to 450 ℃ at the same heating rate, calcining for 3 hours, and naturally cooling to room temperature under the mixed atmosphere to obtain the bifunctional cobalt/cobalt oxide Schottky junction catalyst.
Example 2
The preparation method of the bifunctional cobalt/cobalt oxide Schottky junction catalyst comprises the following steps:
(1) 1.16g of Co (NO 3)2·6H2 O, 0.30g of NH 4 F and 1.20g of urea are dissolved in 70mL of deionized water at normal temperature and pressure, and the solution is subjected to ultrasonic treatment for 0.5h to obtain a homogeneous cobalt-based precursor solution;
(2) Cutting a commercial foam nickel substrate material with the thickness of 1mm to 3mm multiplied by 4mm, respectively soaking the commercial foam nickel substrate material in a 1M hydrochloric acid solution, absolute ethyl alcohol and deionized water, and ultrasonically cleaning the commercial foam nickel substrate material for 20 minutes to remove oxide impurities possibly existing on the surface; then vertically placing the cleaned foam nickel into a 100mL polytetrafluoroethylene lining, pouring the cobalt-based precursor solution obtained in the step (1), and placing the cobalt-based precursor solution into an electrothermal blowing drying oven to perform heating reaction for 2h at the temperature of 100 ℃; and after cooling to room temperature, taking out, respectively washing with absolute ethyl alcohol and deionized water for 3 times, then placing in a vacuum drying oven, and drying for 12 hours at the temperature of 100 ℃ to obtain the nano needle cobalt-based precursor uniformly growing on the 3D foam nickel large framework.
(3) Placing the nano needle cobalt-based precursor obtained in the step (2) in a corundum ark and placing the corundum ark at the center of a tube furnace, heating NH 3/Ar mixed gas (ammonia accounts for 5% of the volume of the mixed gas) to 250 ℃ at a heating rate of 1 ℃/min, calcining for 2h at the temperature, further heating to 420 ℃ at the same heating rate, calcining for 2h, and naturally cooling to room temperature under the mixed atmosphere to obtain the bifunctional cobalt/cobalt oxide Schottky junction catalyst.
Example 3
The preparation method of the bifunctional cobalt/cobalt oxide Schottky junction catalyst comprises the following steps:
(1) 1.16g of Co (NO 3)2·6H2 O, 0.30g of NH 4 F and 1.20g of urea are dissolved in 70mL of deionized water at normal temperature and pressure, and the solution is subjected to ultrasonic treatment for 1h to obtain a homogeneous cobalt-based precursor solution;
(2) Cutting a commercial foam nickel substrate material with the thickness of 1mm to 3mm multiplied by 4mm, respectively soaking in 1M hydrochloric acid solution, absolute ethyl alcohol and deionized water, and ultrasonically cleaning for 30min to remove oxide impurities possibly existing on the surface; then vertically placing the cleaned foam nickel into a 100mL polytetrafluoroethylene lining, pouring the cobalt-based precursor solution obtained in the step (1), and placing the cobalt-based precursor solution into an electrothermal blowing drying oven to perform heating reaction for 2h at 80 ℃; and after cooling to room temperature, taking out, respectively washing with absolute ethyl alcohol and deionized water for 3 times, then placing in a vacuum drying oven, and drying for 12 hours at 120 ℃ to obtain the nano needle cobalt-based precursor uniformly growing on the 3D foam nickel large framework.
(3) Placing the nano needle cobalt-based precursor obtained in the step (2) in a corundum ark and placing the corundum ark at the center of a tube furnace, heating NH 3/Ar mixed gas (ammonia accounts for 5% of the volume of the mixed gas) to 350 ℃ at a heating rate of 5 ℃/min, calcining for 3 hours at the temperature, further heating to 470 ℃ at the same heating rate, calcining for 3 hours, and naturally cooling to room temperature under the mixed atmosphere to obtain the bifunctional cobalt/cobalt oxide Schottky junction catalyst.
Example 4
The preparation method of the bifunctional cobalt/cobalt oxide Schottky junction catalyst comprises the following steps:
(1) 1.32g of Co (NO 3)2·6H2 O, 0.21g of NH 4 F and 0.95g of urea are dissolved in 70mL of deionized water at normal temperature and pressure, and the solution is subjected to ultrasonic treatment for 0.5h to obtain a homogeneous cobalt-based precursor solution;
(2) Cutting a commercial foam nickel substrate material with the thickness of 1mm to 3mm multiplied by 4mm, respectively soaking the commercial foam nickel substrate material in a 1M hydrochloric acid solution, absolute ethyl alcohol and deionized water, and ultrasonically cleaning the commercial foam nickel substrate material for 10 minutes to remove oxide impurities possibly existing on the surface; then vertically placing the cleaned foam nickel into a 100mL polytetrafluoroethylene lining, pouring the cobalt-based precursor solution obtained in the step (1), and placing the cobalt-based precursor solution into an electrothermal blowing drying oven to perform heating reaction for 2h at 120 ℃; and after cooling to room temperature, taking out, respectively washing with absolute ethyl alcohol and deionized water for 3 times, then placing in a vacuum drying oven, and drying for 12 hours at 80 ℃ to obtain the nano needle cobalt-based precursor uniformly growing on the 3D foam nickel large framework.
(3) Placing the nano needle cobalt-based precursor obtained in the step (2) in a corundum ark and placing the corundum ark at the center of a tube furnace, heating NH 3/Ar mixed gas (ammonia accounts for 5% of the volume of the mixed gas) to 300 ℃ at a heating rate of 2 ℃/min, calcining for 3 hours at the temperature, further heating to 450 ℃ at the same heating rate, calcining for 3 hours, and naturally cooling to room temperature under the mixed atmosphere to obtain the bifunctional cobalt/cobalt oxide Schottky junction catalyst.
Example 5
The preparation method of the bifunctional cobalt/cobalt oxide Schottky junction catalyst comprises the following steps:
(1) 1.05g of Co (NO 3)2·6H2 O, 0.33g of NH 4 F and 1.07g of urea are dissolved in 70mL of deionized water at normal temperature and pressure, and the solution is subjected to ultrasonic treatment for 0.5h to obtain a homogeneous cobalt-based precursor solution;
(2) Cutting a commercial foam nickel substrate material with the thickness of 1mm to 3mm multiplied by 4mm, respectively soaking the commercial foam nickel substrate material in a 1M hydrochloric acid solution, absolute ethyl alcohol and deionized water, and ultrasonically cleaning the commercial foam nickel substrate material for 10 minutes to remove oxide impurities possibly existing on the surface; then vertically placing the cleaned foam nickel into a 100mL polytetrafluoroethylene lining, pouring the cobalt-based precursor solution obtained in the step (1), and placing the cobalt-based precursor solution into an electrothermal blowing drying oven to perform heating reaction for 2h at 120 ℃; and after cooling to room temperature, taking out, respectively washing with absolute ethyl alcohol and deionized water for 3 times, then placing in a vacuum drying oven, and drying for 12 hours at 80 ℃ to obtain the nano needle cobalt-based precursor uniformly growing on the 3D foam nickel large framework.
(3) Placing the nano needle cobalt-based precursor obtained in the step (2) in a corundum ark and placing the corundum ark at the center of a tube furnace, heating NH 3/Ar mixed gas (ammonia accounts for 5% of the volume of the mixed gas) to 300 ℃ at a heating rate of 2 ℃/min, calcining for 3 hours at the temperature, further heating to 450 ℃ at the same heating rate, calcining for 3 hours, and naturally cooling to room temperature under the mixed atmosphere to obtain the bifunctional cobalt/cobalt oxide Schottky junction catalyst.
Comparative example 1
A preparation method of a cobalt oxide nano catalyst comprises the following steps:
(1) 1.16g of Co (NO 3)2·6H2 O, 0.30g of NH 4 F and 1.20g of urea are dissolved in 70mL of deionized water at normal temperature and pressure, and the solution is subjected to ultrasonic treatment for 0.5h to obtain a homogeneous cobalt-based precursor solution;
(2) Cutting a commercial foam nickel substrate material with the thickness of 1mm to 3mm multiplied by 4mm, respectively soaking the commercial foam nickel substrate material in a 1M hydrochloric acid solution, absolute ethyl alcohol and deionized water, and ultrasonically cleaning the commercial foam nickel substrate material for 10 minutes to remove oxide impurities possibly existing on the surface; vertically placing the cleaned foam nickel into a 100mL polytetrafluoroethylene lining, pouring the cobalt-based precursor solution obtained in the step (1), and placing the cobalt-based precursor solution into an electrothermal blowing drying oven to heat for 2h at 120 ℃; and after cooling to room temperature, taking out, respectively washing with absolute ethyl alcohol and deionized water for 3 times, then placing in a vacuum drying oven, and drying for 12 hours at 80 ℃ to obtain the nano needle cobalt-based precursor uniformly growing on the 3D foam nickel large framework.
(3) Placing the nano needle cobalt-based precursor obtained in the step (2) in a corundum ark, placing the corundum ark at the center of a tube furnace, heating NH 3/Ar mixed gas (ammonia accounts for 5% of the volume of the mixed gas) to 300 ℃ at a heating rate of 2 ℃/min, calcining for 3h at the temperature, further heating to 400 ℃ at the same heating rate, calcining for 3h, and naturally cooling to room temperature under the mixed atmosphere to obtain the cobalt oxide nano catalyst.
The difference between this comparative example and example 1 is: the target temperature of the comparative temperature-rising calcination is 400 ℃, and the obtained product is the cobalt oxide nano catalyst.
Comparative example 2
A preparation method of a cobalt nano catalyst comprises the following steps:
(1) 1.16g of Co (NO 3)2·6H2 O, 0.30g of NH 4 F and 1.20g of urea are dissolved in 70mL of deionized water at normal temperature and pressure, and the solution is subjected to ultrasonic treatment for 0.5h to obtain a homogeneous cobalt-based precursor solution;
(2) Cutting a commercial foam nickel substrate material with the thickness of 1mm to 3mm multiplied by 4mm, respectively soaking the commercial foam nickel substrate material in a 1M hydrochloric acid solution, absolute ethyl alcohol and deionized water, and ultrasonically cleaning the commercial foam nickel substrate material for 10 minutes to remove oxide impurities possibly existing on the surface; then vertically placing the cleaned foam nickel into a 100mL polytetrafluoroethylene lining, pouring the cobalt-based precursor solution obtained in the step (1), and placing the cobalt-based precursor solution into an electrothermal blowing drying oven to heat for 2h at 120 ℃; and after cooling to room temperature, taking out, respectively washing with absolute ethyl alcohol and deionized water for 3 times, then placing in a vacuum drying oven, and drying for 12 hours at 80 ℃ to obtain the nano needle cobalt-based precursor uniformly growing on the 3D foam nickel large framework.
(3) Placing the nano needle cobalt-based precursor obtained in the step (2) in a corundum ark and placing the corundum ark at the center of a tube furnace, heating NH 3/Ar mixed gas (ammonia accounts for 5% of the volume of the mixed gas) to 300 ℃ at a heating rate of 2 ℃/min, calcining for 3 hours at the temperature, further heating to 500 ℃ at the same heating rate, calcining for 3 hours, and naturally cooling to room temperature under the mixed atmosphere to obtain the cobalt nano catalyst.
The difference between this comparative example and example 1 is: the target temperature of the temperature rise calcination of the comparative example is 500 ℃, and the obtained product is a cobalt nano catalyst.
The structure and properties of the products of example 1 and comparative examples 1 to 2 were tested as follows:
(1) Microscopic structural analysis
Performing scanning electron microscope morphology analysis on the cobalt-based precursor prepared in the step (2) in the embodiment 1, wherein the result is shown in a figure 2, the cobalt-based precursor is in a nano needle array and uniformly grows on a 3D foam nickel large framework in a coating manner, and the diameter of the nano needle is 50-200 nm;
The dual-function cobalt/cobalt oxide schottky junction catalyst prepared in example 1 was subjected to structural analysis by a scanning electron microscope and a transmission electron microscope, and as shown in fig. 3 (a) and fig. 5, the sample remained in a uniform nanoneedle array after calcination at a high temperature of 450 ℃; the high-resolution transmission electron microscope image of the sample can judge that the metal cobalt/cobalt oxide Schottky junction catalyst is a nano needle array with the radius of 50-200 nm.
The cobalt oxide nanocatalyst prepared in comparative example 1 was analyzed by scanning electron microscopy and as shown in fig. 3 (b), the sample remained a uniform nanoneedle array after calcination at 400 ℃.
The cobalt nanocatalyst prepared in comparative example 2 was analyzed by scanning electron microscopy and as shown in fig. 3 (c), after calcination at a high temperature of 500 c, the original nanoneedle morphology of the sample collapsed, indicating that the calcined sample polymerized at a higher temperature, which would be detrimental to the exposure of the catalytically active sites.
(2) Phase analysis
As a result of phase analysis of the catalyst products obtained in example 1 and comparative examples 1 to 2, as shown in fig. 4, it can be seen that in comparative example 1, the target temperature for the temperature-raising calcination was 400 ℃, and the main phase of the obtained product was cobalt oxide, which was compared with a standard card "PDF: 09-0402'; in example 1, the target temperature for the temperature-raising calcination was 450 ℃, and the main phase of the obtained product was cobalt/cobalt oxide and standard card "PDF:01-1255 "and" PDF: 09-0402'; in comparative example 2, the target temperature for the temperature-raising calcination was 500 ℃, and the main phase of the obtained product was metallic cobalt, which was compared with a standard card "PDF:01-1255 ".
(3) Electrochemical oxygen evolution Performance study
The testing method comprises the following steps: the three different catalyst products obtained in example 1 and comparative examples 1-2 were cut to a length of 1cm by a width of 1cm, sandwiched between platinum sheet electrode clips as working electrodes, carbon rods as counter electrodes, saturated calomel electrodes as reference electrodes, and 1M KOH as electrolyte to form a standard three-electrode system, which was tested for electrochemical performance using a GAMRY electrochemical workstation. The electrocatalytic oxygen evolution activity was characterized by an initial Linear Sweep Voltammetry (LSV) curve and the stability by an LSV curve after 5000 cycles of endurance testing.
Analysis of results: as shown in fig. 6 and 7, the bi-functional cobalt/cobalt oxide schottky junction catalyst prepared in example 1 can drive oxygen evolution reaction with current density of 100ma·cm -2 only by using 320mV overpotential, and the continuous enhancement of OER performance after 5000 cycles of cyclic test shows excellent OER activity and stability, compared with the cobalt oxide nanocatalyst and cobalt nanocatalyst prepared in comparative examples 1-2, which have poor OER activity and undesirable stability.
(4) Electrocatalytic oxygen reduction performance study
The testing method comprises the following steps: the electrocatalytic oxygen reduction performance of the bifunctional cobalt/cobalt oxide schottky junction catalyst was studied by a CHI760 e-type electrochemical workstation and a rotating disk electrode of 4mm diameter.
Analysis of results: as shown in fig. 8, 9 and 10, the half-wave potential of the electrocatalytic oxygen reduction reaction of the bifunctional cobalt/cobalt oxide schottky junction catalyst prepared in example 1 in an alkaline environment is 830mV, which is equivalent to the performance of noble metal Pt/C (purchased from alfa eastern corporation, 20% Pt supported on carbon black), and has better stability; the number of transferred electrons in the ORR process was calculated to be 3.74 by the Koutecky-Levich equation, indicating that the electrocatalytic oxygen reduction reaction of the bifunctional cobalt/cobalt oxide schottky junction catalyst is a process approaching 4 electrons.
(5) Use in zinc air batteries
1) Oxygen electrode material for liquid zinc air battery
The testing method comprises the following steps: the dual-function cobalt/cobalt oxide Schottky junction catalyst is used as an oxygen electrode material of a liquid zinc-air battery, and the battery is subjected to electrochemical performance test
Analysis of results: as a result, as shown in fig. 11 and 12, the peak power density of the battery was as high as 154.32mw·cm -2, and the constant current charge-discharge cycle time was more than 1000 hours, with superior battery performance as an oxygen electrode over the commercial Pt/C-IrO 2 noble metal combination catalyst (Pt/C available from alfa eastern sa, irO 2 available from alfa Ding Shiji (shanghai), inc.).
2) Cathode material for flexible solid zinc-air battery
The testing method comprises the following steps: the bi-functional cobalt/cobalt oxide schottky junction catalyst was used as the positive electrode material for a flexible solid zinc air cell and the electrochemical performance of the cell was discussed.
Analysis of results: as a result, as shown in fig. 13 and 14, the peak power density of the battery is 106.75mw·cm -2, the constant current charge-discharge cycle time exceeds 30 hours, and the international report on the electrochemical performance of the flexible solid zinc-air battery is very little reported at present.
The results show that the bifunctional cobalt/cobalt oxide Schottky junction catalyst has optimal electrocatalytic oxygen evolution and oxygen reduction performance, which benefits from the Mort Schottky heterojunction between the metallic cobalt and the cobalt oxide with stable interface structures and the special electronic effect thereof, the two-dimensional nano needle structure and the synergistic effect of two active components; in addition, the catalytic material shows excellent electrochemical performance as an oxygen electrode catalyst for rechargeable zinc-air batteries, indicating that the cobalt/cobalt oxide schottky junction catalyst can be effectively applied to rechargeable zinc-air batteries as a cost-effective transition metal catalyst to reduce the production cost of zinc-air batteries.
It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (8)
1. The application of the bifunctional cobalt/cobalt oxide Schottky junction catalyst as an oxygen electrode catalytic material in a rechargeable zinc-air battery is characterized in that the preparation method of the bifunctional cobalt/cobalt oxide Schottky junction catalyst comprises the following steps:
(1) Preparation of a homogeneous precursor solution: dissolving a cobalt source, a surfactant and a precipitator in deionized water, and performing ultrasonic treatment to obtain a homogeneous precursor solution;
(2) Preparing a nano needle cobalt-based precursor: placing the pretreated foam nickel substrate into a polytetrafluoroethylene lining, adding the homogeneous precursor solution obtained in the step (1) into the polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a drying oven for hydrothermal reaction; after the reaction product is cooled to room temperature, washing and drying are sequentially carried out to obtain a nano needle cobalt-based precursor which uniformly grows on the foam nickel substrate;
(3) Preparation of a bifunctional cobalt/cobalt oxide schottky junction catalyst: pre-reducing the nano needle cobalt-based precursor obtained in the step (2) by preliminary calcination in an argon-ammonia mixed atmosphere, and further heating and calcining to obtain the bifunctional cobalt/cobalt oxide Schottky junction catalyst;
In the step (3), the temperature rising rate of the preliminary calcination is 1-5 ℃/min, the target temperature is 250-350 ℃, and the calcination time is 2-4 h after reaching the target temperature; the temperature rising rate of the temperature rising and calcining is 1-5 ℃/min, the range of the target temperature t 1 is 400 ℃ < t 1 < 500 ℃, and the calcining time is 2-4 h after reaching the target temperature.
2. The use of a bi-functional cobalt/cobalt oxide schottky junction catalyst according to claim 1 as an oxygen electrode catalytic material in a rechargeable zinc air cell, wherein in step (1) the cobalt source is one or more of Co(NO3)2·6H2O、CoCl2·6H2O、Co(OAc)2·4H2O、Co(C5H7O2)3; the surfactant is one or more of NH 4F、NH4 Cl, polyethylene glycol, glycerol, polyvinylpyrrolidone and cetyltrimethylammonium bromide; the precipitant is one or more of ammonium hydroxide, urea and cyclohexanetetramine.
3. The use of a bifunctional cobalt/cobalt oxide schottky junction catalyst as an oxygen electrode catalyst material in a rechargeable zinc-air cell according to claim 1, wherein in step (1), the molar ratio of cobalt source, surfactant and precipitant is 1:1 to 3:3 to 7.
4. The use of a bifunctional cobalt/cobalt oxide schottky junction catalyst as an oxygen electrode catalyst material in a rechargeable zinc-air cell according to claim 1, wherein in step (1), the time of the ultrasonic treatment is 0.5-1 h.
5. The use of a bifunctional cobalt/cobalt oxide schottky junction catalyst as an oxygen electrode catalyst material in a rechargeable zinc-air cell according to claim 1, wherein in step (2), the pretreatment method is: the foamed nickel substrate was cut to a desired size and sonicated in 1M hydrochloric acid solution, absolute ethanol and deionized water, respectively, for 10 to 30 minutes to remove oxide impurities that may be present on the surface.
6. The use of a bifunctional cobalt/cobalt oxide schottky junction catalyst as an oxygen electrode catalyst material in a rechargeable zinc-air battery according to claim 1, wherein in step (2), the hydrothermal reaction is performed at a temperature of 80-120 ℃ for a time of 2-4 hours; the washing liquid for washing is one or more of absolute ethyl alcohol and deionized water; the drying temperature is 80-120 ℃ and the drying time is 8-12 h.
7. The use of a bifunctional cobalt/cobalt oxide schottky junction catalyst as an oxygen electrode catalyst material in a rechargeable zinc-air battery according to claim 1, wherein in the step (3), the volume flow of the mixed gas is 100-150 sccm, and the volume ratio of ammonia gas is 5-10%.
8. The use of a bifunctional cobalt/cobalt oxide schottky junction catalyst as oxygen electrode catalytic material in rechargeable zinc-air cells according to claim 1, wherein the catalyst is structurally characterized by a coated nanoneedle array uniformly grown on a foam nickel large framework, and the diameter of the nanoneedle is 50-200 nm.
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