CN111653789B - Zinc-air battery catalyst and preparation method thereof - Google Patents
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Abstract
The invention relates to a zinc-air battery catalyst and a preparation method thereof, wherein the zinc-air battery catalyst consists of a plurality of catalytic particle units, each catalytic particle unit comprises an inner layer and an outer layer formed on the outer surface of the inner layer, the inner layer is carbon nano-fiber, the outer layer consists of metal oxide nano-particles coating the carbon nano-fiber, and the metal oxide nano-particles are AB with oxygen vacancy2X4Wherein A and B are different transition metals, and X is a chalcogen element. By forming an outer layer structure composed of metal oxide nanoparticles on the surface of the carbon nanofiber, similar to a coaxial cable structure, the cooperation of the coaxial cable structure and oxygen vacancies can improve metal oxides (such as NiCo)2O4Etc.) and improve the intrinsic catalytic activity of the material, and also avoid metal oxides (e.g., NiCo)2O4Etc.) agglomeration of nanoparticles under long cycling, improving their stability.
Description
Technical Field
The invention belongs to the field of catalysts, relates to a zinc-air battery catalyst with high efficiency, low cost and long service life, and particularly relates to a zinc-air battery catalyst, a preparation method and application thereof.
Background
With the increasing severity of the problems of environmental pollution, energy crisis and the like, the demand of people for developing novel energy storage devices with high efficiency and low price is pressing day by day. Among them, zinc-air batteries are receiving particular attention due to their environmental friendliness and high energy density. In zinc-air batteries, the oxygen reduction (ORR) reaction plays a crucial role. Currently, commercial Pt and Pt-based catalysts are the most representative and widely used oxygen reduction catalysts. However, their high price and scarce reserves also limit their further commercial use. Therefore, it is necessary to find a non-Pt electrocatalyst which is efficient, stable and cheap, which is also a research hotspot in the energy field today.
Among the non-noble metal ORR catalysts, transition metal oxides, especially spinel metal oxides, have attracted attention because of their low cost, high efficiency, long life and simplicity of preparation. However, the lower conductivity of transition metal oxides is still one of the important factors affecting their performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a zinc-air battery catalyst with high efficiency, low cost and long service life.
In order to achieve the purpose, the invention adopts the technical scheme that: a zinc-air battery catalyst is composed of a plurality of catalytic particle units, wherein each catalytic particle unit comprises an inner layer and an outer layer formed on the outer surface of the inner layer, the inner layer is carbon nanofiber, the outer layer is composed of metal oxide nanoparticles coating the carbon nanofiber, and the metal oxide nanoparticles are AB with oxygen vacancies2X4Wherein A and B are different transition metals, and X is a chalcogen element.
Optimally, the diameter of the carbon nanofiber is 10-800 nm, and the length of the carbon nanofiber is 1-100 mu m.
Optimally, the particle size of the metal oxide nanoparticles is 10-100 nm.
Further, the metal oxide nanoparticles are NiCo2O4。
Further, the metal oxide nanoparticles are obtained by gelling a precursor solution containing A and B, performing heat treatment under inert gas conditions, and cooling in air.
The invention also aims to provide a preparation method of the zinc-air battery catalyst, which comprises the following steps:
(a) performing electrostatic spinning on the polymer, and calcining to obtain the carbon nanofiber;
(b) dispersing the carbon nanofibers in a solution containing A and B precursors for gelation, carrying out heat treatment under the condition of inert gas, and cooling in the air.
Preferably, in step (a), the polymer is polyacrylonitrile.
Further, in the step (a), the polyacrylonitrile is dissolved in N, N-dimethylformamide to form a solution, and then the solution is injected into an electrostatic spinning machine to carry out electrostatic spinning under the condition of high voltage of 18-20 kV to obtain the fiber yarn; and after drying, calcining at 700-1000 ℃ in an inert gas atmosphere to obtain the carbon nanofiber.
Optimally, in step (b), Ni (NO) is added3)2·6H2O and Co (NO)3)2·6H2Dissolving O in ethanol, then adding propylene oxide and the carbon nanofiber, stirring, and gelatinizing at 50-90 ℃; and calcining the gelled product at 300-400 ℃ in an inert atmosphere, and cooling in air.
Further, in the step (b), the Ni (NO)3)2·6H2O、Co(NO3)2·6H2The proportion of the O, the carbon nano-fiber and the propylene oxide is 0.05-0.14 mM: 0.15 to 0.25mM Co (NO)3)2·6H2O：0.2～0.5g：1.5～2.5g。
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the zinc-air battery catalyst of the invention forms an outer layer structure composed of metal oxide nano particles on the surface of carbon nano fiber, is similar to a coaxial cable structure, and the matching of the coaxial cable structure and oxygen vacancy can improve metal oxide (such as NiCo)2O4Etc.) and improve the intrinsic catalytic activity of the material, and also avoid metal oxides (e.g., NiCo)2O4Etc.) the agglomeration of nanoparticles under long cycles, improving their stability. Compared with other composite material methods, the preparation method of the zinc-air battery catalyst can obtain the coaxial cable structure, and can improve the specific surface area of the material to the maximum extent, so that the method for preparing the oxygen vacancy by changing the calcination atmosphere is very simple.
Drawings
FIG. 1 is a schematic flow chart of the preparation of the zinc-air battery catalyst in example 1 and comparative example 1;
fig. 2 is a test chart of the zinc-air battery catalysts in example 1 and comparative example 1: a) CNF prepared by electrostatic spinning; b) NiCo2O4A topography of the nanoparticles; c) NiCo2O4The topography of @ CNF (Zinc-air cell catalyst in comparative example 1); d) NiCo2O4The topography of @ CNF-OVs (zinc-air battery catalyst in example 1); e) NiCo2O4TEM image of @ CNF-OVs; e) NiCo2O4HRTEM image of @ CNF-OVs; g) NiCo2O4The elemental profile of @ CNF-OVs;
fig. 3 is a graph of electrochemical performance of different products: a) linear Sweep Voltammogram (LSV); b) tafel plot; c) the number of electron transfers; d) at O2CNF, NiCo under saturated 0.1M KOH2O4、NiCo2O4@CNF、NiCo2O4HO of @ CNF-OVs and commercial Pt/C2 -Content percentage (rotation speed 1600 rpm); e) NiCo2O4The cycling stability test curves for @ CNF-OVs and Pt/C; f) CNF, NiCo2O4、NiCo2O4@ CNF and NiCo2O4The Electrochemical Impedance (EIS) curve of @ CNF-OVs, the inset is the impedance fitting equivalent circuit;
fig. 4 is a graph of electrochemical performance of different products in zinc-air cell test data: a) NiCo2O4The discharge polarization curves of @ CNF-OVs and Pt/C catalysts; b) NiCo2O4Discharge curves at @ CNF-OVs and Pt/C of 10mA cm-2Discharge capacity at a constant current density of (a); c) with NiCo2O4Rate performance under different current densities in a zinc-air battery taking @ CNF-OVs and Pt/C as catalysts; d) using NiCo2O4@ CNF-OVs and Pt/C as catalysts in a zinc-air cell at 5mA cm-2Long cycle performance;
FIG. 5 is a graph of product properties for different ratios of feed;
FIG. 6 is a graph of the properties of the gelled product after treatment at different temperatures.
Detailed Description
Zinc of the invention-an air cell catalyst comprised of a plurality of catalytic particulate units comprising an inner layer and an outer layer formed on an outer surface of the inner layer, characterized in that: the inner layer is carbon nanofiber, the outer layer is composed of metal oxide nanoparticles coating the carbon nanofiber, and the metal oxide nanoparticles are AB with oxygen vacancies2X4Wherein A and B are different transition metals, and X is a chalcogen element. By forming an outer layer structure composed of metal oxide nanoparticles on the surface of the carbon nanofiber, similar to a coaxial cable structure, the cooperation of the coaxial cable structure and oxygen vacancies can improve metal oxides (such as NiCo)2O4Etc.) and improve the intrinsic catalytic activity of the material, and also avoid metal oxides (e.g., NiCo)2O4Etc.) agglomeration of nanoparticles under long cycling, improving their stability.
The carbon nanofiber preferably has a diameter of 10 to 800nm and a length of 1 to 100 μm. The particle size of the metal oxide nanoparticles is preferably 10-100 nm. The metal oxide nanoparticles are most preferably NiCo containing oxygen vacancies2O4. The metal oxide nano-particles are obtained by gelatinizing a precursor solution containing A and B, performing heat treatment under the condition of inert gas, and cooling in the air.
The preparation method of the zinc-air battery catalyst comprises the following steps: (a) performing electrostatic spinning on the polymer, and calcining to obtain the carbon nanofiber; (b) dispersing the carbon nanofibers in a solution containing A and B precursors for gelation, and reacting the carbon nanofibers in an inert gas (e.g., N)2Or one or more of other inert gases, the same applies below) and cooling in air. Compared with other composite material methods, the obtained coaxial cable structure can improve the specific surface area of the material to the maximum extent, so that the method for changing the calcining atmosphere to produce the oxygen vacancy is also very simple.
In step (a), the polymer is preferably polyacrylonitrile. Specifically, in the step (a), the polyacrylonitrile is dissolved in N, N-dimethylformamide to form a solution, followed by injectionPutting the fiber into an electrostatic spinning machine, and performing electrostatic spinning under the high voltage condition of 18-20 kV to obtain fiber yarns; and after drying, calcining at 700-1000 ℃ in an inert gas atmosphere to obtain the carbon nanofiber. Specifically, in step (b), Ni (NO) is added3)2·6H2O and Co (NO)3)2·6H2Dissolving O in ethanol, then adding propylene oxide and the carbon nanofiber, stirring, and gelatinizing at 50-90 ℃; and heating the gelled product at 300-400 ℃, and cooling in air. The Ni (NO)3)2·6H2O、Co(NO3)2·6H2The preferable proportion of the O, the carbon nano fiber and the propylene oxide is 0.05-0.14 mM: 0.15 to 0.25mM Co (NO)3)2·6H2O：0.2～0.5g：1.5～2.5g。
The present invention will be further described with reference to examples.
Example 1
This example provides a zinc-air battery catalyst and a preparation method thereof, as shown in fig. 1, including the following steps:
(a) 1.0g of polyacrylonitrile (PAN, (C)3H3N) N, Aldrich, M.W.150000) was dissolved in 10mL of N, N-dimethylformamide (DMF, C) with stirring (30 minutes) at room temperature3H7NO); then sucking the solution into a plastic injector (5 ml) by a stainless steel nozzle (with the inner diameter of 0.4 mm), arranging the plastic injector 10cm away from a receiving plate in electrostatic spinning, applying a high voltage of 18-20 kV in the middle to carry out electrostatic spinning, collecting the cellosilk on the receiving plate after the electrostatic spinning is finished, and drying the cellosilk in a vacuum oven at 80 ℃ for 12 hours; after taking out, in N2Calcining for 3 hours at 800 ℃ in the atmosphere to obtain the required Carbon Nanofiber (CNF);
(b) 0.1mM (i.e., mmol/L, the same applies hereinafter) Ni (NO)3)2·6H2O and 0.2mM Co (NO)3)2·6H2Dissolving O in 2.5mL of ethanol, stirring uniformly (5 minutes), then adding 2.0g of propylene oxide and 0.3g of CNF, and continuing stirring at room temperature for 12 hours to obtain a mixed solution; stirring the mixed solution at 75 ℃ to promote gelation; gelling the productHeating at 350 deg.C for 3 hr under nitrogen condition, and cooling in air for 5 hr to obtain zinc-air battery catalyst (NiCo for short) with oxygen vacancy2O4@ CNF-OVs, also denoted NCO @ CNF-350, NCO @ CNF-2.5).
The resulting zinc-air cell catalysts were tested as shown in fig. 2 (fig. 2a) to 2g)) and fig. 3 (fig. 3a) to 3 f)). Fig. 2a) shows CNFs prepared by electrospinning, which have smooth surfaces, a diameter of about 600nm and a length of several tens of microns. NiCo prepared by sol-gel method2O4The morphology of the nanoparticles is shown in FIG. 2b), with a particle size distribution of about 50 nm. FIGS. 2c) and 2d) show NiCo, respectively2O4@ CNF and NiCo2O4The morphology of @ CNF-OVs shows the structure of nanoparticles coated on fibers. NiCo can be seen on the electrochemical performance diagram of FIG. 32O4@ CNF-OVs vs. CNF, NiCo2O4And NiCo2O4The @ CNF and ORR catalytic performance are greatly improved, the performance is close to commercial Pt/C, the cycling stability is even higher than that of Pt/C, and the resistance of the composite material is greatly reduced compared with the expected resistance.
The above zinc-air battery catalyst was assembled into a zinc-air battery according to a conventional method (disclosed in chinese patent application No. 201910554850.9) and tested, and from the zinc air battery test data of fig. 4, the battery performance was even significantly higher than that of a zinc air battery using commercial Pt/C as a catalyst.
Example 2
This example provides a catalyst and method of preparation which is essentially the same as in example 1 except that: in step (a), taking out the reaction product and adding the reaction product to N2Calcining for 3 hours at 700 ℃ in the atmosphere to obtain the required carbon nanofiber.
Example 3
This pair of examples provides a catalyst and a method of making the same, which is substantially the same as in example 1, except that: in step (a), taking out the reaction product and adding the reaction product to N2Calcining for 3 hours at 1000 ℃ in the atmosphere to obtain the required carbon nanofiber.
The catalysts of examples 2 to 3 were assembled into a zinc-air battery according to a conventional method (disclosed in chinese patent application No. 201910554850.9) and tested; the performance of example 2 is about 10% lower than that of example 1, mainly the degree of carbonization is insufficient; example 3 performed close to example 1.
Example 4
This example provides a catalyst and method of preparation which is essentially the same as in example 1 except that: in step (b), 0.1mM (i.e., mmol/L, the same applies hereinafter) Ni (NO)3)2·6H2O and 0.2mM Co (NO)3)2·6H2O was dissolved in 2.5mL of ethanol, stirred well (5 minutes), and then 1.5g of propylene oxide and 0.5g of CNF, NCO @ CNF-1.5 for short were added.
Example 5
This example provides a catalyst and method of preparation which is essentially the same as in example 1 except that: in step (b), 0.1mM (i.e., mmol/L, the same applies hereinafter) Ni (NO)3)2·6H2O and 0.2mM Co (NO)3)2·6H2O was dissolved in 2.5mL of ethanol, stirred well (5 minutes), and then 2.5g of propylene oxide and 0.2g of CNF, NCO @ CNF-5 for short were added.
Electrochemical performance tests were conducted on the catalysts of examples 1, 4, 5, and the results are shown in FIG. 5, in which NCO @ CNF-2.5 (of example 1) had the best oxygen reduction electrocatalytic performance. The results show that the amount of metal oxide in the outer layer of the carbon fiber cannot be too small, otherwise the catalytic activity of the oxide is not high enough; too much carbon fiber is not needed, otherwise, the carbon fiber is coated compactly, the electrolyte is difficult to soak, and the conductive effect of the carbon fiber is difficult to fully exert.
Example 6
This example provides a catalyst and method of preparation which is essentially the same as in example 1 except that: in the step (b), the gelled products are respectively treated at 300 ℃ under the air condition, and the final product is called NCO @ CNF-300 for short.
Example 7
This example provides a catalyst and method of preparation which is essentially the same as in example 1 except that: in the step (b), the gelled products are respectively treated at 400 ℃ under the air condition, and the final product is called NCO @ CNF-400 for short.
Electrochemical performance tests were conducted on the catalysts of examples 1, 6, and 7, and the results are shown in FIG. 6, in which NCO @ CNF-350 (of example 1) had the best oxygen reduction electrocatalytic performance. The NCO has poor crystallinity and poor performance due to too low temperature; at too high a temperature, part of the NCO is reduced by carbon, which also leads to poor properties.
The catalysts of examples 2 to 5 were assembled into a zinc-air battery according to a conventional method (disclosed in chinese patent application No. 201910554850.9) and tested. The performance of the batteries using the catalysts of examples 2 to 5 was reduced to various degrees as compared to example 1, and the results are shown in table 1.
Table 1 comparison of zinc-air cell performance for each example.
Comparative example 1
This comparative example provides a catalyst and a process for its preparation, which is identical to step (a) of example 1, resulting in CNF.
Comparative example 2
This comparative example provides a catalyst and a process for its preparation, which is identical to step (b) of example 1, giving NiCo2O4And (3) nanoparticles.
Comparative example 3
This comparative example provides a catalyst and method of preparation which is essentially the same as in example 1 except that: in the step (b), the gelated product is heated for 3 hours at 350 ℃ under the air condition, and the obtained product is NiCo for short2O4@ CNF, cannot be used for zinc-air battery performance.
Comparative example 4
This comparative example provides a commercial Pt/C catalyst (Hunan Min Sr Zhuang technology).
The above examples are merely illustrative of the technical concept and features of the present invention, and have similar effects to other oxides as shell layers or to replace other highly conductive inner layers. It is intended that the present invention be understood and implemented by those skilled in the art, and not limited thereto. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (3)
1. A zinc-air battery catalyst comprised of a plurality of catalytic particulate units, said catalytic particulate units comprising an inner layer and an outer layer formed on an outer surface of said inner layer, characterized in that: the inner layer is carbon nano fiber, the outer layer is composed of metal oxide nano particles coating the carbon nano fiber, and the metal oxide nano particles are NiCo with oxygen vacancy2O4；
The preparation method of the zinc-air battery catalyst comprises the following steps:
(a) dissolving polyacrylonitrile in N, N-dimethylformamide to form a solution, then injecting the solution into an electrostatic spinning machine, and carrying out electrostatic spinning under the high-voltage condition of 18-20 kV to obtain a fiber yarn; after drying, calcining at 800 ℃ in an inert gas atmosphere to obtain the carbon nanofiber;
(b) dispersing the carbon nanofibers in a solution containing Ni and Co precursors for gelation, carrying out heat treatment under the condition of inert gas, and cooling in the air;
in step (b), Ni (NO) is added3)2·6H2O and Co (NO)3)2·6H2Dissolving O in ethanol, then adding propylene oxide and the carbon nanofiber, stirring, and gelatinizing at 50-90 ℃; heating the gelled product at 300-400 ℃, and cooling in air; the Ni (NO)3)2·6H2O、Co(NO3)2·6H2O, carbon nano-meterThe ratio of fiber to propylene oxide was 0.1 mM: 0.2 mM: 0.3 g: 2.0 g.
2. The zinc-air battery catalyst of claim 1, wherein: the carbon nanofiber has a diameter of 10-800 nm and a length of 1-100 μm.
3. The zinc-air battery catalyst of claim 1, wherein: the particle size of the metal oxide nanoparticles is 10-100 nm.
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| JP6731199B2 (en) * | 2015-02-18 | 2020-07-29 | 国立大学法人北海道大学 | Catalyst for oxygen reduction reaction and air electrode for metal-air secondary battery |
| CN105226297B (en) * | 2015-10-21 | 2017-09-05 | 苏州大学 | A kind of preparation method of classifying porous air electrode |
| CN105609790B (en) * | 2015-12-14 | 2018-08-07 | 青岛大学 | A kind of preparation method of nickel cobalt/carbon nanotube aerogel zinc and air cell catalyst |
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| CN105289617A (en) * | 2015-11-11 | 2016-02-03 | 东华大学 | Nickel cobalt oxide/carbon nanotube composite catalyst, preparation and application thereof |
| CN110534346A (en) * | 2019-07-24 | 2019-12-03 | 南京晓庄学院 | Spinel-type metal oxide/graphene combination electrode material and preparation method thereof rich in oxygen defect |
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