CN111490259B - Nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material for zinc-air battery and preparation method thereof - Google Patents

Nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material for zinc-air battery and preparation method thereof Download PDF

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CN111490259B
CN111490259B CN201910071813.2A CN201910071813A CN111490259B CN 111490259 B CN111490259 B CN 111490259B CN 201910071813 A CN201910071813 A CN 201910071813A CN 111490259 B CN111490259 B CN 111490259B
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CN111490259A (en
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陈忠伟
张益宁
毛治宇
俞同文
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Suzhou Wotai Fengneng Battery Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/90—Selection of catalytic material

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Abstract

The invention relates to a nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material for a zinc-air battery, wherein the material comprises nitrogen-doped and defect-containing porous carbon and cobalt (II) clusters, the nitrogen-doped and defect-containing porous carbon is used as a carrier, the cobalt (II) clusters are supported in the nitrogen-doped and defect-containing porous carbon pore channel, and the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material is used as a bifunctional catalyst for an oxygen reduction reaction and an oxygen precipitation reaction. The invention also discloses a preparation method of the material. According to the nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material disclosed by the invention, the cobalt cluster material has excellent oxygen reduction and oxygen precipitation reaction activities in a zinc-air battery, and the stability and excellent specific capacity of the zinc-air battery are improved to a great extent. The method has simple and controllable steps and is easy to realize industrial production.

Description

Nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material for zinc-air battery and preparation method thereof
Technical Field
The invention relates to the field of energy conversion and storage materials and devices, in particular to a nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material for a zinc-air battery and a preparation method thereof.
Background
The metal-air battery is a novel battery, and is a chemical battery which takes active metal, such as lithium, zinc, magnesium, aluminum and the like, as a negative electrode and oxygen as a positive electrode, wherein the oxygen is obtained from air through a positive electrode porous material. The conversion between chemical energy and electrochemical energy is achieved by oxygen reduction and oxygen evolution reactions. Among all the different kinds of metal-air batteries, zinc-air batteries are receiving wide attention due to the cheap and easy availability of zinc and the high energy density of 1218Wh/kg, and are one of the most promising next-generation battery technologies with commercial prospects. However, as the most important component of the zinc-air battery, the oxygen reduction and oxygen evolution reaction of the air electrode portion generally has problems of overpotential excess and activity decay after many cycles due to its slow reaction kinetics. Although the noble metals platinum and iridium have good catalytic activity and stability and can solve the above problems to some extent, due to their high cost, it is a great challenge in the field to find alternative non-noble metal catalysts with high activity and high stability.
In the prior art, no public report is found about the cobalt cluster material loaded by the carbon pore channel doped with nitrogen and containing defects. Although nitrogen-doped porous carbon materials have been reported, for example, CN102247869A discloses a spherical nitrogen-doped carbon-supported non-noble metal oxygen reduction catalyst and a preparation method thereof; CN101884932A discloses a nitrogen-doped carbon nanofiber oxygen reduction catalyst and a preparation method and application thereof; CN104689857A discloses a preparation method of a nitrogen-doped porous carbon material, a catalyst containing the material and application; CN107359320A discloses nitrogen-doped porous carbon/MoS2A sodium ion battery cathode and a preparation method thereof; CN103265008B discloses a nitrogen-doped porous carbon and a preparation method thereof. Meanwhile, zinc-air batteries have some reports on application, such as CN103477480B discloses a core-shell structure bifunctional catalyst for metal-air batteries/fuel cells; CN200953374Y discloses a zinc-air battery, which comprises an air electrode having a protruding portion contacting with the inner wall of the battery case, wherein the air electrode and the battery case form an air flow channel, and the air electrode is in a wave shape composed of a plurality of units. However, these reports differ from the present invention mainly in that: 1. different materials, titanium nitride materials which do not exist in other reports also exist in the invention; 2. the loading method is different, and the invention focuses on the loading of the pore channel, but not the loading of the material per se in other reports. 3. There are differences in the synthesis methods. 4. Is clearly different from other materials used in zinc-air batteries.
The material is a nitrogen-doped and defect-containing carbon pore channel-loaded cobalt cluster material and application of a zinc-air battery containing the material. The porous carbon doped with nitrogen and containing defects is characterized in that defects are generated due to imperfect arrangement of molecules or atoms in the porous carbon material, and more active molecules or atoms are exposed. The porous carbon containing defects promotes the special structure to have more active sites and higher specific surface area, and more cobalt clusters are loaded, thereby being beneficial to the high capacity and stability of the zinc-air battery.
Disclosure of Invention
The invention aims to provide a nitrogen-doped and defect-containing porous carbon pore channel-loaded cobalt cluster material for a zinc-air battery and a preparation method thereof. The nitrogen-doped and defect-containing carbon pore channel-loaded cobalt cluster material provided by the invention has excellent specific capacity, good stability and low cost in a zinc-air battery, is suitable for industrial production and has a wide application field.
The object of the present invention and the technical problem to be solved are achieved by the following technical means. The nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material for the zinc-air battery comprises nitrogen-doped and defect-containing porous carbon and cobalt (II) clusters, wherein the nitrogen-doped and defect-containing porous carbon is used as a carrier, the cobalt (II) clusters are supported in the nitrogen-doped and defect-containing porous carbon pore channel, and the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material is used as a bifunctional catalyst for an oxygen reduction reaction and an oxygen precipitation reaction.
The cobalt cluster material is loaded on porous carbon pore channels which are doped with nitrogen and contain defects in the zinc-air battery, wherein the weight ratio of the nitrogen-doped porous carbon to the titanium nitride is (85% -95%): (5% -15%).
The zinc-air battery is prepared by loading a cobalt cluster material with a nitrogen-doped and defect-containing porous carbon pore channel, wherein the grain size of the cobalt cluster is 9.8-14.1 nm.
The cobalt cluster material is loaded on porous carbon pore channels which are doped with nitrogen and contain defects in the zinc-air battery, wherein the size of the porous carbon pore channels is 7.1-20.5 nm.
The nitrogen-doped and defect-containing porous carbon pore channel-supported cobalt cluster material for the zinc-air battery is characterized in that the pore volume of the nitrogen-doped and defect-containing porous carbon pore channel-supported cobalt cluster material is 107.8cm3Table of the ratio of/gArea of 1917m2/g。
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the method for preparing the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material for the zinc-air battery, which is provided by the invention, the method comprises the following steps:
placing carbon in ammonia gas flow to absorb water vapor at 70-90 ℃;
b. b, immersing the product obtained in the step a into a saturated solution of cobalt acetylacetonate/ethyl acetate for 4-8 hours, and then filtering and collecting the product;
c. and (c) calcining the product obtained in the step (b) under a certain condition in an ammonia atmosphere to obtain the nitrogen-doped and defect-containing porous carbon pore channel-loaded cobalt cluster material.
The preparation method as described above, wherein the calcination conditions in the step c are: temperature 700-: 1-3 h.
By the technical scheme, the invention (name) at least has the following advantages:
(1) the nitrogen-doped porous carbon pore channel loaded cobalt cluster material containing the defects is prepared by compounding cobalt clusters and nitrogen-doped porous carbon containing the defects in pore channels: on one hand, the cobalt cluster has better oxygen reduction and oxygen precipitation reaction activities, and the carbon material has very high conductivity and is beneficial to the transmission of electrons; on the other hand, the cobalt clusters are compounded with nitrogen-doped porous carbon containing defects, the uniform distribution of cobalt nanoparticles is promoted by utilizing the limited domain effect of pore channel loading, and the porous structure in the material is favorable for increasing the surface area of the cobalt nanoparticles, so that the oxygen reduction and oxygen precipitation reaction activities of the cobalt active material are enhanced.
(2) According to the nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material provided by the invention, the nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material is used as a bifunctional catalyst for an oxygen reduction reaction and an oxygen precipitation reaction in a zinc-air battery, so that the stability and the excellent specific capacity of the zinc-air battery are improved to a great extent.
(3) The method has simple and controllable steps and is easy to realize industrial production.
In summary, the nitrogen-doped and defect-containing porous carbon pore channel-loaded cobalt cluster material and the preparation method thereof provided by the invention provide application of the material in a zinc-air battery, so that the material is more practical and has industrial utilization value. The battery material has the advantages and practical values, does not have similar design publication or use in similar products, is innovative, has great improvement on the preparation method or function, has great technical progress, produces good and practical effects, has multiple enhanced effects compared with the existing battery material, is more suitable for practical use, has industrial wide utilization value, and is a novel, advanced and practical new design.
The foregoing is a summary of the present invention, and the following is a detailed description of the preferred embodiments of the present invention in order to provide a clear understanding of the technical features of the present invention.
The specific preparation method and structure of the present invention are given in detail by the following examples.
Drawings
Fig. 1a is a comparison XRD graph of nitrogen doped and defect containing porous carbon tunnel-supported cobalt cluster material prepared in example 1 according to the present invention versus nitrogen doped carbon tunnel-supported cobalt cluster material prepared in comparative example 1 and KJ-600 porous carbon of comparative example 2; fig. 1b is a raman spectroscopy characterization plot of nitrogen-doped and defect-containing porous carbon tunnel-supported cobalt cluster materials prepared in example 1 according to the present invention and nitrogen-doped carbon tunnel-supported cobalt cluster materials prepared in comparative example 1 and KJ-600 porous carbon of comparative example 2; FIGS. 1c, 1d, 1e correspond to I for the nitrogen doped carbon-channel supported cobalt cluster material prepared in comparative example 1 and the nitrogen doped and defect-containing porous carbon-channel supported cobalt cluster material prepared in example 1 and the KJ-600 porous carbon of comparative example 2, respectively, according to the inventionD/IGA profile map of (a); FIG. 1f shows nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 according to the present invention, nitrogen-doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1, and those of comparative example 2BET test comparison plot of KJ-600 porous carbon; fig. 1g is a plot of the pore size distribution of nitrogen-doped, defect-containing porous carbon channel-supported cobalt cluster materials prepared in example 1 in accordance with the present invention versus nitrogen-doped carbon channel-supported cobalt cluster materials prepared in comparative example 1 and KJ-600 porous carbon of comparative example 2;
fig. 2a is a dark field TEM global view of a nitrogen doped and defect containing porous carbon pore supported cobalt cluster material prepared in example 1 according to the present invention; fig. 2b is a selected area diffraction pattern of the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material prepared in example 1 according to the present invention; fig. 2c is a dark field TEM local high resolution magnified view of the nitrogen doped and defect containing porous carbon pore supported cobalt cluster material prepared in example 1 according to the present invention; fig. 2d and 2f are bright field TEM global images of nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 according to the present invention; fig. 2e is a bright field TEM local high resolution magnified view of the nitrogen doped and defect containing porous carbon pore channel loaded cobalt cluster material prepared in example 1 according to the present invention; fig. 2g, 2h and 2i are scanned graphs of the electron energy loss spectra of carbon, cobalt and nitrogen elements in selected regions of the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material prepared in example 1 according to the present invention;
fig. 3a is a XPS characterized C1s plot of a nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster material prepared in example 1 according to the present invention; fig. 3b is a XPS-characterized N1s plot of a nitrogen-doped and defect-containing porous carbon pore channel-supported cobalt cluster material prepared in example 1 according to the present invention; fig. 3c is a XPS-characterized map of Co2p from a nitrogen-doped and defect-containing porous carbon pore channel-supported cobalt cluster material prepared in example 1 according to the present invention; fig. 3d is a diagram of Co elements characterized by a nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material XAS prepared in example 1 according to the present invention;
fig. 4a is a graph of oxygen reduction activity of nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 according to the present invention versus nitrogen-doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1 and Pt/C samples prepared in comparative example 3; fig. 4b is a graph of oxygen evolution activity for nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 according to the present invention versus nitrogen doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1 and Ir/C samples prepared in comparative example 4; fig. 4C is a Tafel plot of oxygen reduction reaction performance of nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 according to the present invention versus nitrogen-doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1 and Pt/C samples prepared in comparative example 3; FIG. 4d is a Tafel plot of the oxygen evolution reaction performance of nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 in accordance with the present invention versus nitrogen doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1 and Ir/C samples prepared in comparative example 4;
fig. 5 is a graph of zinc-air cell performance for nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster materials prepared in example 1, nitrogen-doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1, Pt/C samples prepared in comparative example 3, and Ir/C sample hybrid materials prepared in comparative example 4, in accordance with the present invention;
fig. 6 is a graph of the zinc-air cell stability performance of nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster materials prepared in example 1, nitrogen-doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1, Pt/C samples prepared in comparative example 3, and Ir/C sample mixed materials prepared in comparative example 4, in accordance with the present invention;
fig. 7a is a bright field TEM global view of a nitrogen doped and defect containing porous carbon pore channel loaded cobalt cluster material prepared in example 2 according to the present invention; fig. 7b is a dark field TEM local high resolution magnified view of the nitrogen doped and defect containing porous carbon pore supported cobalt cluster material prepared in example 2 according to the present invention;
fig. 8a is a dark field TEM global view of nitrogen doped and defect containing porous carbon pore supported cobalt cluster material prepared in example 3 according to the present invention; fig. 8b is a dark field TEM local high resolution magnified view of a nitrogen doped and defect containing porous carbon pore channel loaded cobalt cluster material prepared in example 2 according to the present invention;
FIG. 9a is a dark field TEM global view of a porous carbon material prepared in comparative example 1 according to the present invention; FIG. 9b is a dark field TEM local high resolution magnified view thereof;
fig. 10 is a TEM image of a porous carbon material prepared in comparative example 2 according to the present invention;
fig. 11 is a zinc-air cell made of a nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster material according to the present invention.
Detailed Description
The present invention is further illustrated by the following figures and examples, which are to be understood as merely illustrative and not restrictive. Furthermore, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings herein, and such equivalents may fall within the scope of the invention as defined in the appended claims.
According to the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material for the zinc-air battery, the material comprises nitrogen-doped and defect-containing porous carbon and cobalt (II) clusters, the nitrogen-doped and defect-containing porous carbon is used as a carrier, the cobalt (II) clusters are supported in the nitrogen-doped and defect-containing porous carbon pore channel, and the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material is used as a dual-function catalyst for an oxygen reduction reaction and an oxygen precipitation reaction. Which will be discussed in detail below with respect to specific embodiments.
Example 1
Commercially available KJ-600 carbon (available from Acksolff) 1g was taken at 80 ℃ and placed in a stream of ammonia to adsorb water vapor, which was then immersed in a saturated solution of cobalt acetylacetonate/ethyl acetate for 6 hours, followed by filtration. The resulting sample was placed in a muffle furnace and calcined at 800 ℃ for 1 hour under an ammonia atmosphere. TGA analysis showed that the mass ratio of nitrogen-doped porous carbon therein was 89%.
The obtained doped and defect-containing porous carbon pore channel supported cobalt cluster material is used as a catalyst, a linear voltammetry scanning test is carried out on a rotating disk electrode, the rotating speed is 1600rpm, the oxygen used in the test is saturated with 0.1mol/L potassium hydroxide solution, and the measured result is shown in fig. 4.
Example 2
The same operation as in example 1 was performed except that the mass ratio of the nitrogen-doped porous carbon was adjusted to specifically:
commercially available KJ-600 carbon (available from Acksonobel) 1.1g was taken at 80 ℃ and placed in a stream of ammonia to adsorb water vapor, which was then immersed in a saturated solution of cobalt acetylacetonate/ethyl acetate for 6 hours, followed by filtration. The resulting sample was placed in a muffle furnace and calcined at 800 ℃ for 1 hour under an ammonia atmosphere. TGA analysis indicated that the mass ratio of nitrogen-doped porous carbon therein was 95%.
Example 3
The same operation as in example 1 was carried out except that the mass ratio of the nitrogen-doped porous carbon was adjusted to specifically:
0.95g of commercially available KJ-600 carbon (available from Acksonobel) was taken at 80 ℃ and placed in a stream of ammonia to adsorb water vapor, which was then immersed in a saturated solution of cobalt acetylacetonate/ethyl acetate for 6 hours, followed by filtration. The resulting sample was placed in a muffle furnace and calcined at 800 ℃ for 1 hour under an ammonia atmosphere. TGA analysis showed that the mass ratio of nitrogen-doped porous carbon therein was 85%.
Comparative example 1
Commercially available KJ-600 carbon (available from Acksonobel) 1g was immersed in a saturated solution of cobalt acetylacetonate/ethyl acetate for 6 hours, followed by filtration. The resulting sample was placed in a muffle furnace and calcined at 800 ℃ for 1 hour under an ammonia atmosphere. TGA analysis showed that the mass ratio of nitrogen-doped porous carbon therein was 87%.
Comparative example 2
Under an ammonia atmosphere, 1g of commercially available KJ-600 carbon (available from Acksonobel) was placed in a muffle furnace and calcined at 800 ℃ for 1 hour.
Comparative example 3
A20.0 mg sample (46 wt%) of commercial Pt/C obtained from Tanaka Kikinzoku Kogyo, Japan was added with 3.6mL of ethanol (Guangzhou chemical Co., Ltd.) and 0.4mL of a 5% Nafion solution (Dupont Co., Ltd.) and ultrasonically dispersed uniformly. And transferring 10 mu L of suspension liquid onto the surface of a glassy carbon electrode (d is 5mm), drying at 45 ℃, and forming a layer of uniformly dispersed catalyst thin film on the surface. Drying, and making into working electrode in three-electrode system (saturated Ag/AgCl electrode as reference electrode, platinum wire as counter electrode, and electrolyte O2Saturated 0.1mol/L KOH aqueous solution) were subjected to electrocatalytic oxygen reduction performance test.
Comparative example 4
A commercial Ir/C sample (20 wt%) from Premetek, 1.0mg, was ultrasonically dispersed uniformly by adding 4.0mL of ethanol (Guangzhou chemical Co., Ltd.), 1.0mL of isopropanol (Guangzhou chemical Co., Ltd.), and 25. mu.L of 5% Nafion solution (Dupont Co., Ltd.). 10 mul of the suspension was transferred onto the surface of a glassy carbon electrode (d ═ 5mm), and dried at 45 ℃ to form a uniformly dispersed catalyst thin film on the surface. After drying, the obtained product is used as a working electrode, and in a three-electrode system (a saturated Ag/AgCl electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and an electrolyte is N2Saturated 0.1mol/L KOH aqueous solution) for electrocatalytic oxygen evolution performance tests.
The drawings illustrate the following:
fig. 1a is a XRD comparison of nitrogen doped and defect containing porous carbon tunnel-supported cobalt cluster material prepared in example 1 according to the present invention with nitrogen doped carbon tunnel-supported cobalt cluster material prepared in comparative example 1 and KJ-600 porous carbon of comparative example 2. It can be seen that the three newly appearing peaks in the nitrogen-doped and defect-containing porous carbon pore channel-supported cobalt cluster material prepared in example 1 are diffraction peaks of metallic cobalt atoms, the structure of which is a cubic structure, and the space group is Fm3m, indicating that the cobalt precursor is reduced to a cobalt cluster. The grain size of the cobalt clusters is approximately 12 nm. The porous carbon size was 1.35 nm. And the cobalt cluster grain size in the nitrogen-doped porous carbon pore channel supported cobalt cluster material prepared in comparative example 1 was 22.5 nm. These findings indicate that the material prepared in comparative example 1 is a mechanical mixture of nitrogen-doped porous carbon and cobalt clusters.
Fig. 1b is a raman spectroscopy characterization plot of the nitrogen doped and defect containing porous carbon tunnel supported cobalt cluster material prepared in example 1 according to the present invention and the nitrogen doped carbon tunnel supported cobalt cluster material prepared in comparative example 1 and the KJ-600 porous carbon of comparative example 2. The concentration of the cobalt cluster material loaded by nitrogen-doped and defect-containing porous carbon pore channels is 1340 cm and 1580cm-1C at peak due to defect6The vibration peak of the ring. And example 1ID/IGValue 1.96I of comparative example 1D/IGThe value 1.50 is higher, indicating that the former has more defects.
FIGS. 1c, 1d, 1e correspond to I for the nitrogen doped carbon-channel supported cobalt cluster material prepared in comparative example 1 and the nitrogen doped and defect-containing porous carbon-channel supported cobalt cluster material prepared in example 1 and the KJ-600 porous carbon of comparative example 2, respectively, according to the inventionD/IGA profile of (2). The redder and brighter the figure indicates less defects. The results show that the material prepared in example 1 has the most defects.
Fig. 1f is a BET test comparison of nitrogen-doped and defect-containing porous carbon tunnel-supported cobalt cluster material prepared in example 1 according to the present invention with nitrogen-doped carbon tunnel-supported cobalt cluster material prepared in comparative example 1 and KJ-600 porous carbon of comparative example 2. g is the pore size distribution plot for the nitrogen-doped and defect-containing porous carbon tunnel-supported cobalt cluster material prepared in example 1 according to the present invention, the nitrogen-doped carbon tunnel-supported cobalt cluster material prepared in comparative example 1, and the KJ-600 porous carbon of comparative example 2. The results showed that the specific surface area of the commercial KJ porous carbon of comparative example 2 was 1302m2Per g, pore volume 4.1cm3(ii) in terms of/g. The specific surface area of the nitrogen-doped and defect-containing porous carbon pore channel-loaded cobalt cluster material prepared in the example 1 is increased to 1917m2Per g, pore volume 107.8cm3/g。
Fig. 2a is a dark field TEM global view of nitrogen doped and defect containing porous carbon pore supported cobalt cluster material prepared in example 1 according to the present invention. It can be seen from the figure that the white cobalt clusters are uniformly distributed in the carbon. The uniformity of cobalt cluster distribution can be further demonstrated by combining fig. 2g, 2h and 2i with the scanned electron energy loss spectra of carbon, cobalt and nitrogen in selected regions of fig. 2f of the nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material prepared in example 1 according to the present invention. Fig. 2b is a selected area diffraction pattern of the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material prepared in example 1 according to the present invention, showing that the cobalt cluster is a polycrystalline nanoparticle. Fig. 2c is a dark field TEM local high resolution magnified view of the nitrogen doped and defect containing porous carbon pore supported cobalt cluster material prepared in example 1 according to the present invention; fig. 2d and 2f are bright field TEM global images of nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 according to the present invention; figure 2e is a bright field TEM local high resolution magnified view of the nitrogen doped and defect containing porous carbon pore channel loaded cobalt cluster material prepared in example 1 according to the present invention. The above results indicate that the cobalt clusters are supported in the carbon channels.
FIG. 3a is a XPS characterization of C1s plots for nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster material prepared in example 1 according to the present invention with C-C, C-N and C-O peaks at 284.6eV, 285.6 eV and 288.8eV respectively, with the C-N bond indicating nitrogen doping in the carbon lattice; fig. 3b is a XPS-characterized N1s plot of nitrogen-doped and defect-containing porous carbon pore-supported cobalt cluster material prepared in example 1 according to the present invention, wherein 398.2eV, 399.9eV and 401.3eV are nitrogen in pyridine, nitrogen in pyrrole and quaternary nitrogen, respectively; FIG. 3c is a XPS characterization of Co2p for nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster material prepared in example 1 according to the present invention, wherein 803.1eV and 785.2eV are Co respectivelysat,2p1/2And Cosat,2p3/2And 795.9eV is Co2p1/2780.5eV is Co2p3/2. Fig. 3d is a graph of the element Co, as characterized by the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material XAS prepared in example 1 according to the present invention, indicating the presence of Co-N-C bonds in this material.
FIG. 4a shows nitrogen-doped and defect-containing porous carbon pore channel-supported cobalt cluster material prepared in example 1 according to the present invention and nitrogen-doped carbon pore channel prepared in comparative example 1Oxygen reduction activity profile of the supported cobalt cluster material and the Pt/C sample prepared in comparative example 3. The results show that the initial voltage of the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material is 0.938V, the half-wave potential is 0.847V, the initial voltage is obviously higher than that of comparative example 1, the initial voltage is 0.925V, the half-wave potential is 0.816V, and the performance of the material is better than that of commercial Pt/C. FIG. 4C is a Tafel plot of the oxygen reduction reaction performance of the above three materials, with a Tafel slope of 57.4mV/dec, 59.6mV/dec higher than Pt/C, and 76.4mV/dec for nitrogen-doped porous carbon pore channel supported cobalt cluster materials. Fig. 4b is a graph of oxygen precipitation activity for nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 according to the present invention, nitrogen-doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1, and Ir/C samples prepared in comparative example 4. It can be seen from the figure that at 10mA/cm2The potential of the nitrogen-doped porous carbon pore channel-supported cobalt cluster material containing defects is 1.593V, which is 78mV lower than that of the nitrogen-doped porous carbon pore channel-supported cobalt cluster material and 42mV lower than that of commercial Ir/C. FIG. 4d is a Tafel plot of the oxygen evolution reaction performance of the three materials, wherein the Tafel slope of the nitrogen doped and defect-containing porous carbon pore channel supported cobalt cluster material is 70.1mV/dec, both lower than 84.8mV/dec for the nitrogen doped porous carbon pore channel supported cobalt cluster material and 100mV/dec for a commercial Ir/C catalyst.
Fig. 5 is a graph of zinc-air cell performance of nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 according to the present invention, nitrogen-doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1, Pt/C samples prepared in comparative example 3, and Ir/C sample mixed materials prepared in comparative example 4. The result shows that the energy density of the battery assembled by the porous carbon pore channel loaded cobalt cluster material doped with nitrogen and containing defects reaches 135mW/cm2105mW/cm higher than that of a battery assembled by nitrogen-doped porous carbon pore channel loaded cobalt cluster material2And 110mW/cm of Pt/C and Ir/C assembled battery2。
Fig. 6 is a graph of the stability performance of zinc-air batteries of nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster materials prepared in example 1 according to the present invention, nitrogen-doped carbon pore channel supported cobalt cluster materials prepared in comparative example 1, Pt/C samples prepared in comparative example 3, and Ir/C sample mixed materials prepared in comparative example 4. The results show that the cell stability time for the nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster material assembly is 250 hours, which is higher than 150 hours for the nitrogen doped porous carbon pore channel supported cobalt cluster material assembly cell and 21 hours for the Pt/C and Ir/C assembly cell.
Fig. 7a is a bright field TEM global view of a nitrogen doped and defect containing porous carbon pore channel loaded cobalt cluster material prepared in example 2 according to the present invention; fig. 7b is a dark field TEM local high resolution magnified view of the nitrogen doped and defect containing porous carbon pore supported cobalt cluster material prepared in example 2 according to the present invention. It can be seen from the figure that the black cobalt cluster particles are more uniformly distributed in the nitrogen-doped defect-containing carbon channels.
Fig. 8a is a dark field TEM global view of nitrogen doped and defect containing porous carbon pore supported cobalt cluster material prepared in example 3 according to the present invention; fig. 8b is a dark field TEM local high resolution magnified view of the nitrogen doped and defect containing porous carbon pore channel loaded cobalt cluster material prepared in example 2 according to the present invention. It can be seen from the figure that the white cobalt cluster particles are more uniformly distributed in the nitrogen-doped defect-containing carbon channels.
FIG. 9a is a dark field TEM global view of a porous carbon material prepared in comparative example 1 according to the present invention; FIG. 9b is a local high resolution magnified view of its dark field TEM. As can be seen from the figure, the white cobalt clusters are relatively uniformly distributed in the carbon pores.
Fig. 10 is a TEM image of the porous carbon material prepared in comparative example 2 according to the present invention. As can be seen from the figure, the calcined porous carbon was successfully prepared.
In summary, the nitrogen-doped and defect-containing porous carbon pore channel-loaded cobalt cluster material disclosed by the invention has the advantages that the cobalt cluster has better oxygen reduction and oxygen precipitation reaction activities, and the carbon material has high conductivity and is favorable for electron transmission. The cobalt clusters and the nitrogen-doped carbon pores containing defects are compounded, and the uniform distribution of cobalt nanoparticles is promoted by utilizing the limited domain effect of pore channel loading, so that the oxygen reduction and oxygen precipitation reaction activities of the cobalt active material are enhanced. And the porous structure in the material is beneficial to increasing the surface area of the material, so that the stability of the zinc-air battery is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (4)

1. A nitrogen-doped and defect-containing porous carbon pore-supported cobalt cluster material for a zinc-air battery, wherein the material comprises nitrogen-doped and defect-containing porous carbon and cobalt clusters, the nitrogen-doped and defect-containing porous carbon is a carrier, the cobalt clusters are supported in the nitrogen-doped and defect-containing porous carbon pore, and the nitrogen-doped and defect-containing porous carbon pore-supported cobalt cluster material is used as a bifunctional catalyst for an oxygen reduction reaction and an oxygen precipitation reaction; wherein, the weight ratio of the nitrogen-doped porous carbon to the cobalt cluster material is (85-95%): (5% -15%); wherein the crystal grain size of the cobalt cluster is 9.8-14.1nm, and the pore volume of the nitrogen-doped and defect-containing porous carbon pore channel supported cobalt cluster material is 107.8cm3(ii)/g, specific surface area 1917m2/g。
2. The zinc-air battery of claim 1, wherein the porous carbon pore channel size is 7.1-20.5 nm.
3. A method of preparing a nitrogen doped and defect containing porous carbon pore channel supported cobalt cluster material for a zinc-air battery according to any one of claims 1 to 2, the method comprising the steps of:
a, placing carbon in ammonia gas flow to adsorb water vapor at 70-90 ℃;
b, immersing the product obtained in the step a into a saturated solution of cobalt acetylacetonate/ethyl acetate for 4-8 hours, and then filtering and collecting the product;
and c, calcining the product obtained in the step b under certain conditions in an ammonia atmosphere to obtain the nitrogen-doped and defect-containing porous carbon pore channel-loaded cobalt cluster material.
4. The production method according to claim 3, wherein the calcination conditions in the step c are: temperature 700-: 1-3 h.
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