CN115548357A - Zinc-air battery air electrode catalyst and preparation method and application thereof - Google Patents
Zinc-air battery air electrode catalyst and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 9
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract 2
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- 238000009826 distribution Methods 0.000 description 1
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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
- 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
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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
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- H01M4/90—Selection of catalytic material
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- 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
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention belongs to the field of zinc-air batteries, and discloses a zinc-air battery air electrode catalyst, and a preparation method and application thereof. The molecular formula of the catalyst is FeSAC/NC, and the Fe-N-C active sites with the structure of atomic level are distributed on the fir and nitrogen-doped carbon materials derived from ZIF-8. The preparation steps are as follows: firstly, synthesizing a nitrogen-doped carbon material NC; adding nitrogen-doped carbon material NC to Zn (NO) 3 ) 2 ,Fe(NO 3 ) 3 And 2-methylimidazole in methanol for 24 hours, washing with ethanol, drying in vacuum, and pyrolyzing in a tubular furnace to obtain the catalyst FeSAC/NC. The invention adopts a method of growing Fe-ZIF-8 on a nitrogen-doped carbon material NC for re-pyrolysis to prepare the FeSAC/NC catalyst, the prepared FeSAC/NC catalyst is used for a quasi-solid zinc-air battery, and the power density can reach 82.1mW/cm 2 And the cycle is stabilized for 80h.
Description
Technical Field
The invention belongs to the technical field of zinc-air batteries, and particularly relates to a zinc-air battery air electrode catalyst, and a preparation method and application thereof.
Background
Since the 21 st century, people have devoted themselves to the development of various renewable energy sources, to the promotion of diversified energy utilization, to the reduction of the usage proportion of fossil energy, to the enhancement of energy safety, and to the alleviation of the deterioration of the global environment. Among them, zinc-air batteries are widely concerned and studied as a new generation of efficient green energy conversion and storage devices.
The Oxygen Reduction Reaction (ORR) is the basic reaction in the air electrode of zinc-air batteries, but the high overpotential and slow kinetics of ORR severely hamper the development and application of both batteries. At present, the Pt group noble metal catalyst has excellent performance in the ORR reaction, but due to the defects of scarcity, high cost, low durability and selectivity in the reaction and the like of the Pt group noble metal, the Pt group noble metal catalyst has a limitation on wider market prospect.
Therefore, the development of non-noble metal ORR catalysts with lower cost, more abundant reserves and more excellent performance is urgently needed to promote the development of zinc-air batteries, which is also a research hotspot and focus in the field at present. Monatomic catalysts (SAC) have been rapidly developed in recent years due to their outstanding advantages such as maximum atom utilization, abundant interfacial effects, excellent catalytic activity and selectivity. Various monatomic catalysts used for the ORR reaction are widely studied, and among them, the monatomic catalyst using the iron nitrogen carbon (Fe-N-C) dispersed at the atomic level as the main active site has remarkable advantages of activity, selectivity and the like, and is the leading catalyst in the current ORR research field. Because the synthesis process of metal-organic frameworks (MOFs) can be designed and various modification options after synthesis are available, the MOFs is used as a superior precursor, and the metal nitrogen-carbon catalytic active sites with atomic-level dispersion obtained by pyrolysis are widely researched. Among them, the zeolite type imidazolium salt framework (ZIF-8) with high nitrogen content and large specific surface area is a good candidate material for directly synthesizing SACs by pyrolysis. However, collapse and aggregation of the MOFs crystals cannot be avoided in the pyrolysis process, and the pyrolyzed MOFs crystals cannot reach a good mass transfer channel and continuous conductivity required by ORR. In application, the dispersed particles also require a perfluorosulfonic acid-based polymer (Nafion solution) having poor conductivity as a binder, resulting in poor cell performance in practical applications.
The research and development of non-noble metal and high-practicability zinc-air battery air electrode catalysts are urgent matters of technologists in the field.
Disclosure of Invention
In view of the defects and shortcomings of the prior art, the invention aims to provide an air electrode catalyst FeSAC/NC for an integral high-activity zinc-air battery and a preparation method thereof, and solves the following problems: (1) how to replace expensive and resource-limited precious metal-based ORR catalysts with non-precious metal-based ORR catalysts; (2) how to improve the peak power density and the cycle stability of the air electrode catalyst applied to the liquid/quasi-solid zinc-air battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the molecular formula of the catalyst is FeSAC/NC, and the structure is that Fe-N-C active sites with atomic-level dispersion are uniformly distributed on fir and nitrogen-doped carbon materials derived from ZIF-8.
The invention provides a preparation method of a zinc-air battery air electrode catalyst, which adopts the following technical scheme that the preparation method comprises the following steps:
s1, weighing 20g of ammonium chloride, and dissolving the ammonium chloride in 500mL of deionized water to prepare an ammonium chloride solution;
s2, putting the fir wood blocks of 2cm multiplied by 0.5cm into the ammonium chloride solution prepared in the S1, stirring for 24h, fishing out, placing in an oven at the temperature of 80 ℃, and drying for 8h to obtain the nitrogen-doped fir wood blocks;
s3, placing the nitrogen-doped fir wood block prepared in the S2 into a tubular furnace, heating to 900 ℃ under the argon condition, keeping for 2 hours, and naturally cooling to obtain a nitrogen-doped porous carbon material NC I;
s4, mixing 1190mg of Zn (NO) 3 ) 2 ·6H 2 O and 121mg Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 25mL of methanol at room temperature to prepare a methanol dispersion liquid A;
s5, dissolving 1314mg 2-methylimidazole in 15mL of methanol at room temperature to prepare a methanol dispersion liquid B; (ii) a
S6, adding the nitrogen-doped porous carbon material NC I prepared in 200mg S3 into the methanol dispersion liquid A prepared in S4, stirring for 6 hours to obtain a methanol solution containing the nitrogen-doped porous carbon material NC I,
s7, adding the methanol dispersion liquid B prepared in the S5 into the methanol solution containing the nitrogen-doped porous carbon material NC I prepared in the S6, stirring for 24 hours, and taking out the reacted nitrogen-doped porous carbon material NC I to obtain a nitrogen-doped porous carbon material NC II;
s8, washing the nitrogen-doped porous carbon material NC II taken out of the S7 with ethanol, and then drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain Fe-ZIF-8/NC;
and S9, heating the Fe-ZIF8/NC obtained in the S8 to 900 ℃ under the condition of argon-hydrogen mixed gas in a tubular furnace, keeping for 3 hours, and naturally cooling to obtain the catalyst FeSAC/NC.
Preferably, in S3, the temperature is 5-8 ℃ min -1 And the rate of temperature rise.
Preferably, in S9, the volume ratio of the argon-hydrogen mixture gas is 5% hydrogen: 95% argon.
Preferably, in S9, the temperature is 3-5 ℃ min -1 And the rate of temperature rise.
An air electrode catalyst of a zinc-air battery is applied to the zinc-air battery.
Advantageous technical effects
1. The used iron metal content is high, and the price is low. The invention creatively designs the Fe-N-C catalyst which is loaded on the composite porous nitrogen-doped carbon material derived from the fir and the ZIF-8 and is dispersed at the atomic level. Because the formed atomically dispersed Fe-N-C active sites have unique electronic structure, unsaturated coordination bonds and optimized charge distribution, O can be effectively adsorbed in the ORR 2 And catalyzes the subsequent O-O bond breakage, thereby achieving higher ORR half-wave potential (0.9V) and lower Tafel slope (87 mV/dec), which is superior to that of the noble metal Pt/C catalyst (half-wave potential: 0.86V, tafel slope: 94 mV/dec).
2. The performance is good when the electrolyte is applied to a liquid/quasi-solid zinc-air battery: (1) the invention obtains the FeSAC/NC catalyst by uniformly growing the ZIF-8 containing Fe on the porous nitrogen-doped carbon material derived from the fir and then thermally decomposing. The nitrogen-doped carbon material derived from the cedar has an ordered porous structure and a continuous conductive network, so that the FeSAC/NC catalyst has good mass transfer effect and conductivity. Use of FeSAC/NC catalyst in liquid Zinc air cell, peakThe value power density and the cycle stability can reach 187.9mV/cm 2 And 450h, better than with noble metals (20%/Pt/C + RuO) 2 ) Liquid zinc-air battery prepared with catalyst (peak power density: 83.5mV/cm 2 And, cycle stability: 72h) And the battery performance is obviously improved. (2) The FeSAC/NC catalyst provided by the invention is applied to a quasi-solid zinc-air battery, and has excellent performance. In the test of the quasi-solid zinc-air battery, a perfluoro sulfonic polymer (Nafion solution) with poor conductivity is not required to be added as a binder, the FeSAC/NC catalyst is directly used as an air electrode, and the peak power density and the cycling stability of the battery can reach 82.1mV/cm 2 And 80h, better than with noble metals (20% Pt/C + RuO) 2 ) Quasi-solid zinc-air cell (22 mV/cm) prepared by catalyst 2 And 5 h), the battery performance is remarkably improved.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of NC (comparative example 1), CNC (comparative example 2) and FeSAC/NC (example 1);
FIG. 2 is a Scanning Electron Micrograph (SEM) of NC (comparative example 1), fe-ZIF8/NC (Fe-ZIF-8/NC obtained in S8 in example 1) and FeSAC/NC (example 1), a Transmission Electron Micrograph (TEM) of FeSAC/NC (example 1) and an Energy Dispersive Spectrum (EDS) of FeSAC/NC (example 1);
FIG. 3 is a graph comparing ORR performance of FeSAC/NC (example 1) and Pt/C (20%);
FIG. 4 is a graph based on FeSAC/NC (example 1) and Pt/C (20%) + RuO 2 An assembled liquid zinc-air battery performance analysis chart;
fig. 5 is a graph showing the performance analysis of a quasi-solid zinc-air cell assembled based on FeSAC/NC (example 1).
Detailed Description
In order to make the invention clearer and clearer, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
The molecular formula of the catalyst is FeSAC/NC, and the structure is that Fe-N-C active sites with atomic-level dispersion are uniformly distributed on wood and a porous composite nitrogen-doped carbon material derived from ZIF-8. The preparation method comprises the following steps:
s1, weighing 20g of ammonium chloride and dissolving in 500mL of deionized water to prepare an ammonium chloride solution;
s2, putting the fir wood blocks of 2cm multiplied by 0.5cm into the ammonium chloride solution prepared in the S1, stirring for 24h, fishing out, placing in an oven at the temperature of 80 ℃, and drying for 8h to obtain the nitrogen-doped fir wood blocks;
s3, placing the nitrogen-doped fir wood block prepared in the S2 into a tube furnace, and performing argon gas treatment at 5-8 ℃ for min -1 Heating to 900 ℃ at the heating rate, keeping for 2 hours, and naturally cooling to obtain a nitrogen-doped porous carbon material NC I;
s4, mixing 1190mg of Zn (NO) 3 ) 2 ·6H 2 O and 121mg Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 25mL of methanol at room temperature to prepare a methanol dispersion liquid A;
s5, dissolving 1314mg 2-methylimidazole in 15mL of methanol at room temperature to prepare a methanol dispersion liquid B; (ii) a
S6, adding the nitrogen-doped porous carbon material NC I prepared in 200mg S3 into the methanol dispersion liquid A prepared in S4, stirring for 6 hours to obtain a methanol solution containing the nitrogen-doped porous carbon material NC I,
s7, adding the methanol dispersion liquid B prepared in the S5 into the methanol solution containing the nitrogen-doped porous carbon material NC I prepared in the S6, stirring for 24 hours, and taking out the reacted nitrogen-doped porous carbon material NC I to obtain a nitrogen-doped porous carbon material NC II;
s8, washing the nitrogen-doped porous carbon material NC II obtained in the step S7 by using ethanol, and then drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain Fe-ZIF-8/NC;
s9, under the condition of argon-hydrogen mixed gas (the volume ratio of hydrogen is 5%) in a tubular furnace, the Fe-ZIF8/NC obtained in the S8 is carried out at the temperature of 3-5 ℃ for min -1 Heating to 900 ℃ at the heating rate, keeping the temperature for 3 hours, and naturally cooling to obtain the catalyst FeSAC/NC.
Comparative example 1
The difference from example 1 is that: s4, S5, S6, S7, S8 and S9 are not experienced.
The obtained target product number is NC.
Comparative example 2
The difference from example 1 is that: in S4, methanol dispersion A contained NO Fe (NO) 3 ) 3 ·9H 2 O, otherwise, the same as in example 1.
The obtained target product number is CNC.
Catalyst Structure characterization
FIG. 1 is an X-ray powder diffraction pattern of the catalysts NC (comparative example 1), CNC (comparative example 2) and FeSAC/NC (example 1) prepared. As can be seen from fig. 1: the prepared catalyst FeSAC/NC shows a nitrogen-doped carbon pattern similar to NC and CNC, and a Fe species peak does not appear, which indicates that a Fe species crystal phase is not formed.
Fig. 2 (a) is an SEM image of the prepared catalyst NC (comparative example 1), showing that the structure of the cedar-derived nitrogen-doped carbon material is well preserved, and exhibits an ordered arrangement of interconnected channels. FIG. 2 (b) is an SEM image of Fe-ZIF8/NC obtained in S8 of example 1, showing that Fe-ZIF-8 crystals are uniformly grown in the NC pore channels. FIG. 2 (c) is an SEM picture of a prepared catalyst FeSAC/NC (example 1), and it can be seen that the morphology of Fe-ZIF-8 is maintained after pyrolysis, and the surface becomes rough due to volatilization of Zn and skeleton carbonization under high temperature conditions. FIGS. 2 (d) and (e) are TEM images of the prepared catalyst FeSAC/NC, and no appearance of lattice fringes was observed, indicating that no nanoparticles of Fe species were formed. FIG. 2 (f) is an EDS image of FeSAC/NC showing that Fe element is uniformly dispersed in the catalyst. The results show that Fe active sites uniformly dispersed on an atomic scale exist in FeSAC/NC.
Catalyst ORR catalytic Performance test
The prepared catalysts FeSAC/NC (example 1), NC (comparative example 1) and CNC (comparative example 2) were each tested under CHI760E electrochemical workstation, with the following conditions: the temperature was 25 ℃. Mixing 4mg of catalyst, 500 mu L of absolute ethyl alcohol and 50 mu L of Nafion solution (5 wt%) for ultrasonic treatment for more than 30min to form a uniform mixed solution, sucking 15 mu L of the mixed solution, dripping the mixed solution on a disc electrode, and testing after waiting for 5 min. A three-electrode system was formed with the disc electrode as the working electrode, the platinum wire electrode as the counter electrode, and the silver/silver chloride electrode (Ag/AgCl) as the reference electrode, and tested in 0.1M KOH electrolyte. Convert the voltage data to vs. rhe by the following equation:
E vs.RHE ＝E vs.Ag/AgCl +0.059pH+0.197
fig. 3 is an experimental characterization of different catalysts ORR, as can be seen in fig. 3 (a, b): under the same test conditions, feSAC/NC (example 1) showed the highest half-wave potential (0.90V) and the lowest Tafel slope (87 mV dec) compared to NC (comparative example 1), CNC (comparative example 2) and Pt/C (20%) -1 ) The FeSAC/NC is shown to have excellent ORR catalytic activity due to the fact that the FeSAC/NC supports the iron-nitrogen-carbon active sites with high activity and dispersed atoms.
Catalyst zinc air cell performance test
The FeSAC/NC catalyst prepared in example 1 was combined with Pt/C (20%) + RuO 2 (mass ratio 1. The liquid zinc-air cell was tested using 99.9% pure zinc plates (10 x 3 x 0.02cm) as the negative electrode and 6M KOH (containing 0.2M Zn (OAc) as the electrolyte 2 ) The air electrode cathode is prepared by compressing four components of the aqueous solution, the ion exchange membrane, the foamed nickel, the carbon paper coated with the catalyst and the gas diffusion layer. The quasi-solid zinc-air battery uses alkaline polyvinyl alcohol PVA hydrogel (containing KOH, 18M/L) as a solid electrolyte, zinc foil as an anode, and a prepared 2X 0.5cm monolithic catalyst FeSAC/NC is directly used as an air electrode.
FIG. 4 shows FeSAC/NC and Pt/C (20%) + RuO 2 And (5) performance characterization of the assembled liquid zinc-air battery. As can be seen from FIG. 4, the FeSAC/NC based assembled liquid zinc-air cell has a higher peak power density (187.9 mW/cm) 2 ) Better cycling stability (450 h). Commercial noble metal catalyst (20% Pt/C + RuO) 2 ) The peak power density of the assembled liquid zinc-air battery is only 84mW/cm 2 The cycling stability was also poor (225 h).
Figure 5 is a quasi-solid zinc-air cell performance characterization based on a monolithic catalyst FeSAC/NC assembly. As can be seen from FIG. 5, the FeSAC/NC-based assembled quasi-solid zinc-air cell also showed excellent peak power density (82.1W/cm) 2 ) And good cycling stability (80 h). Is superior to the use of noble metals (20% Pt)/C+RuO 2 ) Quasi-solid zinc-air cell (22 mV/cm) prepared by catalyst 2 ，5h)。
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims. 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 (6)
1. The air electrode catalyst of the zinc-air battery is characterized in that the molecular formula of the catalyst is FeSAC/NC, and the structure is that Fe-N-C active sites with atomic-level dispersion are uniformly distributed on China fir and nitrogen-doped carbon materials derived from ZIF-8.
2. A method for preparing the air electrode catalyst of the zinc-air battery according to claim 1, which is characterized by comprising the following steps:
s1, weighing 20g of ammonium chloride and dissolving in 500mL of deionized water to prepare an ammonium chloride solution;
s2, putting the fir wood blocks of 2cm multiplied by 0.5cm into the ammonium chloride solution prepared in the S1, stirring for 24h, fishing out, placing in an oven at the temperature of 80 ℃, and drying for 8h to obtain the nitrogen-doped fir wood blocks;
s3, placing the nitrogen-doped fir wood block prepared in the S2 into a tubular furnace, heating to 900 ℃ under the argon condition, keeping for 2 hours, and naturally cooling to obtain a nitrogen-doped porous carbon material NC I;
s4, mixing 1190mg of Zn (NO) 3 ) 2 ·6H 2 O and 121mg Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 25mL of methanol at room temperature to prepare a methanol dispersion liquid A;
s5, dissolving 1314mg 2-methylimidazole in 15mL of methanol at room temperature to prepare a methanol dispersion liquid B; (ii) a
S6, adding the nitrogen-doped porous carbon material NC I prepared in 200mg S3 into the methanol dispersion liquid A prepared in S4, stirring for 6 hours to obtain a methanol solution containing the nitrogen-doped porous carbon material NC I,
s7, adding the methanol dispersion liquid B prepared in the S5 into the methanol solution of the nitrogen-doped porous carbon material NC I prepared in the S6, stirring for 24 hours, and taking out the reacted nitrogen-doped porous carbon material NC I to obtain a nitrogen-doped porous carbon material NC II;
s8, washing the nitrogen-doped porous carbon material NC II obtained in the step S7 by using ethanol, and then drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain Fe-ZIF-8/NC;
and S9, heating the Fe-ZIF8/NC obtained in the S8 to 900 ℃ under the condition of argon-hydrogen mixed gas in a tubular furnace, keeping the temperature for 3 hours, and naturally cooling to obtain the catalyst FeSAC/NC.
3. The method for preparing an air electrode catalyst of a zinc-air battery according to claim 2, wherein in S3, the temperature is controlled at 5-8 ℃ min -1 And the rate of temperature rise.
4. The method for preparing an air electrode catalyst of a zinc-air battery according to claim 2, wherein in S9, the volume ratio of argon to hydrogen in the argon-hydrogen mixture is 95:5.
5. the method for preparing an air electrode catalyst of a zinc-air battery according to claim 2, wherein in S9, the temperature is 3-5 ℃ per minute -1 And the rate of temperature rise.
6. An air electrode catalyst of a zinc-air battery is characterized by being applied to the zinc-air battery.
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