CN114105143A - Preparation method of iron carbide/porous carbon aerogel zinc-air battery cathode catalyst with defect structure - Google Patents
Preparation method of iron carbide/porous carbon aerogel zinc-air battery cathode catalyst with defect structure Download PDFInfo
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- CN114105143A CN114105143A CN202111409541.6A CN202111409541A CN114105143A CN 114105143 A CN114105143 A CN 114105143A CN 202111409541 A CN202111409541 A CN 202111409541A CN 114105143 A CN114105143 A CN 114105143A
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Abstract
The invention discloses a preparation method of a defect-structure iron carbide/porous carbon aerogel zinc-air battery cathode catalyst, and belongs to the field of metal-air batteries. The carbon aerogel adopts chitosan and potassium ferricyanide as raw materials to successfully prepare the cathode catalyst of the zinc-air battery. The carbon aerogel has a rich defect structure and a hierarchical pore structure, and shows excellent catalytic activity when used as a cathode catalyst of a zinc-air battery. The oxygen reduction (ORR) activity of conventional carbon nanomaterials in alkaline electrolytes is not ideal relative to commercial Pt/C. Therefore, the method has important significance for improving the ORR catalytic performance of the carbon material under the alkaline condition and replacing a noble metal Pt-based catalyst to be applied to the zinc-air battery. In the invention, the chitosan source is rich, and the obtained iron carbide/porous carbon aerogel with a defect structure has excellent ORR catalytic performance under an alkaline condition, thereby being an energy conversion material with great prospect.
Description
Technical Field
The invention belongs to the field of metal-air batteries, and particularly relates to a preparation method of a defect-structure iron carbide/porous carbon aerogel zinc-air battery cathode catalyst.
Background
The core of the zinc-air cell is the catalyst. The key indexes of the catalyst are catalytic activity and stability, the higher the catalytic activity is, the higher the current density is, and the better the stability is, the longer the battery life is. Most of the prior electrocatalysts mainly have structures of noble metal nano particles combined with carbon materials, and the commonly used noble metal is platinum. At present, 20 wt% Pt/C series catalysts are commonly used in domestic production and scientific research. However, the commercialization of zinc-air batteries is seriously hindered by the problems of high price, low reserves, etc. of Pt. The development of low-cost, high-performance oxygen reduction (ORR) catalysts is a key to addressing the shortage of platinum resources, reducing fuel cell costs, and enabling fuel cell commercialization. Research shows that the iron-based/carbon material has certain catalytic activity on an ORR process in an alkaline electrolyte and has the potential of replacing Pt. Therefore, it is an important subject to improve the ORR catalytic performance of the iron-based carbon material under alkaline conditions for application to zinc-air batteries. Using chitosan and potassium ferricyanide as carbon source and iron source respectively, utilizing positive charge formed by dissolving chitosan in acetic acid aqueous solution through amino protonation and [ Fe (CN) in potassium ferricyanide solution6]3-Forming Fe-chitosan hydrogel by electrostatic interaction, and forming Fe by vacuum freeze drying and pyrolysis3And C/C aerogel, and then carrying out heat treatment on the C/C aerogel to remove part of carbon atoms to form the iron carbide/porous carbon aerogel nano material with a defect structure. The obtained nano material has good conductivity, ordered structure and easy processing. The method solves the problems of complex process, high cost and the like of the traditional method, improves the catalytic efficiency, reduces the use amount of the platinum catalyst, and improves the stability and the service life of the catalyst product.
Disclosure of Invention
The invention utilizes renewable chitosan with rich sources as a raw material to prepare the iron carbide/porous carbon aerogel with a defect structure which can be used as a cathode catalyst of a zinc-air battery.
The preparation method is simple in preparation process, does not need expensive equipment, and the obtained product is high in quality and good in performance and has bright prospect in future large-scale application of the zinc-air battery.
A preparation method of a defect-structure iron carbide/porous carbon aerogel zinc-air battery catalyst comprises the following steps:
1) preparing 200 mL of chitosan acetic acid water solution with the mass fraction of 0.3%, dripping the chitosan acetic acid water solution into 0.1M potassium ferricyanide solution, slowly stirring and soaking to obtain the iron-chitosan hydrogel;
2) preparing the iron-chitosan hydrogel into iron-chitosan aerogel by utilizing freeze drying;
3) calcining the iron-chitosan aerogel in a tubular furnace at 700 ℃ for 1 hour in an argon atmosphere to obtain iron carbide/carbon aerogel;
4) removing the nano-particles such as iron oxide in the iron carbide/carbon aerogel by using hydrochloric acid aqueous solution with the concentration of 3M to obtain the iron carbide/carbon aerogel;
5) the ORR catalytic activity of the product under 0.1M KOH electrolyte is tested by an electrochemical workstation and a rotating disc electrode;
6) and (3) assembling the obtained iron carbide/carbon aerogel material as a cathode catalyst material into a primary zinc-air battery, and testing the battery performance of the primary zinc-air battery.
The invention has the following advantages:
the raw materials used by the invention are mainly chitosan obtained by deacetylating chitin extracted from shells of arthropods such as shrimps, crabs and insects, and the chitosan has the advantages of wide raw material source, environmental protection, green and high safety, and is a huge renewable resource.
The iron carbide/porous carbon aerogel with the defect structure prepared by the method can be used as a zinc-air battery cathode catalyst with excellent performance, and has high catalytic activity and good stability.
The iron carbide/porous carbon aerogel with the defect structure prepared by the method can be synthesized in a large amount, does not need expensive equipment, and can be widely used in zinc-air batteries.
Drawings
Fig. 1 is an SEM image of the iron carbide/porous carbon aerogel obtained in example 1, and it is clearly seen that the iron carbide/porous carbon aerogel has a distinct macroporous-mesoporous structure;
fig. 2 is an XPS test of the iron carbide/porous carbon aerogel having a defect structure obtained in example 1, wherein the catalyst mainly consists of C, N, O, Fe elements, the N element mainly exists in the form of graphite nitrogen and pyridine nitrogen, and the O element mainly comes from air oxidation.
FIG. 3 shows ORR catalytic activity of iron carbide/porous carbon aerogel obtained in example 1 in alkaline electrolyte, and half-wave potential of 0.78V in 0.1M KOH electrolyte; after 15 hours of testing in 0.1M KOH electrolyte, the cell density remained at the initial 97%; the capacity density of the primary zinc-air battery assembled by the zinc-air battery reaches 150 mW cm-2。
FIG. 4 shows ORR catalytic activity of the iron carbide/porous carbon aerogel with defect structure obtained in example 2 in alkaline electrolyte, and half-wave potential of 0.84V in 0.1M KOH electrolyte; stability in alkaline electrolyte, the cell density can still maintain 93% of the initial density after 15 hours of testing in 0.1M KOH electrolyte; the capacity density of the primary zinc-air battery assembled by the battery reaches 200 mW cm-2。
FIG. 5 shows ORR catalytic activity of the iron carbide/nitrogen-doped porous carbon aerogel with a defect structure obtained in example 3 in an alkaline electrolyte, wherein the half-wave potential of the iron carbide/nitrogen-doped porous carbon aerogel with a defect structure in a 0.1M KOH electrolyte is 0.87V; stability in alkaline electrolyte, after 15 hours of test in 0.1M KOH electrolyte, the cell density can also maintain the initial 95 percent capacity density of the primary zinc-air cell assembled by the cell to reach 254 mW cm-2。
Fig. 6 shows, from top to bottom, a half-wave potential of 0.84V for the iron carbide/porous carbon aerogel having a defect structure in a 0.1M KOH electrolyte, and a half-wave potential of 0.87V for the iron carbide/nitrogen-doped porous carbon aerogel having a defect structure in a 0.1M KOH electrolyte, respectively.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
1) Preparing 200 mL of chitosan acetic acid aqueous solution with the mass fraction of 1-3%, dripping the chitosan acetic acid aqueous solution into 0.1M potassium ferricyanide solution, slowly stirring and soaking to obtain the iron-chitosan hydrogel;
2) preparing the iron-chitosan hydrogel into metal chitosan aerogel by utilizing freeze drying;
3) calcining the iron-chitosan aerogel in a tubular furnace at 700 ℃ for 1 hour in an argon atmosphere to obtain nitrogen/sulfur co-doped carbon aerogel;
4) removing nanoparticles such as iron oxide in the iron carbide/carbon aerogel by using hydrochloric acid aqueous solution with the concentration of 3M to obtain the iron carbide/porous carbon aerogel;
5) the ORR catalytic activity of the product under 0.1M KOH electrolyte is tested by an electrochemical workstation and a rotating disk electrode;
6) and (3) assembling the obtained iron carbide/carbon aerogel material as a cathode catalyst material into a primary zinc-air battery, and testing the battery performance of the primary zinc-air battery.
Example 2
1) Preparing 200 mL of chitosan acetic acid aqueous solution with the mass fraction of 0.3%, dripping the chitosan acetic acid aqueous solution into 0.1M potassium ferricyanide solution, slowly stirring and soaking to obtain iron-chitosan hydrogel;
2) preparing the metal-chitosan hydrogel into iron-chitosan aerogel by utilizing freeze drying;
3) calcining the iron-chitosan aerogel in a tubular furnace at 700 ℃ for 1 hour in an argon atmosphere to obtain iron carbide/carbon aerogel;
4) removing nanoparticles such as iron oxide in the iron carbide/carbon aerogel by using hydrochloric acid aqueous solution with the concentration of 3M to obtain the iron carbide/porous carbon aerogel;
5) carrying out high-temperature heat treatment (1000 ℃, 1 hour) on the obtained iron carbide/porous carbon aerogel to remove a part of carbon atoms to obtain the iron carbide/porous carbon aerogel with a defect structure;
6) the ORR catalytic activity of the product under 0.1M KOH electrolyte is tested by an electrochemical workstation and a rotating disk electrode;
7) and (3) assembling the obtained iron carbide/carbon aerogel material as a cathode catalyst material into a primary zinc-air battery, and testing the battery performance of the primary zinc-air battery.
Example 3
1) Preparing 200 mL of chitosan acetic acid aqueous solution with the mass fraction of 1-3%, dripping the chitosan acetic acid aqueous solution into 0.1M potassium ferricyanide solution, slowly stirring and soaking to obtain the iron-chitosan hydrogel;
2) preparing the iron-chitosan hydrogel into iron-chitosan aerogel by utilizing freeze drying;
3) calcining the iron-chitosan aerogel in a tubular furnace at 700 ℃ for 1 hour in an argon atmosphere to obtain iron carbide/carbon aerogel;
4) removing nanoparticles such as iron oxide in the iron carbide/carbon aerogel by using hydrochloric acid aqueous solution with the concentration of 3M to obtain the iron carbide/porous carbon aerogel;
5) calcining the obtained iron carbide/porous carbon aerogel in a tubular furnace at 800 ℃ for 2h in an ammonia atmosphere for nitrogen doping treatment to obtain iron carbide/nitrogen doped porous carbon aerogel with a defect structure;
6) the ORR catalytic activity of the product under 0.1M KOH electrolyte is tested by an electrochemical workstation and a rotating disk electrode;
7) and (3) assembling the obtained iron carbide/carbon aerogel material as a cathode catalyst material into a primary zinc-air battery, and testing the battery performance of the primary zinc-air battery.
Claims (6)
1. A method for preparing an iron carbide/porous carbon aerogel having a defect structure, characterized in that the method comprises the following steps:
1) adding a certain amount of chitosan into an acetic acid aqueous solution, and stirring to obtain a chitosan aqueous solution;
2) dripping the chitosan aqueous solution into the potassium ferricyanide aqueous solution, stirring and soaking to obtain the iron-chitosan hydrogel;
3) preparing the iron-chitosan hydrogel into iron-chitosan aerogel by utilizing freeze drying;
4) calcining the iron-chitosan aerogel in a tubular furnace by a certain carbonization process to obtain iron carbide/carbon aerogel;
5) removing nanoparticles such as iron oxide in the iron carbide/carbon aerogel by using a hydrochloric acid aqueous solution to obtain the iron carbide/porous carbon aerogel;
6) the electrochemical performance of the product was tested using an electrochemical workstation and a rotating disk electrode.
2. The method according to claim 1, wherein the concentration of the aqueous acetic acid solution in the step 1) is 0.3% by mass, and the dissolution temperature is 20 to 25 ℃.
3. The method according to claim 1, wherein the concentration of the aqueous solution of potassium ferricyanide in step 2) is 0.1M, and the dissolution temperature is 20 to 25 ℃.
4. The method according to claim 1, wherein the carbonization process in step 4) is performed at 700 ℃ for 1 hour in an argon atmosphere.
5. The method according to claim 1, wherein the hydrochloric acid concentration in the step 5) is 0.5M, and the soaking time is 12 hours.
6. The test method as claimed in claim 1, wherein in the step 6), the oxygen reduction performance of the material is tested by mainly using cyclic voltammetry, linear sweep voltammetry, chronoamperometry and the like, and the voltage range is-1.0-0.2V; a three-electrode test apparatus, a reference electrode of Ag/AgCl/KCl saturated solution, and an electrolyte solution of 0.1M potassium hydroxide solution were used.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920237A (en) * | 2022-05-31 | 2022-08-19 | 中南大学 | Novel single-layer graphene aerogel and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114920237A (en) * | 2022-05-31 | 2022-08-19 | 中南大学 | Novel single-layer graphene aerogel and preparation method and application thereof |
| CN114920237B (en) * | 2022-05-31 | 2024-03-15 | 中南大学 | Single-layer graphene aerogel and preparation method and application thereof |
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Application publication date: 20220301 |