CN110911701A - Oxygen reduction catalyst, and preparation method and application thereof - Google Patents

Oxygen reduction catalyst, and preparation method and application thereof Download PDF

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Publication number
CN110911701A
CN110911701A CN201911022828.6A CN201911022828A CN110911701A CN 110911701 A CN110911701 A CN 110911701A CN 201911022828 A CN201911022828 A CN 201911022828A CN 110911701 A CN110911701 A CN 110911701A
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oxygen reduction
reduction catalyst
thermal cracking
oxygen
catalyst according
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杨玲玲
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy 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
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of an oxygen reduction catalyst, which comprises the following steps: taking the waste tire pyrolytic carbon black, carrying out primary thermal cracking, then washing, and then carrying out secondary thermal cracking to obtain the oxygen reduction catalyst. The invention also discloses an oxygen reduction catalyst, which is prepared according to the preparation method of the oxygen reduction catalyst. The invention also discloses the application of the oxygen reduction catalyst in a proton exchange membrane fuel cell. The invention provides an oxygen reduction catalyst which takes pyrolytic carbon black of waste tires as a raw material and has excellent catalytic performance and high stability, aiming at the problems of development limitation of proton exchange membrane fuel cells, overhigh price of the oxygen reduction catalyst and pollution of waste tires.

Description

Oxygen reduction catalyst, and preparation method and application thereof
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to an oxygen reduction catalyst and a preparation method and application thereof.
Background
With the development of society in recent years, the energy crisis is a big problem facing all over the world and urgently needing to be solved. The fuel cell is considered as a novel clean energy source which can replace the traditional fossil fuel, and has the advantages of high efficiency (45-60%), no pollution, strong feasibility, flexible installation place and the like. Fuel cells can be classified into the following categories according to the difference in the electrolyte used: phosphoric acid fuel cells, alkaline fuel cells, solid oxide fuel cells, direct methanol fuel cells, proton exchange membrane fuel cells.
Compared with other fuel cells, a Proton Exchange Membrane Fuel Cell (PEMFC) uses a perfluorinated sulfonic acid resin polymer as an electrolyte, has the advantages of less environmental pollution, low working temperature, and avoidance of corrosion of materials caused by electrolyte phosphoric acid in a phosphoric acid fuel cell, and researchers consider the proton exchange membrane fuel cell to be the best power supply device. In recent years, the development of fuel cells has been greatly advanced all over the world, and fuel cell-equipped automobiles are now on the market, but the high cost and low commercialization of cathode oxygen reduction catalysts are the main reasons that limit the further commercialization of fuel cells.
The oxygen reduction catalyst which is commercialized at present is Pt/C, however, the platinum has limited reserves in nature and high price, and further large-scale commercial application of the fuel cell is seriously hindered. In addition, Pt/C is easy to be poisoned and deactivated, so that the development of low-cost and good-performance catalyst is urgent. The TM-N/C catalyst is the most promising non-noble metal catalyst to replace the Pt/C noble metal catalyst, and realize the commercialization of PEMFCs.
With the development of the automotive industry, the disposal of used tires has become an increasingly serious environmental problem. The waste tires not only cause huge waste of resources, but also become more and more black pollution.
Disclosure of Invention
The invention provides an oxygen reduction catalyst, a preparation method and application thereof based on technical problems in the background art, and provides the oxygen reduction catalyst which takes waste tire pyrolytic carbon black as a raw material, has excellent catalytic performance and high stability, aiming at the problems of development limitation of proton exchange membrane fuel cells, overhigh price of the oxygen reduction catalyst and pollution of waste tires.
The invention provides a preparation method of an oxygen reduction catalyst, which comprises the following steps: taking the waste tire pyrolytic carbon black, carrying out primary thermal cracking, then washing, and then carrying out secondary thermal cracking to obtain the oxygen reduction catalyst.
Preferably, the temperature of the first thermal cracking is 700-.
Preferably, the primary thermal cracking is carried out in an ammonia atmosphere.
Preferably, the temperature of the secondary thermal cracking is 850-.
Preferably, the secondary thermal cracking is performed in a mixed gas atmosphere of nitrogen and ammonia.
Preferably, the specific operation steps of washing are: cooling the waste tire pyrolytic carbon black subjected to primary thermal cracking to room temperature, then placing the waste tire pyrolytic carbon black into an acidic aqueous solution, stirring for 8-24h at 80-100 ℃, filtering, washing a filter cake with water and ethanol in sequence until the pH of a washing liquid is neutral, and baking for 24-36h at 60-100 ℃.
Preferably, the concentration of the acidic aqueous solution is 0.3 to 1 mol/L.
Preferably, the acidic aqueous solution is an aqueous sulfuric acid solution.
The first thermal cracking and the first thermal cracking are both carried out in a quartz crucible, and a tubular furnace is adopted for carrying out thermal cracking.
The water is deionized water.
The invention also provides an oxygen reduction catalyst, which is prepared according to the preparation method of the oxygen reduction catalyst.
The invention also provides an application of the oxygen reduction catalyst in a proton exchange membrane fuel cell.
The invention firstly proposes that the waste tire pyrolytic carbon black is used as a raw material, and the fuel cell cathode non-noble metal oxygen reduction catalyst with low cost and good catalytic performance is prepared by a proper method, so that the waste tire can be reasonably disposed, the resource is recycled, the waste is changed into valuable, the invention has great significance for environmental protection, the production cost of the fuel cell cathode catalyst can be greatly reduced, and a new thought is provided for further commercialization of the fuel cell and solving the problem of energy exhaustion worldwide; the oxygen reduction catalyst obtained by the invention has excellent catalytic performance, high stability and good methanol resistance; and the preparation method is simple and easy to operate.
Drawings
FIG. 1 is an XPS plot of oxygen reduction catalysts prepared in examples 3-7.
FIG. 2 is a graph showing pore size distribution of oxygen reduction catalysts obtained in examples 3 to 7.
FIG. 3 is a plot of cyclic voltammograms of the oxygen reduction catalyst prepared in example 5.
FIG. 4 is a graph of a methanol resistance test of the oxygen reduction catalyst prepared in example 4.
FIG. 5 is a graph showing the accelerated durability ADT of the oxygen-reducing catalyst obtained in example 4.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A method of preparing an oxygen reduction catalyst comprising the steps of:
taking waste tire pyrolytic carbon black, and carrying out primary thermal cracking for 2h at 700 ℃ in an ammonia atmosphere;
cooling the waste tire pyrolytic carbon black subjected to primary thermal cracking to room temperature, then placing the waste tire pyrolytic carbon black into a sulfuric acid aqueous solution with the concentration of 0.3mol/L, stirring for 8 hours at 100 ℃, filtering, washing a filter cake with water and ethanol in sequence until the pH value of a washing liquid is neutral, and baking for 24 hours at 100 ℃;
then carrying out secondary thermal cracking for 0.5h at 1100 ℃ in a mixed gas atmosphere of nitrogen and ammonia, cooling to room temperature to obtain the oxygen reduction catalyst, wherein the volume fraction of nitrogen in the mixed gas is 20%, and N is used2-20 is as defined in the specification.
Example 2
A method of preparing an oxygen reduction catalyst comprising the steps of:
taking waste tire pyrolytic carbon black, and carrying out primary thermal cracking for 20min at 1000 ℃ in an ammonia atmosphere;
cooling the waste tire pyrolytic carbon black subjected to primary thermal cracking to room temperature, then placing the waste tire pyrolytic carbon black into a sulfuric acid aqueous solution with the concentration of 1mol/L, stirring the mixture for 24 hours at the temperature of 80 ℃, filtering the mixture, sequentially washing a filter cake with water and ethanol until the pH value of a washing liquid is neutral, and baking the filter cake for 36 hours at the temperature of 60 ℃;
then carrying out secondary thermal cracking for 2h at 850 ℃ in the mixed gas atmosphere of nitrogen and ammonia, cooling to room temperature to obtain the oxygen reduction catalyst, wherein the volume fraction of nitrogen in the mixed gas is 40%, and N is used2-40.
Example 3
A method of preparing an oxygen reduction catalyst comprising the steps of:
taking waste tire pyrolytic carbon black, and carrying out primary thermal cracking for 1h at 950 ℃ in an ammonia atmosphere;
cooling the waste tire pyrolytic carbon black subjected to primary thermal cracking to room temperature, then placing the waste tire pyrolytic carbon black into a sulfuric acid aqueous solution with the concentration of 0.5mol/L, stirring for 8 hours at 100 ℃, removing unstable impurities, filtering, sequentially filtering and washing a filter cake with water and ethanol until the pH value of a washing liquid is 7, and then baking for 24 hours at 100 ℃;
then carrying out secondary thermal cracking for 2h at 900 ℃ in the mixed gas atmosphere of nitrogen and ammonia, cooling to room temperature to obtain the oxygen reduction catalyst, wherein the volume fraction of nitrogen in the mixed gas is 20%, and N is used2-20 is as defined in the specification.
Example 4
The volume fraction of nitrogen in the mixed gas is 40 percent, and N is used2-40 represents, otherwise, the same as example 3.
Example 5
The volume fraction of nitrogen in the mixed gas is 60 percent, and N is used2-60 represents, otherwise, the same as example 3.
Example 6
The volume fraction of nitrogen in the mixed gas is 80 percent, and N is used2-80, otherwise the same as in example 3.
Example 7
The second thermal cracking is carried out in a nitrogen atmosphere with N2-100, otherwise the same as in example 3.
Test example 1
The oxygen reduction catalysts obtained in examples 3 to 7 were examined, and the results are shown in FIGS. 1 to 2, and FIG. 1 is an XPS chart of the oxygen reduction catalysts obtained in examples 3 to 7, in which N is2-20、N2-40、N2-60、N2-80、N2-100 is example 3, example 4, example 5, example 6, example 7 in that order; FIG. 2 is a graph showing the pore size distribution of the oxygen reduction catalysts obtained in examples 3 to 7, wherein N is2-20、N2-40、N2-60、N2-80、N2-100 is example 3, example 4, example 5, example 6, example 7 in that order;
as can be seen from fig. 1, the N element in the oxygen reduction catalyst exists mainly in four forms, pyridine nitrogen, pyrrole nitrogen, graphite nitrogen, nitrogen oxide; the graphite nitrogen and the pyridine nitrogen are respectively related to the limiting current density and the initial potential of the oxygen reduction catalyst, and the pyrrole nitrogen and the nitrogen oxide have no influence on the catalytic activity of the oxygen reduction catalyst;
as can be seen from fig. 2, the oxygen reduction catalyst mainly has the characteristic of multilevel mesopores, and the pore sizes are mainly concentrated at 6, 30, 36, 43 and 50 nm; the mesoporous nature of the oxygen reduction catalyst favors O2、H+Etc. (rate control step of oxygen reduction); in addition, the oxygen reduction catalyst has a relatively high pore volume, from 0.05 to 1.10cm3(ii)/g; the above results show that the oxygen reduction catalyst has many favorable structural characteristics, such as high specific surface area, pore volume and multi-stage mesoporous property, and the unique structural characteristics are favorable for O2And provides an effective catalytically active site structure.
Test example 2
The oxygen reduction catalyst prepared in example 5 was examined, and the results are shown in FIG. 3, in which FIG. 3 is a cyclic voltammogram of the oxygen reduction catalyst prepared in example 5; as can be seen from FIG. 3, when the volume fraction of nitrogen in the mixed gas is 60% (N)2-60), the resulting oxygen reduction catalyst had a half-wave potential of 0.36V, an initial potential of 0.57V, and only 0.14V and 0.11V lower than commercial Pt/C.
Test example 3
The oxygen reduction catalyst obtained in example 4 was examined, and the results are shown in FIGS. 4 to 5, and FIG. 4 is a graph showing the methanol resistance test of the oxygen reduction catalyst obtained in example 4, wherein N is2-40 is example 4, Pt/C is Pt/C catalyst; FIG. 5 is a graph showing the accelerated durability ADT of the oxygen reduction catalyst obtained in example 4, wherein initial is the 1 st turn 1000thcycles is circle 1000;
as can be seen from FIG. 4, when 3M methanol was added to the 0.1M KOH electrolyte, the current of the oxygen reduction catalyst decreased only 15%, while the current of Pt/C decreased sharply by 80%, which had excellent methanol resistance;
as can be seen from FIG. 5, the half-wave potential of the oxygen reduction catalyst after 1000 cycles of the test from 1 to 1000 cycles of the linear sweep curve of the oxygen reduction catalyst in 0.1M KOH electrolyte was substantially unchanged, while the half-wave potential of Pt/C was shifted negative by 27 mV.
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 person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. A method for preparing an oxygen reduction catalyst, comprising the steps of: taking the waste tire pyrolytic carbon black, carrying out primary thermal cracking, then washing, and then carrying out secondary thermal cracking to obtain the oxygen reduction catalyst.
2. The method for preparing an oxygen reduction catalyst as claimed in claim 1, wherein the temperature of the first thermal cracking is 700 ℃ and 1000 ℃ and the time is 20min-2 h.
3. The method for producing an oxygen-reducing catalyst according to claim 1 or 2, wherein the primary thermal cracking is carried out in an ammonia gas atmosphere.
4. The method for preparing an oxygen-reducing catalyst according to any of claims 1 to 3, wherein the temperature of the secondary thermal cracking is 850 ℃ and 1100 ℃ for 0.5 to 2 hours.
5. The method for producing an oxygen-reducing catalyst according to any one of claims 1 to 4, wherein the secondary thermal cracking is carried out in a mixed gas atmosphere of nitrogen and ammonia.
6. The method for producing an oxygen-reducing catalyst according to any one of claims 1 to 5, wherein the washing is carried out by the following specific steps: cooling the waste tire pyrolytic carbon black subjected to primary thermal cracking to room temperature, then placing the waste tire pyrolytic carbon black into an acidic aqueous solution, stirring for 8-24h at 80-100 ℃, filtering, washing a filter cake with water and ethanol in sequence until the pH of a washing liquid is neutral, and baking for 24-36h at 60-100 ℃.
7. The method for producing an oxygen-reducing catalyst according to claim 6, wherein the concentration of the acidic aqueous solution is 0.3 to 1 mol/L.
8. The method for producing an oxygen-reducing catalyst according to claim 6, wherein the acidic aqueous solution is an aqueous sulfuric acid solution.
9. An oxygen reduction catalyst, characterized by being produced by the method for producing an oxygen reduction catalyst according to any one of claims 1 to 8.
10. Use of an oxygen reduction catalyst according to claim 9 in a proton exchange membrane fuel cell.
CN201911022828.6A 2019-10-25 2019-10-25 Oxygen reduction catalyst, and preparation method and application thereof Pending CN110911701A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5369215A (en) * 1992-04-06 1994-11-29 S-P Reclamation, Inc. Depolymerization method for resource recovery from polymeric wastes
CN102214516A (en) * 2011-03-17 2011-10-12 南开大学 Method for preparing capacitor electrode material from waste tire pyrolytic carbon
CN102916203A (en) * 2012-11-07 2013-02-06 武汉理工大学 Cathode non-platinum catalyst of proton exchange membrane fuel cell and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5369215A (en) * 1992-04-06 1994-11-29 S-P Reclamation, Inc. Depolymerization method for resource recovery from polymeric wastes
CN102214516A (en) * 2011-03-17 2011-10-12 南开大学 Method for preparing capacitor electrode material from waste tire pyrolytic carbon
CN102916203A (en) * 2012-11-07 2013-02-06 武汉理工大学 Cathode non-platinum catalyst of proton exchange membrane fuel cell and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨玲玲: "《安徽师范大学硕士学位论文》", 30 March 2016 *

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