CN112186208B - Nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst and preparation method and application thereof - Google Patents
Nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst and preparation method and application thereof Download PDFInfo
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- CN112186208B CN112186208B CN202011099758.7A CN202011099758A CN112186208B CN 112186208 B CN112186208 B CN 112186208B CN 202011099758 A CN202011099758 A CN 202011099758A CN 112186208 B CN112186208 B CN 112186208B
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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
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- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
Abstract
The invention discloses a nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst, and a preparation method and application thereof. The method comprises the steps of mixing polyphenylene sulfide, benzophenone and dioctyl phthalate, and heating to a molten state to obtain a casting solution; then preparing the casting solution into a polyphenylene sulfide film; mixing an oxidant, deionized water and acid to obtain a blending solution; placing the polyphenylene sulfide film into the blending liquid to react until the blending liquid is emulsion, and then filtering, washing and drying; and carbonizing in ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst. The catalyst can be used as a positive electrode material of a zinc-air battery and a fuel battery. The method adopts polyphenylene sulfide with high sulfur content as a precursor, and prepares the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst through one-time pyrolysis, wherein the catalyst has a large number of active sites.
Description
Technical Field
The invention relates to a preparation method of an oxygen reduction catalyst, in particular to a nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst, and a preparation method and application thereof.
Background
The continuous deterioration of the global environment stimulates the development of new energy storage and conversion devices such as fuel cells, batteries and super capacitors, wherein the advantages of high energy density, low price, good safety and the like of the fuel cells are considered as an energy device with unique prospects, but the slow cathodic oxygen reduction reaction of the fuel cells is one of the main challenges limiting the commercial development of the fuel cells.
Currently, noble metal (Pt) based catalysts are mainly used commercially as oxygen reduction catalysts. However, the limited reserves, high costs, poor stability, etc. have severely hampered the large-scale application of noble metals (Pt) in fuel cells. The porous carbon material has received wide attention from researchers due to its excellent characteristics such as conductivity, stability, morphology and functionality. Therefore, the development of a low-cost, excellent-performance, and efficient carbon-based oxygen reduction catalyst to replace the expensive Pt-based catalyst is currently the focus of the commercialization of fuel cells.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem of providing a nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst, and a preparation method and application thereof.
The technical scheme for solving the technical problem is to provide a preparation method of a nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst, which is characterized by comprising the following steps:
(1) mixing polyphenylene sulfide, benzophenone and dioctyl phthalate, and heating to a molten state to obtain a casting film solution; then preparing the casting solution into a polyphenylene sulfide film;
mixing an oxidant, deionized water and acid to obtain a blending solution;
(2) placing the polyphenylene sulfide film into the blending liquid to react until the blending liquid is emulsion, and then filtering, washing and drying;
(3) carbonizing the product obtained in the step 2) in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method adopts polyphenylene sulfide with high sulfur content as a precursor, and prepares the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst through one-time pyrolysis, wherein the catalyst has a large number of active sites. In addition, the catalyst retains part of the unique pore channel structure of the polyphenylene sulfide membrane, and the decomposition of sulfur in the heat treatment process can produce a large number of pore defects, thereby being beneficial to the transmission of electrons.
(2) The preparation method is simple in preparation process and does not have a complex post-treatment process. The structural composition of the polyphenylene sulfide is improved through oxidation modification treatment, and the problem of melt agglomeration of the polyphenylene sulfide in a high-temperature environment is solved.
(3) The catalyst prepared by the method has unique morphology and extremely large specific surface area.
(4) The catalyst prepared by the method shows outstanding oxygen reduction reaction activity under acid and alkali conditions, has good cycle stability, and is an ideal fuel cell oxygen reduction electrocatalyst.
Drawings
FIG. 1 is an SEM photograph of the catalyst obtained in example 4 of the present invention, at 11000 times magnification;
FIG. 2 is an SEM photograph of the catalyst obtained in example 4 of the present invention, at a magnification of 110000 times;
FIG. 3 is a TEM image at 30000 times magnification of the catalyst obtained in example 4 of the present invention;
FIG. 4 is a TEM image of a 100000-fold amplification of the catalyst obtained in example 4 of the present invention;
FIG. 5 is an XPS spectrum of the catalyst obtained in example 4 of the present invention;
FIG. 6 is an XPS spectrum corresponding to the N element of the catalyst obtained in example 4 of the present invention;
FIG. 7 is a CV diagram of the catalyst obtained in example 4 of the present invention tested under alkalinity;
FIG. 8 is a graph of the LSV of the catalyst obtained in example 4 of the present invention tested at a basic speed of 1600 rpm;
FIG. 9 is a CV diagram of the catalyst obtained in example 4 of the present invention tested under acidic conditions;
FIG. 10 is a graph of the LSV of the catalyst obtained in example 4 of the present invention tested at an acidic rotation speed of 1600 rpm;
FIG. 11 is a charge-discharge polarization curve and a power density curve of a zinc-air battery assembled by using the catalyst obtained in example 4 of the present invention as a cathode;
FIG. 12 shows 10mA/cm of a zinc-air battery assembled with the catalyst obtained in example 4 of the present invention as a cathode2A constant current discharge curve;
FIG. 13 is an XRD pattern of the catalysts obtained in example 1, example 2, example 3 and example 4 of the present invention;
FIG. 14 is a Raman graph of the catalysts obtained in example 1, example 2, example 3 and example 4 of the present invention;
FIG. 15 is a drawing showing the adsorption/desorption of the catalysts obtained in example 1, example 2, example 3 and example 4 of the present invention;
Detailed Description
The present invention will be further described with reference to the following examples and accompanying drawings. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.
The invention provides a preparation method (short for method) of a nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst, which is characterized by comprising the following steps:
(1) mixing polyphenylene sulfide resin, benzophenone and dioctyl phthalate, heating to a molten state (265-280 ℃) to obtain a casting solution; then transferring the casting solution to a metal flat plate with the temperature of 160-280 ℃ (preferably 245-280 ℃), carrying out film forming treatment on the metal flat plate by using a metal film forming rod, then transferring the metal flat plate to a distilled water coagulating bath at room temperature for rapid solidification, finally soaking the metal flat plate in ethanol to extract benzophenone, taking out and drying the benzophenone to obtain the microporous polyphenylene sulfide film;
the mass ratio of the polyphenylene sulfide to the benzophenone to the dioctyl phthalate is 4-8: 8-16: 1-4 (preferably 4:10: 1);
mixing an oxidant, deionized water and acid, and stirring for 1-5 min to obtain a blending solution;
the mass ratio of the oxidant to the deionized water to the acid is 3-6: 0.1-1 (preferably 5:5: 0.1); the oxidant is hydrogen peroxide, nitric acid, potassium permanganate, concentrated sulfuric acid, hypochlorous acid, perchloric acid or sodium hypochlorite; the acid is hydrochloric acid, phosphoric acid, glacial acetic acid or boric acid;
(2) cutting or chopping the microporous polyphenylene sulfide membrane to facilitate oxidation modification treatment, then putting the microporous polyphenylene sulfide membrane into the blending liquid, stirring the microporous polyphenylene sulfide membrane for 12 to 72 hours (preferably 12 hours) at 50 to 100 ℃ (preferably 80 ℃) until the blending liquid is emulsion, then filtering the blending liquid to obtain a white powdery substance, washing and drying the white powdery substance;
in the step 2), the washing process is to wash the mixture to be neutral by using deionized water; the drying environment is a vacuum oven at 60-80 ℃.
(3) And (3) putting the product obtained in the step 2) into a tubular furnace, and carbonizing at 800-1100 ℃ for 1-4 h in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
Preferably, in step 3), carbonization is carried out at 1100 ℃ for 2 h.
The invention also provides a nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst (catalyst for short) prepared by the preparation method of the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
The invention also provides application of the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst, which is characterized in that the catalyst is used as anode materials of zinc-air batteries and fuel batteries; the zinc-air battery takes the catalyst as a positive electrode material and takes the catalyst as the positive electrode material at a concentration of 1mg/cm2The zinc-air battery is assembled by taking a zinc sheet as a negative electrode and 6M KOH solution as alkaline electrolyte.
Example 1
blending hydrogen peroxide, deionized water and hydrochloric acid in a beaker according to a mass ratio of 50:50:1, and stirring for 2min to obtain a blended solution;
and 3, putting the product obtained in the step 2 into a tubular furnace, and carbonizing for 2h at 800 ℃ in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
Example 2
blending hydrogen peroxide, deionized water and hydrochloric acid in a beaker according to a mass ratio of 50:50:1, and stirring for 2min to obtain a blended solution;
and 3, putting the product obtained in the step 2 into a tubular furnace, and carbonizing for 2h at 900 ℃ in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
Example 3
blending hydrogen peroxide, deionized water and hydrochloric acid in a beaker according to a mass ratio of 50:50:1, and stirring for 2min to obtain a blended solution;
and 3, putting the product obtained in the step 2 into a tubular furnace, and carbonizing for 2h at 1000 ℃ in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
Example 4
blending hydrogen peroxide, deionized water and hydrochloric acid in a beaker according to a mass ratio of 50:50:1, and stirring for 2min to obtain a blended solution;
and 3, putting the product obtained in the step 2 into a tubular furnace, and carbonizing for 2h at 1100 ℃ in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
As can be seen from fig. 1, the obtained catalyst has unique morphology and channel structure, which is beneficial to the transport of protons in the catalytic process.
As can be seen from fig. 2, a large number of pore defects are distributed on the surface of the catalyst, and the pore defects are caused by the desulfurization process during the temperature rise, and the large number of pore defects are beneficial to increasing the specific surface area of the catalyst and increasing the catalytic active sites.
As can be seen from fig. 3, the catalyst is a porous carbon structure with uniform distribution.
As can be seen from fig. 4, the interior of the catalyst is also enriched with a number of pore defects, which further confirms the porous character of the catalyst.
As can be seen from fig. 5, the N and S elements were successfully doped into the carbon matrix.
As can be seen from FIG. 6, the N element in the catalyst mainly exists in two forms of pyridine-N (pyridine-N) and graphite-N (graphite-N), and the N in the two forms plays an important supporting role in the reaction of the oxidation source.
The oxidability characterization of the catalyst is completed by testing on Chenghua 760E electrochemical workstation and rotating disk electrode. The alkaline test conditions were oxygen saturated 0.1M KOH electrolyte, the auxiliary electrode was a Pt plate and the reference electrode was Ag/AgCl. The acidic test condition was 0.5M H saturated with oxygen2SO4The electrolyte, the auxiliary electrode were Pt sheets, and Hg/Hg was used as a reference electrode2Cl2. Wherein the rotation speed of the LSV test is 1600 rpm.
As can be seen from the CV test results of fig. 7, the catalyst obtained in example 4 has a significant redox peak at 0.79V vs. rhe, which indicates that the catalyst has excellent oxygen reduction catalytic activity under alkaline conditions.
As can be seen from the LSV test results of FIG. 8, the half-wave potential of the catalyst obtained in example 4 was 0.861V vs. RHE, and the limiting current density was 5.72mA/cm2Comparison with commercial Pt/C catalyst (half-wave potential 0.843V vs. RHE, limiting current density 5.38mA/cm2) The catalytic performance of (A) is equivalent.
As can be seen from the CV test results in fig. 9, similar to the test results under the alkaline condition, the catalyst obtained in example 4 has a significant redox peak around 0.59V vs. rhe, indicating that the catalyst has good catalytic activity under the acidic condition as well.
As can be seen from the LSV test results of FIG. 10, the half-wave potential of the catalyst obtained in example 4 was 0.648V vs. RHE, and the limiting current density was 5.68mA/cm2The performance is comparable to that of a commercial Pt/C catalyst (half-wave potential 0.773V vs. RHE, limiting current density 5.18 mA/cm)2)。
From the above test results, the prepared catalyst has good oxygen reduction catalytic activity under both acidic and alkaline conditions.
The catalyst obtained in this example was used as a positive electrode material at a concentration of 1mg/cm2The zinc-air battery is assembled by taking a zinc sheet as a negative electrode and 6M KOH solution as alkaline electrolyte. The polarization curve and power density curve of charge and discharge of the zinc-air cell were tested on Chenghua 760E electrochemical workstation, as can be seen from FIG. 11, where the power density is 320mA/cm2Then reaches 197mW/cm2And excellent power performance is shown.
The discharge curve of the zinc-air cell was tested on a blue system and it can be seen from FIG. 12 that the catalyst has 865mAh/gZnThe energy density of (2) is superior to the performances reported in most of the prior literatures.
TABLE 1
| Sample(s) | Surface area (m) of specific Surface area2/g) |
| Example 1 | 444.91 |
| Example 2 | 745.86 |
| Example 3 | 954.25 |
| Example 4 | 1254.04 |
Table 1 shows data of specific surface areas of the catalysts obtained in example 1, example 2, example 3 and example 4 of the present invention; from the results in Table 1, it was found that the catalyst had an extremely high specific surface area, and that the specific surface area of example 4 reached 1254.04m2(ii) in terms of/g. The high specific surface area has a remarkable promoting effect on catalytic reaction, which also indicates that the polyphenylene sulfide has a very wide prospect as a precursor of the catalyst.
As can be seen from fig. 13, the catalysts obtained in examples 1 to 4 all have typical characteristic peaks of graphitic carbon, and two peaks appearing near 23 ° and 43 ° represent the (002) and (100) crystal planes of graphitic carbon, respectively.
As can be seen from FIG. 14, the catalysts obtained in examples 1 to 4 all had higher ID/IGThis indicates that the material has significant defect characteristics. And with increasing carbonization temperature in examples 1 to 4, ID/IGThe value gradually increases and the defects significantly increase.
As can be seen from FIG. 15, the catalysts prepared in examples 1-4 all have typical type IV adsorption and desorption curves, which illustrate the coexistence of micropores and mesopores in the material.
Example 5
blending hydrogen peroxide, deionized water and hydrochloric acid in a beaker according to a mass ratio of 50:50:1, and stirring for 2min to obtain a blended solution;
and 3, putting the product obtained in the step 2 into a tubular furnace, and carbonizing for 2h at 1100 ℃ in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
Example 6
blending hydrogen peroxide, deionized water and hydrochloric acid in a beaker according to a mass ratio of 50:50:1, and stirring for 2min to obtain a blended solution;
and 3, putting the product obtained in the step 2 into a tubular furnace, and carbonizing for 2h at 1100 ℃ in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
Example 7
blending hydrogen peroxide, deionized water and hydrochloric acid in a beaker according to a mass ratio of 50:50:1, and stirring for 2min to obtain a blended solution;
and 3, putting the product obtained in the step 2 into a tubular furnace, and carbonizing for 2h at 1100 ℃ in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
Nothing in this specification is said to apply to the prior art.
Claims (10)
1. A preparation method of a nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst is characterized by comprising the following steps:
(1) mixing polyphenylene sulfide, benzophenone and dioctyl phthalate, and heating to a molten state to obtain a casting film solution; then the casting solution is formed into a film and solidified, and benzophenone is extracted out to prepare a microporous polyphenylene sulfide film;
mixing an oxidant, deionized water and acid to obtain a blending solution; the acid is hydrochloric acid, phosphoric acid, glacial acetic acid or boric acid;
(2) placing the polyphenylene sulfide film into the blending liquid to react until the blending liquid is emulsion, then filtering to obtain a white powdery substance, washing and drying;
(3) carbonizing the product obtained in the step 2) in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
2. The method for preparing the nitrogen-sulfur co-doped carbon-based oxygen reduction catalyst according to claim 1, wherein the process for preparing the polyphenylene sulfide film from the casting solution comprises the following steps: transferring the casting solution onto a 245-280 ℃ metal flat plate, performing film formation treatment on the metal flat plate by using a metal film forming rod, transferring the metal flat plate into distilled water for solidification, finally soaking the metal flat plate into ethanol to extract benzophenone, taking out the benzophenone, and drying the benzophenone to obtain the microporous polyphenylene sulfide film.
3. The preparation method of the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst according to claim 1, wherein in the step 1), the mass ratio of the polyphenylene sulfide to the benzophenone to the dioctyl phthalate is 4-8: 8-16: 1-4.
4. The preparation method of the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst according to claim 1, wherein in the step 1), the mass ratio of the oxidant, the deionized water and the acid is 3-6: 0.1-1; the oxidant is hydrogen peroxide, nitric acid, potassium permanganate, concentrated sulfuric acid, hypochlorous acid, perchloric acid or sodium hypochlorite.
5. The method for preparing a nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst according to claim 1, wherein the step 2) is: and (2) putting the polyphenylene sulfide film into the blending liquid, stirring for 12-72 hours at 50-100 ℃ until the blending liquid is emulsion, filtering to obtain a white powdery substance, washing and drying.
6. The method for preparing the nitrogen-sulfur co-doped carbon-based oxygen reduction catalyst according to claim 1 or 5, wherein in the step 2), the rinsing process is to rinse the catalyst to be neutral by using deionized water; the drying environment is a vacuum oven at 60-80 ℃.
7. The method for preparing a nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst according to claim 1, wherein the step 3) is: and (3) putting the product obtained in the step 2) into a tubular furnace, and carbonizing at 800-1100 ℃ for 1-4 h in an ammonia atmosphere to obtain the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst.
8. The nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst obtained by the preparation method of the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst according to any one of claims 1 to 7.
9. Use of the nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst according to claim 8, wherein the catalyst is used as a positive electrode material of zinc-air batteries and fuel cells.
10. Use of nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst according to claim 9, characterized in that the catalyst is used as positive electrode material at 1mg/cm2The zinc-air battery is assembled by taking a zinc sheet as a negative electrode and 6M KOH solution as alkaline electrolyte.
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