CN113178582A - Proton exchange membrane fuel cell anti-reversal electrode PtIr/CNT catalyst and preparation method thereof - Google Patents
Proton exchange membrane fuel cell anti-reversal electrode PtIr/CNT catalyst and preparation method thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 88
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- 238000001035 drying Methods 0.000 claims description 13
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- 238000005406 washing Methods 0.000 claims description 10
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- 239000002245 particle Substances 0.000 claims description 7
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- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000706 filtrate Substances 0.000 claims description 2
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 claims description 2
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 4
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- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The invention provides a proton exchange membrane fuel cell anti-reversal anode catalyst, which takes a PtIr alloy as an active component and a carbon nano tube as a carrier, wherein the molar ratio of Pt to Ir is 6-1: 1; when the anode catalyst provided by the invention is used for the anode catalyst layer of the fuel cell, no extra anti-reversal additive is needed to be added, agglomeration caused by directly adding iridium oxide or iridium is avoided, better performance can be kept after the fuel cell has frequent repeated reversal, and the reversal tolerance of the membrane electrode is obviously improved.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a fuel cell anti-reversal anode catalyst and a preparation method thereof, which can effectively relieve adverse effects caused by frequent reversal of a cell in the operation process, thereby prolonging the durability and the service life of the cell.
Background
Proton exchange membrane fuel cells have been developed at a high rate in recent years due to their high efficiency, quietness, no pollution, etc., but their durability is still an obstacle to large-scale commercialization. During the operation of the fuel cell, a cell voltage reversal phenomenon caused by insufficient supply of fuel occurs, in which case the anode voltage rapidly rises to 1.5V or more, and water electrolysis of the carbon support and water is forced to occur to maintain the current balance. At the moment, the anode potential is higher than the cathode potential, the voltage is reversed, the carbon carrier is corroded, the platinum catalyst is degraded, the catalyst layer structure collapses, and finally the performance of the battery is irreversibly attenuated.
The occurrence of voltage reversal phenomena can be prevented by some system control strategies, such as monitoring of the cell voltage and the reactant gas stoichiometry, purging the anode with air or nitrogen when parking, etc. However, system control strategies often require the addition of additional systems to the battery system, which increases cost and complexity. Therefore, some material-based strategies have been developed, such as the introduction of anti-reversal additives, such as electrolytic water catalysts like Ir, Ru, etc., into the anode catalytic layer; in addition, some corrosion-resistant supports, such as metal oxide supports, are also used, but the oxides reduce the initial activity of the battery due to their lower electrical conductivity.
CN111029599A discloses a fuel cell anti-reversal catalyst and a preparation method thereof, wherein the catalyst is an iridium oxide and niobium composite doped titanium dioxide catalyst, and after the anti-reversal catalyst is introduced into an anode, the water electrolysis time in the reversal period can be effectively prolonged, and the carbon corrosion in the reversal period is effectively relieved. However, the catalyst provided by the invention is an anti-reversal additive, which needs to be added into an anode catalyst, and the anti-reversal additive needs to be prepared additionally and needs high temperature, and in addition, the initial performance of the battery is reduced obviously due to poor conductivity of the oxide.
Disclosure of Invention
Based on the technical problems, the invention focuses on a one-pot preparation method and application of the anti-reversal catalyst, and aims to introduce a second metal to improve the water electrolysis activity of the catalyst, so that the reversal tolerance performance of the membrane electrode is improved, and the durability of the membrane electrode is improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
in one aspect, the invention provides a fuel cell anti-reversal anode catalyst, which takes a PtIr alloy as an active component and a carbon nanotube as a carrier; the molar ratio of Pt to Ir is 6-1: 1.
based on the technical scheme, preferably, the particle size of the PtIr alloy is 1.6-1.9 nm; the mass proportion of the active component to the carrier is 0.1-0.8: 1, and the molar ratio of Pt to Ir is 3: 1.
Based on the technical scheme, the mass proportion of the active component to the carrier is preferably 0.2-0.7: 1.
In another aspect, the present invention provides a method for preparing the above-mentioned anti-reversal catalyst, wherein the method is a polyol reflux method, and is completed in one pot without multiple steps.
The polyol reflux method comprises the following steps:
(1) pretreatment of the support
The method comprises the following steps: weighing carbon nanotubes, adding the carbon nanotubes into a mixed solution of commercially available concentrated sulfuric acid (with a mass fraction of about 98%) and commercially available concentrated nitric acid (with a mass fraction of about 68%), and stirring to obtain a mixed solution 1, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 5: 1-1: 5, preferably 3: 1;
step two: diluting the mixed solution 1 with deionized water, filtering and washing until the pH value of the filtrate is neutral, and then drying filter residues to obtain the carrier;
(2) preparation of PtIr/CNT catalyst
Step three: adding a mixed solution of ethylene glycol and water in a certain volume ratio into a three-neck flask, and uniformly stirring to obtain a solution 1; adding the carbon nano tube treated by the acid into the solution 1, and performing ultrasonic dispersion to obtain slurry 1;
step four: adding a certain amount of Ir and Pt precursors into the slurry 1, and uniformly stirring to obtain slurry 2;
step five: and introducing nitrogen into the slurry 2 to remove oxygen, adjusting the pH to be more than 10 by using a NaOH solution, transferring the slurry into an oil bath pot to react, refluxing the slurry for 6-12 hours at the temperature of 120-160 ℃, and naturally cooling the slurry. The pH of the slurry after the reaction was adjusted to 2 or less with a hydrochloric acid solution and stirred for 1 hour. And centrifuging and washing the product with deionized water, drying overnight in vacuum, and finely grinding to obtain the PtIr/CNT catalyst.
Further, in the first step, the stirring temperature is 60-130 ℃, and preferably 60 ℃; the stirring time is 1-6 h, preferably 3 h.
Further, in the third step, the volume ratio of the ethylene glycol to the water is 1: 3-3: 1, preferably 1: 1;
further, the Pt precursor is one of chloroplatinic acid, potassium chloroplatinate and platinum acetylacetonate; the Ir precursor is one of chloro-iridic acid, iridium trichloride and iridium acetylacetonate.
In still another aspect, the present invention provides a fuel cell anode catalyst layer, wherein the anode catalyst layer is prepared by using the above anti-reversal catalyst, and the anode catalyst layer does not need to be additionally added with an anti-reversal additive.
The invention also protects the application of the anode catalyst layer of the fuel cell in the fuel cell.
The invention has the advantages of
1. The anti-reversal catalyst provided by the invention uses the carbon nano tube with better stability as a catalyst carrier, and simultaneously introduces iridium with excellent electrolytic water performance to form a PtIr molar ratio of 6: 1-1: 1, Pt and Ir have interaction, the PtIr alloy not only reduces the agglomeration of the Pt and the Ir and is uniformly dispersed on a carbon carrier, but also avoids the agglomeration caused by directly adding iridium oxide or iridium, and can keep better performance after frequent and repeated anode reversal of a fuel cell, thereby obviously improving the anode tolerance performance of a membrane electrode. When the proportion of Pt is too high, the catalyst has poor anti-reversal performance, and when the proportion of Ir is too high, the performance after preparation into a battery is poor because Ir has no HOR activity.
2. The preparation method of the antipole catalyst provided by the invention is simple and can be prepared by only one-step thermal reduction method. The carbon nanotube carrier has wide sources, and the carbon nanotubes with excellent various performances are commercialized and have wide acquisition ways. The carbon nano tube is treated by the mixed acid, so that the carbon nano tube forms more defects and functional groups and can better anchor metal atoms. In the method provided by the invention, ethylene glycol is simultaneously used as a solvent and a reducing agent, and can fully reduce precursors of Pt and Ir after refluxing for 6-12h under a relatively mild condition, and formed particles are relatively dispersed. When the reflux time is less than 6h, the reduction of the precursors of Pt and Ir is insufficient, the percentage content of the metal on the prepared catalyst is far less than the calculated amount, and when the reflux time is more than 12h, the metal particles on the catalyst carrier are seriously aggregated, so that the active site of the metal can not be completely exposed, and the catalytic activity is reduced.
3. The positive electrode catalyst of the proton exchange membrane fuel cell with the PtIr alloy as the active component has higher initial performance and anti-reversal performance.
4. Compared with the prior art, the anode catalyst layer prepared by the anti-reversal catalyst has the advantages that the steps are simple, a reversal inhibitor does not need to be mixed during preparation, and the agglomeration degree of the physical mixed iridium oxide is reduced.
In conclusion, the anti-reversal catalyst provided by the invention is simple in preparation method, excellent in initial performance and excellent in reversal tolerance, and can still maintain higher cell performance after frequent reversal, so that the anti-reversal catalyst can be popularized and used in the field of fuel cells.
Drawings
FIG. 1 is an XRD pattern of a portion of a PtIr/CNT catalyst made in accordance with the present invention;
FIG. 2 shows Pt prepared in example 1 of the present invention3Ir1TEM image of/CNT catalyst;
FIG. 3 is a TEM image of the agglomerated Ir particles after the reversal of the polarity in comparative example 3 according to the present invention;
FIG. 4 shows commercial Pt/C and Pt/CNT and Pt prepared by the present invention3Ir1CV curve of/CNT;
FIG. 5 shows commercial Pt/C and Pt/CNT and Pt prepared according to the present invention3Ir1OER Performance of/CNTA curve;
FIG. 6 shows commercial Pt/C and Pt/CNT and Pt prepared by the present invention3Ir1ECSA decay profile after accelerated decay test of CNT catalyst;
FIG. 7 is an I-V curve before and after 50 reverse polarity tests for a cell made with commercial Pt/C;
FIG. 8 is an I-V curve before and after 50 reverse polarity tests for a Pt/CNT fabricated cell made according to the present invention;
FIG. 9 shows Pt prepared according to the present invention3Ir1I-V curves of the battery prepared by the CNT before and after 50 times of reverse polarity tests;
FIG. 10 shows Pt prepared according to the present invention3Ir1TEM images of/CNT catalyst before and after reversal;
fig. 11 is an I-V curve before and after 50 reverse polarity tests for a cell prepared with the catalyst described in comparative example 3.
Detailed Description
Example 1
1g of carbon nano tube is dispersed in concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 3:1 (total volume is 200mL), the used concentrated sulfuric acid and concentrated nitric acid are commercial concentrated sulfuric acid and concentrated nitric acid, stirring and heating are carried out for 3h at 60 ℃, a large amount of deionized water is added, suction filtration and washing are carried out until the pH value is 7.0, and the mixture is placed into an oven for drying.
Adding 155mg of acid-treated carbon nano tube into a three-neck flask, adding 20mL of deionized water and 20mL of ethylene glycol, performing ultrasonic dispersion for 30min, and then adding 3.7mg/mL of chloroplatinic acid and 2.7mg/mL of iridium trichloride to ensure that the molar ratio of Pt to Ir is 3:1, total metal molar weight of 0.2mM, then introducing nitrogen to remove oxygen for 30min, and then adjusting the pH to above 10 with 2mol/L NaOH solution. Moving the three-neck flask to 140 ℃ oil bath for heating for 10h, keeping nitrogen introduced during the heating, naturally cooling to room temperature after the reaction is finished, adding 3mol/L hydrochloric acid solution to adjust the pH of the solution to be below 2.0, stirring for 30min at room temperature, repeatedly washing with deionized water, drying in a drying oven in vacuum, and carefully grinding to obtain the catalyst Pt3Ir1/CNT。
Mixing Pt3Ir1Preparation of CNT into Anode catalyst layer: catalyst, isopropanol and 5% Nafion solutionPreparing catalyst slurry, performing ultrasonic homogenization, and spraying the catalyst slurry to two sides of a Nafion 211 membrane, wherein the mass ratio of isopropanol to the catalyst is 60: 1, the I/C ratio in the slurry was 0.7.
Assembling the anode catalyst layer into a fuel cell, wherein the anode catalyst loading is 0.2mgcm-2The cathode catalyst used by the fuel cell is 70 percent Pt/C (calculated by noble metal), and the Pt loading amount in the cathode catalyst layer is 0.4mg cm-2。
FIG. 1 is an XRD pattern of PtIr/CNT catalysts prepared according to the present invention with different molar ratios of Pt and Ir, and it can be seen that the prepared catalysts have typical diffraction peaks of alloys of Pt and Ir.
Taking example 1 as an example, FIG. 2 shows Pt prepared in example 1 of the present invention3Ir1TEM image of/CNT catalyst, PtIr alloy has average particle size of 1.69nm and no significant agglomeration on carbon nanotubes.
FIG. 4 shows commercial Pt/C and Pt/CNT and Pt prepared by the present invention3Ir1CV curves for/CNT, from which it can be seen that Pt prepared by the present invention3Ir1The peak current of the hydrogen adsorption area of the/CNT catalyst is obviously higher than that of the commercialized Pt/C and Pt/CNT, and the electrochemical active area is higher.
FIG. 5 shows commercial Pt/C and Pt/CNT and Pt prepared according to the present invention3Ir1OER performance curve of/CNT. The PEMFC can generate a reverse pole phenomenon in the running process under a complex working condition, the anode potential can reach 1.5V or more at the moment, carbon corrosion is caused, and the carbon corrosion can be relieved if the water electrolysis reaction is promoted. Therefore, the better the OER performance of the anode catalyst, the better the membrane electrode tolerance in the counter-electrode case. It can be seen that Pt prepared by the present invention3Ir1The OER activity of the/CNT catalyst is higher than that of commercial Pt/C and Pt/CNT, so that the membrane electrode prepared by the catalyst prepared by the invention has better antipolar tolerance performance.
FIG. 6 shows commercial Pt/C and Pt/CNT and Pt prepared according to the present invention3Ir1ECSA decay Pattern after accelerated decay test of/CNT catalyst, wherein the accelerated decay test is performed in 0.5M sulfuric acid solution saturated with nitrogen, and CV scan range is 0.8E1.6V, sweep rate 50mV/s, sweep 200 cycles. It can be seen that Pt is after accelerated decay test3Ir1The ECSA attenuation of the/CNT was only 19.6%, while the commercial Pt/C attenuation was 54.7%.
Therefore, the catalyst provided by the invention can effectively improve the counter electrode tolerance of the membrane electrode.
FIGS. 7-9 show commercial Pt/C and Pt/CNT and Pt prepared according to the present invention, respectively3Ir1Battery performance diagram assembled by anode catalyst layer prepared by CNT (carbon nano tube), wherein the cathode catalyst is 70% of Pt/C, and the Pt loading in the cathode catalyst layer is 0.4mg cm-2The loading capacity of the anode catalyst is 0.2mgcm-2(in terms of noble metal). The fuel cell was initiated 50 times for reversal and the IV curves before and after reversal were tested, as can be seen in FIG. 7, at 1000mA cm after 50 reversal tests-2At current density, the cell performance of the commercial Pt/C catalyst assembly decayed by 23.5%, the cell performance of the Pt/CNT assembly decayed by 10.2% after the reverse pole, compared to the Pt of example 13Ir1The performance of the battery prepared by the CNT is only attenuated by 4.1 percent after the reverse pole.
FIG. 10 shows Pt prepared according to the present invention3Ir1TEM images of the/CNT catalyst before and after reversal, from which Pt can be seen3Ir1The difference of the/CNT catalyst before and after the anode reversal is not obvious, and FIG. 3 is a TEM image of an Ir particle part agglomerated after the anode reversal, and the image shows that the Ir particle is agglomerated obviously, so that the PtIr alloy avoids agglomeration caused by directly adding iridium, can keep better performance after the fuel cell is subjected to frequent anode reversal for multiple times, and obviously improves the anode tolerance performance of the membrane electrode.
Therefore, the anti-reversal catalyst provided by the invention can effectively improve the durability of the frequent reversal of the fuel cell.
Example 2
1g of carbon nano tube is dispersed in concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 3:1, stirring and heating at 60 ℃ for 3h, adding a large amount of deionized water, filtering and washing until the pH is 7.0, and drying in an oven.
Treating with 155mg of acidAdding the carbon nano tube into a three-neck flask, and adding 20mL of deionized water and 20mL of ethylene glycol according to the volume ratio of 1: 1 (total 40mL), ultrasonically dispersing for 30min, and then adding 3.7mg/mL chloroplatinic acid and 2.7mg/mL iridium trichloride so that the molar ratio of Pt and Ir is 2: 1, chloroplatinic acid and iridium trichloride in a total metal molar amount of 0.2mM, then introducing nitrogen to remove oxygen for 30min, and then adjusting the pH to be more than 10 by using a 2mol/L NaOH solution. Moving the three-neck flask to 140 ℃ oil bath for heating for 10h, keeping nitrogen introduced during the heating, naturally cooling to room temperature after the reaction is finished, adding 3mol/L hydrochloric acid solution to adjust the pH of the solution to be below 2.0, stirring for 30min at room temperature, repeatedly washing with deionized water, drying in a drying oven in vacuum, and carefully grinding to obtain the catalyst Pt2Ir1/CNT。
From Pt2Ir1The procedure of preparing anode catalyst layer from/CNT is the same as that of example 1, and the anode catalyst layer is assembled into a fuel cell, and the cathode catalyst used in the fuel cell is the same as that of example 1.
Example 2 was taken as an example, due to the catalyst Pt prepared in example 22Ir1the/CNT increases the content of Ir and has OER performance superior to Pt3Ir1The ECSA decay was only 15.3% after accelerated decay testing for the/CNT, and the voltage loss after reverse polarity testing for the cell assembled with the catalyst prepared in example 2 was 6.8%, much less than commercial Pt/C.
Example 3
1g of carbon nano tube is dispersed in concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 3:1, stirring and heating at 60 ℃ for 3h, adding a large amount of deionized water, filtering and washing until the pH is 7.0, and drying in an oven.
Adding 155mg of acid-treated carbon nano tube into a three-neck flask, and adding 20mL of deionized water and 20mL of ethylene glycol according to the volume ratio of 1: 1 (total 40mL), ultrasonically dispersing for 30min, and then adding 3.7mg/mL chloroplatinic acid and 2.7mg/mL iridium trichloride so that the molar ratio of Pt and Ir is 6: 1, chloroplatinic acid and iridium trichloride in a total metal molar amount of 0.2mM, then introducing nitrogen to remove oxygen for 30min, and then adjusting the pH with a 2mol/L NaOH solutionTo above 10. Moving the three-neck flask to 140 ℃ oil bath for heating for 10h, keeping nitrogen introduced during the heating, naturally cooling to room temperature after the reaction is finished, adding 3mol/L hydrochloric acid solution to adjust the pH of the solution to be below 2.0, stirring for 30min at room temperature, repeatedly washing with deionized water, drying in a drying oven in vacuum, and carefully grinding to obtain the catalyst Pt6Ir1/CNT。
From Pt6Ir1The procedure of preparing anode catalyst layer from/CNT is the same as that of example 1, and the anode catalyst layer is assembled into a fuel cell, and the cathode catalyst used in the fuel cell is the same as that of example 1.
Example 3, example 3 prepared Pt6Ir1The ECSA decay after accelerated decay testing for the/CNT catalyst was 27.8%, and the voltage loss after reverse polarity testing for the cell assembled with the catalyst prepared in example 3 was 8.9%, less than the commercial Pt/C.
Comparative example 1
The only difference from example 1 is that the anode catalyst used in comparative example 1 was commercialized Pt/C.
Comparative example 2
The difference from example 1 is that the catalyst support used in comparative example 2 was acid-treated CNT, the acid treatment step was the same as in example 1, the active metal was Pt, no Ir was present, and the preparation method was the same, which is compared with fig. 3 to 5. The catalyst prepared in comparative example 2 had an ECSA decay of 31.8% after accelerated decay test, although less than commercial Pt/C, the ECSA decay after accelerated decay test was much greater than Pt due to the lack of Ir addition3Ir1A CNT. The cell assembled with the catalyst prepared in comparative example 2 had a voltage loss after the reverse polarity test of 10.2%, which was greater than examples 1, 2, 3, but less than the commercial Pt/C. It is shown that the addition of Ir plays an important role in catalyst stability.
Comparative example 3
The difference from example 1 is that the anode catalyst used in the cell of comparative example 3 was Pt/CNT physically mixed commercial Ir black prepared according to the present invention (Ir content was the same as in example 1), the electrode cathode catalyst was prepared at 70% Pt/C, and the Pt loading in the cathode catalyst layer was 0.4mg cm-2The anode catalyst layer is 0.2mg cm-2Pt/CNT (as noble metal) +0.05mg cm-2Ir black. After the reverse polarity test, the voltage loss was 6.9% at 1000 Watts, which is greater than that of example 1. Comparative example 3 shows that the anti-reverse catalyst using PtIr alloy as an active component of the present application has excellent anti-reverse performance, as compared to example 1, in which the amount of Pt is increased and the voltage loss is increased in the case where the amount of Ir is the same.
Comparative example 4
The difference from example 1 is only that in the prepared PtIr/CNT catalyst, the molar ratio of Pt to Ir is 1: 2.
comparative example 5
The difference from example 1 is only that in the prepared PtIr/CNT catalyst, the molar ratio of Pt to Ir is 8: 1.
comparative example 6
The only difference from example 1 is that the catalyst prepared is Ir/CNT, where the Ir loading is the same as the total loading of Pt and Ir in example 1.
TABLE 1 Performance data for anode catalysts of the examples and comparative examples
In conclusion, the PtIr/CNT catalyst provided by the invention can enable the PEMFC to still maintain higher catalytic activity under the condition of frequent reversal, and improves the reversal tolerance of the membrane electrode, thereby improving the durability of the PEMFC, and being capable of being popularized and used in the field of fuel cells.
Claims (10)
1. The proton exchange membrane fuel cell anti-reversal anode catalyst is characterized in that the anti-reversal anode catalyst takes a PtIr alloy as an active component and a carbon nano tube as a carrier, and the molar ratio of Pt to Ir is 6-1: 1.
2. the antipole anode catalyst according to claim 1, wherein the particle size of the PtIr alloy is 1.6 to 1.9nm, and the mass ratio of the active component to the carrier is 0.1 to 0.8: 1; the molar ratio of Pt to Ir is 3: 1.
3. The antipole anode catalyst according to claim 2, wherein the mass specific gravity of the active component and the carrier is 0.2 to 0.7: 1.
4. A method for preparing the catalyst according to claim 1, wherein the PtIr alloy is prepared by a polyol reflux method, and the method for preparing the catalyst comprises the steps of:
pretreatment of the vector
The method comprises the following steps: weighing carbon nanotubes, adding the carbon nanotubes into a mixed solution of concentrated sulfuric acid and concentrated nitric acid sold in the market, and stirring to obtain a mixed solution 1;
step two: diluting the mixed solution 1 with deionized water, filtering and washing until the pH value of the filtrate is neutral, and then drying filter residues to obtain the carrier;
preparation of PtIr/CNT catalyst
Step three: ultrasonically dispersing the carrier in a mixed solution of ethylene glycol and water, adding precursors of Pt and Ir, introducing nitrogen to remove oxygen, adjusting the pH to be more than 10 by using a NaOH solution, refluxing for 6-12h at 120-160 ℃, then adding hydrochloric acid to adjust the pH to be less than 2, stirring, centrifugally washing a product by using deionized water, and drying in vacuum to obtain the catalyst.
5. The preparation method according to claim 4, wherein in the first step, the stirring temperature is 60-130 ℃; the stirring time is 1-6 h.
6. The method according to claim 4, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 5: 1-1: 5.
7. the preparation method according to claim 4, wherein the Pt precursor is one of chloroplatinic acid, potassium chloroplatinate, and platinum acetylacetonate; the Ir precursor is one of chloro-iridic acid, iridium trichloride and iridium acetylacetonate.
8. The method according to claim 4, wherein the volume ratio of ethylene glycol to water in step three is 1: 3-3: 1.
9. a fuel cell anti-reverse anode catalyst layer, wherein the anode catalyst layer comprises the anti-reverse anode catalyst of claim 1, and the anode catalyst layer does not require an additional anti-reverse additive.
10. Use of the fuel cell anti-reverse anode catalytic layer according to claim 9 in a fuel cell.
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