CN114361486A - High-performance low-cost fuel cell anti-reversal anode catalyst and preparation method thereof - Google Patents
High-performance low-cost fuel cell anti-reversal anode catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a high-performance low-cost fuel cell anti-reversal anode catalyst and a preparation method thereofxIr(1‑x)P2Or PtxRu(1‑x)P2The carrier is a nitrogen-phosphorus double-doped foam carbon film, the content of noble metal in the anode anti-reversal catalyst is low, the cost can be greatly reduced, an anti-reversal substance does not need to be additionally added, and the preparation method is simple.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a high-performance low-cost fuel cell anti-reversal anode catalyst and a preparation method thereof.
Background
When the fuel cell is started or stopped, the load is changed rapidly, impurities block a gas mass transfer channel or water flooding occurs, hydrogen supply on the anode side is insufficient, and normal hydrogen oxidation reaction cannot be carried out. To maintain charge balance, oxidation reactions of other species of the anode catalytic layer occur. Firstly, water in the catalyst layer is electrolyzed, after a period of time, carbon carriers in the catalyst are corroded, the anode potential is gradually higher than the cathode potential, and the anode potential is reversed, so that the catalytic performance of the catalyst is reduced, and even a generated local high-temperature point can burn through a proton exchange membrane to form a short circuit. Aiming at the problem of the counter electrode, the mainstream method is to add a counter electrode resisting substance (mainly comprising noble metals Ru, Ir and oxides thereof) capable of catalyzing oxygen to be separated out into an anode catalyst layer rich in noble metals, inhibit the electrolysis of water, and protect the performance of a fuel cell and the service life of a membrane electrode. For example, publication No. CN111029599B discloses a fuel cell anti-reversal catalyst and a preparation method thereof, wherein the catalyst is an iridium oxide and niobium-doped titanium dioxide nano-catalyst, which can effectively relieve carbon carrier corrosion and platinum particle agglomeration growth during the reversal of the anode side of a fuel cell, but the catalyst provided by the invention is an anti-reversal additive, has no anode hydrogen catalysis effect, and needs to be compounded into an anode catalyst by means of high temperature and the like, so that the formed anti-reversal anode catalyst is not uniformly distributed, and the iridium oxide agglomeration phenomenon is easy to occur in the catalysis process. In addition, the oxides are relatively poor in conductivity, which affects the performance of the fuel cell at high current densities. For example, patent publication No. CN113178582A provides a proton exchange membrane fuel cell anti-reverse-pole anode PtIr/CNT catalyst, in the catalyst, PtIr alloy is an active component, a carbon nanotube is a carrier, and the molar ratio of Pt to Ir is 6-1: 1, the anode catalyst does not need to be additionally added with an anti-reversal additive, so that agglomeration caused by directly adding iridium oxide or iridium is avoided. But the mass proportion of the active component and the carrier in the catalyst is 0.2-0.7: 1, the content of noble metal is high, and the cost is high. In addition, the acting force between the PtIr alloy and the carbon nanotube is not strong, and the alloy is easy to fall off or agglomerate in the catalytic process, resulting in the reduction of catalytic performance.
Therefore, in the prior art, the problems of cost and anti-reversal of the anode catalyst are solved, and a short plate exists, which is shown in that the anti-reversal catalyst is easy to agglomerate, the anti-reversal capability is reduced, the power supply capability and the service life of a fuel cell are influenced, and the hydrogen oxidation catalytic performance and the anti-reversal performance cannot be considered on the basis of realizing low cost, so that the preparation technology of the anti-reversal anode catalyst needs to be further improved, the content of noble metal is reduced, and meanwhile, high catalytic activity and anti-reversal capability are maintained.
Disclosure of Invention
The invention provides a high-performance low-cost fuel cell anti-reversal anode catalyst and a preparation method thereof, aiming at the defects of the prior art.
The method is realized by the following technical scheme:
the anti-reverse anode catalyst for the fuel cell with high performance and low cost comprises Pt as an active componentxIr(1-x)P2Or PtxRu(1-x)P2X is the mole fraction of the noble metal (0.6-0.8), and the carrier is a nitrogen-phosphorus double-doped foam carbon film, namely NPC.
The mass content of noble metal in the anti-reverse anode catalyst is less than or equal to 11 percent and is not zero.
The high-performance low-cost fuel cell anti-reversal anode catalyst is prepared by adopting a sacrificial template method and calcining at high temperature, and comprises the following steps:
1) mixing 2mL of phosphorus-containing compound, 0.03-0.06 g of platinum-containing compound, 0.01-0.02 g of counter electrode raw material, 60mg of melamine and 250mg of silicon dioxide nanospheres in 100mL of deionized water, and stirring for 1h to prepare a uniformly mixed solution;
2) drying the mixed solution into a solid in an environment of 80-100 ℃, and calcining in an argon atmosphere;
3) and (3) after calcining, etching the silicon dioxide nanospheres by using an HF solution, and centrifugally washing to obtain the anode anti-reversal catalyst.
The phosphorus-containing compound is one of hydroxyethylidene diphosphate and phytic acid.
The platinum-containing compound is one of platinum chloride and chloroplatinic acid.
The counter electrode raw material is one of iridium chloride, chloroiridic acid and ruthenium chloride.
The calcination temperature is 850-900 ℃, the heating rate is 5 ℃/min, and the holding time is 2 h.
The volume of HF and water in the HF solution is 1: 10.
the time for etching the silicon dioxide nanospheres is 8-12 hours.
The anode antipole catalyst is used for preparing a membrane electrode in a proton exchange membrane fuel cell.
Has the advantages that:
the anode anti-reverse electrode catalyst provided by the invention has low content of noble metal, can greatly reduce the cost, does not need to additionally add anti-reverse electrode substances, and has a simple preparation method.
According to the invention, the hydrogen reduction catalyst platinum and the oxygen are utilized to precipitate the catalyst Ir (or Ru) and the P to form compound particles which are uniformly dispersed on the nitrogen and phosphorus double-doped three-dimensional carbon film, the electronic interaction between the particles and the carrier can coordinate with the catalytic reaction, so that the catalytic activity is improved, and the compound particles can be stably anchored on the carrier, so that the particles are effectively prevented from falling off and agglomerating in the catalytic process.
Meanwhile, because the catalyst contains oxygen evolution substances, the catalyst can keep better performance when the fuel cell is in reverse polarity, remarkably improves the reverse polarity resistance of the membrane electrode, and prolongs the service life of the membrane electrode.
Drawings
FIG. 1 is a scanning electron micrograph of an anode antipodal catalyst in example 1;
FIG. 2 is a graph comparing polarization curves in Experimental example 1;
FIG. 3 is a graph showing a comparison of anti-reversal properties in Experimental example 1.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A high-performance low-cost fuel cell anti-reversal anode catalyst comprises the following steps:
1) sequentially adding 2mL of phytic acid, 0.03g of chloroplatinic acid, 0.01g of chloroiridic acid, 60mg of melamine and 250mg of silicon dioxide nanospheres into 100mL of deionized water, and stirring for 1h to prepare a mixed solution;
2) putting the mixed solution into a drying oven at 80 ℃ to be dried into a solid, putting the solid into a tubular furnace under the protection of argon, heating to 880 ℃ at the speed of 5 ℃/min, and keeping for 2 hours;
3) etching the calcined product for 12h by using 10mL of HF solution with solute volume ratio of 1:10, removing silicon dioxide nanospheres, centrifugally washing, and vacuum drying overnight to obtain anode antipole catalyst Pt0.7Ir0.3P2@NPC；
Meanwhile, in this example, Pt was further introduced0.7Ir0.3P2@ NPC was prepared as an anode catalyst layer: catalyst Pt0.7Ir0.3P2Preparing the @ NPC, isopropyl alcohol and 5% Nafion solution into catalytic slurry, uniformly performing ultrasonic treatment, spraying the catalytic slurry to the two sides of a proton exchange membrane with the thickness of 12 microns by using an ultrasonic spraying machine, wherein the loading amount of noble metal of the catalyst is 0.2mg/cm2(ii) a The anode catalyst layer is assembled into a membrane electrode, the cathode catalyst layer adopts 60% Pt/C, and the Pt loading capacity is 0.35mg/cm2；
This example uses ICP to measure Pt as anode anti-counter catalyst0.7Ir0.3P2The loading of noble metals in @ NPC resulted as follows: the total loading of noble metals (Pr and Ir) was 5.3 wt%;
the anode antipole catalyst is characterized by a scanning electron microscope, and the result is shown in figure 1, and can be known as follows: the phosphide particles are uniformly distributed on the bubble-shaped carbon film, the particle size is small, and no obvious agglomeration phenomenon exists on the carbon film.
Comparative example 1
A fuel cell anode catalyst is prepared by the following steps:
(1) sequentially adding 2mL of phytic acid, 0.03g of chloroplatinic acid, 60mg of melamine and 250mg of silicon dioxide nanospheres into 100mL of deionized water, and stirring for 1h to prepare a mixed solution;
(2) drying the mixed solution in a drying oven at 80 ℃, putting the dried mixed solution into a tubular furnace under the protection of argon, heating the mixed solution to 880 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours;
(3) placing the calcined substance in a plastic bottle, and etching with 10mLHF solution (solute volume ratio of 1: 10) for 12 h;
(4) centrifugally washing the product with deionized water, and drying in vacuum overnight to obtain the anode anti-reverse-polarity catalyst PtP2@NPC；
(5) To PtP2@ NPC was prepared as an anode catalyst layer: preparing a catalyst, isopropanol and a 5% Nafion solution into catalytic slurry, ultrasonically and uniformly spraying the catalytic slurry to two sides of a proton exchange membrane with the thickness of 12 mu m by using an ultrasonic spraying machine, wherein the loading capacity of noble metal of the catalyst is 0.2mg/cm2；
(6) The anode catalyst layer is assembled into a membrane electrode, the cathode catalyst layer adopts 60% Pt/C, and the Pt loading capacity is 0.35mg/cm2。
Comparative example 2
A fuel cell anode catalyst is prepared by the following steps:
(1) a commercial 20% Pt/C was prepared as the anode catalytic layer: preparing Pt/C, isopropanol and 5% Nafion solution into catalytic slurry, ultrasonically and uniformly spraying the catalytic slurry to two sides of a proton exchange membrane with the thickness of 12 mu m by using an ultrasonic spraying machine,pt loading of 0.25mg/cm2；
(2) The anode catalyst layer is assembled into a membrane electrode, the cathode catalyst layer adopts 60% Pt/C, and the Pt loading capacity is 0.35mg/cm2。
Experimental example 1
And (3) testing the membrane electrode performance:
the prepared membrane electrode (example 1, comparative example 2) was subjected to electrochemical performance testing: the working temperature of the battery is 80 ℃, the gas humidity is 100%, the metering ratio of the cathode and the anode is 2 and 1.8 respectively, and the back pressure is 120 kPa; FIG. 2 shows Pt prepared in example 10.7Ir0.3P2Polarization curves of @ NPC and commercial Pt/C, it can be seen from FIG. 2 that the prepared anode anti-reversal catalyst is 1800.12mA/cm2The catalyst can reach 0.653V, and the catalytic performance is superior to that of commercial Pt/C.
And (3) testing the anti-reversal performance:
the prepared membrane electrode (example 1, comparative example 1) was subjected to a test for anti-reversal properties: the working temperature of the battery is 80 ℃, and the gas flow of the cathode and the anode is 0.5L/min; FIG. 3 shows Pt prepared according to the present invention0.7Ir0.3P2@ NPC and PtP2The anti-reversal capability curve of @ NPC, as can be seen from FIG. 3, the catalyst without addition of the anti-reversal raw material Ir has substantially no anti-reversal capability, while Pt with addition of the anti-reversal catalyst0.7Ir0.3P2The @ NPC has good anti-reversal ability.
Example 2
A high-performance low-cost fuel cell anti-reversal anode catalyst comprises the following steps:
1) sequentially adding 2mL of phytic acid, 0.04g of platinum chloride, 0.01g of ruthenium chloride, 60mg of melamine and 250mg of silicon dioxide nanospheres into 100mL of deionized water, and stirring for 1h to prepare a uniform mixed solution;
2) putting the mixed solution into a drying oven at 80 ℃ to be dried into a solid, putting the solid into a tubular furnace under the protection of argon, heating to 900 ℃ at the speed of 5 ℃/min, and keeping for 2 hours;
3) etching the calcined product with 10mL of HF solution with solute volume ratio of 1:10 for 8h, removing the silicon dioxide nanospheres, and then removing the silicon dioxide nanospheresCentrifugally washing, vacuum drying and standing overnight to obtain the anode antipole catalyst Pt0.8Ru0.2P2@NPC；
Meanwhile, in this example, Pt was further introduced0.8Ru0.2P2@ NPC was prepared as an anode catalyst layer: catalyst Pt0.8Ru0.2P2Preparing the @ NPC, isopropyl alcohol and 5% Nafion solution into catalytic slurry, uniformly performing ultrasonic treatment, spraying the catalytic slurry to the two sides of a proton exchange membrane with the thickness of 12 microns by using an ultrasonic spraying machine, wherein the loading amount of noble metal of the catalyst is 0.2mg/cm2(ii) a The anode catalyst layer is assembled into a membrane electrode, the cathode catalyst layer adopts 60% Pt/C, and the Pt loading capacity is 0.35mg/cm2。
The SEM characterization result is not different from that of example 1; the membrane electrode performance test shows that the prepared anode antipole catalyst is 1800.24mA/cm2The pressure can reach 0.654V; the anti-reversal performance test shows that the prepared anode anti-reversal catalyst has good anti-reversal capability.
Example 3
A high-performance low-cost fuel cell anti-reversal anode catalyst comprises the following steps:
1) sequentially adding 2mL of hydroxyethylidene diphosphonic acid, 0.03g of platinum chloride, 0.02g of iridium chloride, 60mg of melamine and 250mg of silicon dioxide nanospheres into 100mL of deionized water, and stirring for 1h to prepare a uniformly mixed solution;
2) putting the mixed solution into a drying oven at 80 ℃ to be dried into a solid, putting the solid into a tubular furnace under the protection of argon, heating to 900 ℃ at the speed of 5 ℃/min, and keeping for 2 hours;
3) etching the calcined product for 9h by using 10mL of HF solution with solute volume ratio of 1:10, removing silicon dioxide nanospheres, centrifugally washing, and vacuum drying overnight to obtain anode antipole catalyst Pt0.6Ir0.4P2@NPC；
Meanwhile, in this example, Pt was further introduced0.6Ir0.4P2@ NPC was prepared as an anode catalyst layer: catalyst Pt0.6Ir0.4P2Preparing the catalyst slurry from @ NPC, isopropanol and 5% Nafion solution, uniformly ultrasonic treating, and mixingSpraying the mixture to two sides of a proton exchange membrane with the thickness of 12 mu m by an acoustic spraying machine, wherein the loading capacity of the catalyst noble metal is 0.2mg/cm2(ii) a The anode catalyst layer is assembled into a membrane electrode, the cathode catalyst layer adopts 60% Pt/C, and the Pt loading capacity is 0.35mg/cm2。
The SEM characterization result is not different from that of example 1; the membrane electrode performance test shows that the prepared anode antipole catalyst is 1799.89mA/cm2The pressure can reach 0.651V; the anti-reversal performance test shows that the prepared anode anti-reversal catalyst has good anti-reversal capability.
Example 4
A high-performance low-cost fuel cell anti-reversal anode catalyst comprises the following steps:
1) sequentially adding 2mL of hydroxyethylidene diphosphonic acid, 0.04g of chloroplatinic acid, 0.01g of chloroiridic acid, 60mg of melamine and 250mg of silicon dioxide nanospheres into 100mL of deionized water, and stirring for 1h to prepare a mixed solution;
2) putting the mixed solution into a drying oven at 80 ℃ to be dried into a solid, putting the solid into a tubular furnace under the protection of argon, heating to 850 ℃ at the speed of 5 ℃/min, and keeping for 2 hours;
3) etching the calcined product for 8 hours by using 10mL of HF solution with solute volume ratio of 1:10, removing silicon dioxide nanospheres, centrifugally washing, and vacuum drying overnight to obtain anode antipole catalyst Pt0.8Ru0.2P2@NPC；
Meanwhile, in this example, Pt was further introduced0.8Ru0.2P2@ NPC was prepared as an anode catalyst layer: catalyst Pt0.8Ru0.2P2Preparing the @ NPC, isopropyl alcohol and 5% Nafion solution into catalytic slurry, uniformly performing ultrasonic treatment, spraying the catalytic slurry to the two sides of a proton exchange membrane with the thickness of 12 microns by using an ultrasonic spraying machine, wherein the loading amount of noble metal of the catalyst is 0.2mg/cm2(ii) a The anode catalyst layer is assembled into a membrane electrode, the cathode catalyst layer adopts 60% Pt/C, and the Pt loading capacity is 0.35mg/cm2。
The SEM characterization result is not different from that of example 1; the membrane electrode performance test shows that the prepared anode antipole catalyst is 1799.79mA/cm2Can reach 0.655V; the anti-reversal performance test shows that the prepared anode anti-reversal catalyst has good anti-reversal capability.
Example 5
A high-performance low-cost fuel cell anti-reversal anode catalyst comprises the following steps:
1) sequentially adding 2mL of phytic acid, 0.06g of platinum chloride, 0.02g of iridium chloride, 60mg of melamine and 250mg of silicon dioxide nanospheres into 100mL of deionized water, and stirring for 1h to prepare a mixed solution;
2) putting the mixed solution into a drying oven at 80 ℃ to be dried into a solid, putting the solid into a tubular furnace under the protection of argon, heating to 850 ℃ at the speed of 5 ℃/min, and keeping for 2 hours;
3) etching the calcined product for 8 hours by using 10mL of HF solution with solute volume ratio of 1:10, removing silicon dioxide nanospheres, centrifugally washing, and vacuum drying overnight to obtain anode antipole catalyst Pt0.7Ru0.3P2@NPC；
Meanwhile, in this example, Pt was further introduced0.7Ir0.3P2@ NPC was prepared as an anode catalyst layer: catalyst Pt0.7Ru0.3P2Preparing the @ NPC, isopropyl alcohol and 5% Nafion solution into catalytic slurry, uniformly performing ultrasonic treatment, spraying the catalytic slurry to the two sides of a proton exchange membrane with the thickness of 12 microns by using an ultrasonic spraying machine, wherein the loading amount of noble metal of the catalyst is 0.2mg/cm2(ii) a The anode catalyst layer is assembled into a membrane electrode, the cathode catalyst layer adopts 60% Pt/C, and the Pt loading capacity is 0.35mg/cm2。
The SEM characterization result is not different from that of example 1; the membrane electrode performance test shows that the prepared anode antipole catalyst is 1800.34mA/cm2The pressure can reach 0.656V; the anti-reversal performance test shows that the prepared anode anti-reversal catalyst has good anti-reversal capability.
Claims (10)
1. The high-performance low-cost fuel cell anti-reversal anode catalyst is characterized in that the active component of the anti-reversal anode catalyst is PtxIr(1-x)P2Or PtxRu(1-x)P2X is nobleThe metal mole fraction is 0.6-0.8, and the carrier is a nitrogen-phosphorus double-doped foam carbon film.
2. The anti-reverse anode catalyst for the fuel cell of high performance and low cost as claimed in claim 1, wherein the mass content of noble metal in the anti-reverse anode catalyst is less than or equal to 11% and is not zero.
3. The preparation method of the high-performance low-cost fuel cell anti-reversal anode catalyst according to claim 1, characterized in that the catalyst is prepared by high-temperature calcination by a sacrificial template method, and comprises the following steps:
1) mixing 2mL of phosphorus-containing compound, 0.03-0.06 g of platinum-containing compound, 0.01-0.02 g of counter electrode raw material, 60mg of melamine and 250mg of silicon dioxide nanospheres in 100mL of deionized water, and stirring for 1h to prepare a uniformly mixed solution;
2) drying the mixed solution into a solid in an environment of 80-100 ℃, and calcining in an argon atmosphere;
3) and (3) after calcining, etching the silicon dioxide nanospheres by using an HF solution, and centrifugally washing to obtain the anode anti-reversal catalyst.
4. The method of claim 3, wherein the phosphorus-containing compound is one of hydroxyethylidene diphosphate and phytic acid.
5. The method of claim 3, wherein the platinum-containing compound is one of platinum chloride and chloroplatinic acid.
6. The method of claim 3, wherein the counter-electrode raw material is one of iridium chloride, chloroiridic acid and ruthenium chloride.
7. The method for preparing the anti-reversal anode catalyst of the fuel cell with high performance and low cost according to claim 3, wherein the calcining temperature is 850-900 ℃, the heating rate is 5 ℃/min, and the holding time is 2 h.
8. The method of claim 3, wherein the volumes of HF and water in the HF solution are 1: 10.
9. the method for preparing the anti-reversal anode catalyst of the fuel cell with high performance and low cost as claimed in claim 3, wherein the time for etching the silicon dioxide nanospheres is 8-12 h.
10. The use of a high performance low cost fuel cell anti-bounce anode catalyst as defined in claim 1 for the preparation of a membrane electrode for a proton exchange membrane fuel cell.
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