CN109713330B - Fuel cell anode catalyst and preparation method thereof - Google Patents
Fuel cell anode catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a fuel cell anode catalyst, which comprises a carrier and an active material loaded on the carrier; the active material comprises an inner core and a micropore selective permeation layer coated on the surface of the inner core, wherein the inner core is made of noble metal or alloy nano particles thereof, and the micropore selective permeation layer is made of oxide or hydroxide of the noble metal or alloy thereof. The invention also provides a preparation method of the fuel cell anode catalyst.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a material and a method for improving carbon monoxide tolerance of an anode catalyst in a fuel cell.
Background
The fuel cell is a novel sustainable, efficient and environment-friendly energy conversion device. Fuel cells can directly convert the chemical energy of a fuel into electrical energy. Hydrogen is the fuel used by the anode of the fuel cell, and the current major source of hydrogen comes from the reforming of natural gas, which inevitably contains carbon monoxide (CO) at a certain concentration. CO in fuel can severely poison the anode catalyst in a fuel cell, so how to improve CO tolerance of the anode catalyst is of great importance for practical application of the fuel cell.
The existing anode catalyst mainly depends on two strategies for improving CO poisoning resistance: 1) a second binary relatively oxygen-philic metal (such as Ru) is introduced on the surface of the platinum, and the oxidation of CO in an adsorption state on the surface of the platinum is promoted by oxygen-containing species on the surface of the second binary metal, so that the CO poisoning resistance is improved. 2) Pt is compounded with metal oxides such as WO2, MoO2, TiO2 and the like, and the adsorption strength of CO on the surface of platinum is weakened by utilizing the interaction between the oxides and the platinum, so that the CO poisoning resistance is improved. Because the hydrogen oxidation potential of the fuel cell is very low, CO is difficult to oxidize and remove at the moment, and the interaction between the CO and the surface of the noble metal is very strong, so that the CO is difficult to weaken and not adsorb. Thus, both of the current strategies have limited poisoning resistance, and 100ppm of CO impurities in hydrogen fuel can rapidly poison the surface and deactivate the anode catalyst.
Chinese patent CN1418725, in-situ chemical reduction homogeneous deposition method is used to prepare carbon nanotube supported alloy poisoning resistant catalysts such as PtRu, PtSn, PtRuSn, etc. Chinese patent CN101436669, adopts CO2 supercritical fluid to deposit metal organic compound on the conductive carrier, and then reduces to obtain 1-4nm Pt-M alloy catalyst for resisting CO poisoning. Chinese patent CN1832234, a pt au nano catalyst loaded on oxide is synthesized by wet chemical method as an anti-CO poisoning catalyst applied in fuel cells. U.S. Pat. No. 4, 6007934, Emmanuel Auer et al, utilizes low temperature liquid phase formaldehyde to reduce Pt salt and Ru salt step by step or simultaneously, and then low temperature drying to prepare a carbon supported catalyst containing both metals Pt and Ru, both metals being present in a non-alloyed state but highly dispersed on the supported carbon, which has better CO poisoning resistance than commercial PtRu/C catalysts. U.S. Pat. No. 4, 5939220, Alec Gordon Gunner and others, prepared PtCoMo/C and other ternary alloy catalysts by a liquid phase precipitation deposition method, as anode catalysts of proton exchange membrane fuel cells, have certain CO poisoning resistance. As can be seen from the previously published patents, current hydrogen oxidation catalysts resistant to CO poisoning remain primarily Pt-based metal alloy catalysts with limited resistance to poisoning. According to the literature Ehteshami s.m.m.; jia Q,; halder a.; chan s.h.; mukerjee S.Electrochimica Acta 2013,107,155. the platinum-based alloy catalyst in the prior research still has difficulty in meeting the requirement of CO poisoning resistance in the fuel cell, and only 20ppm of CO in the fuel can cause that the activity of various platinum-based alloy catalysts is lost by more than 50% within 1 hour.
Disclosure of Invention
The present invention provides a fuel cell anode catalyst and a preparation method thereof, which can effectively solve the above problems.
The invention is realized by the following steps:
a fuel cell anode catalyst comprising a carrier and an active material supported on the carrier; the active material comprises an inner core and a micropore selective permeation layer coated on the surface of the inner core, wherein the inner core is made of noble metal or alloy nano particles thereof, and the micropore selective permeation layer is made of oxide or hydroxide of the noble metal or alloy thereof.
As a further improvement, the noble metal or alloy thereof nanoparticles are platinum, ruthenium, palladium or platinum-ruthenium alloy nanoparticles.
As a further improvement, the noble metal or the alloy nanoparticles thereof are ruthenium nanoparticles, and the material of the microporous selective permeation layer is hydrated ruthenium oxide.
As a further improvement, the microporous selective permeation layer is used for ensuring the hydrogen to pass through and blocking carbon monoxide.
As a further improvement, the material of the support is carbon, an inorganic oxide, an inorganic nitride or an inorganic carbide.
The invention also provides a preparation method of the fuel cell anode catalyst, which comprises the following steps:
s1, dissolving a precursor of the noble metal or the alloy thereof in water, adding a carrier, mixing, adjusting the pH value to be neutral, and heating to 110-130 ℃ for reaction for 4-8 h;
s2, centrifugally washing after reaction, drying in vacuum, grinding, heating the prepared powder to 140-160 ℃, and continuously reacting for 4-8 hours to obtain carrier/hydrated metal oxide nanoparticles;
s3, performing electrochemical reduction on the prepared carrier/hydrated metal oxide nanoparticles, and controlling the reduction degree to obtain a target catalyst, wherein the target catalyst comprises a carrier and an active material loaded on the carrier; the active material comprises an inner core and a micropore selective permeation layer coated on the surface of the inner core, wherein the inner core is made of noble metal or alloy nano particles thereof, and the micropore selective permeation layer is made of oxide or hydroxide of the noble metal or alloy thereof.
As a further improvement, the precursor of the noble metal or the alloy thereof is hydrated metal oxide nanoparticles of platinum, ruthenium, palladium or platinum-ruthenium alloy.
As a further improvement, the precursor of the noble metal or the alloy thereof is ruthenium trichloride hydrate.
As a further improvement, in step S3, the step of electrochemically reducing the prepared support/hydrated metal oxide nanoparticles comprises:
s31, preparing the prepared carrier/hydrated metal oxide nano particles into ink, and carrying out cyclic voltammetry scanning between 0-0.5V until the curve is stable, wherein the ink comprises 5mg of carrier/hydrated metal oxide nano particles, 0.1m L of 5 wt% nafion solution, and 0.5m L of solvent water and isopropanol respectively.
As a further improvement, in step S1, the reaction is carried out by heating to 118-122 ℃ for 5.5-6.5 h.
The invention has the beneficial effects that: through constructing the selective permeation layer on the surface of the noble metal catalyst, poisoning species such as CO with larger molecular size can be effectively prevented from approaching the catalytic activity center, and hydrogen with smaller molecular size can still permeate the barrier layer to reach the catalytic activity center below the barrier layer and be oxidized. The catalyst can stably work in hydrogen with high concentration CO (100-10000ppm), and can remarkably reduce voltage loss caused by poisoning during the work of a fuel cell using a simply purified reformed gas as an anode fuel, thereby improving the work stability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic representation of the i-t curves of example 1 and comparative experiments A-C.
FIG. 2 is a schematic representation of the i-t curves of examples 1-4.
FIG. 3 is a schematic representation of the i-t curves of examples 4-7.
FIG. 4 is the PEMFC test i-t curve of example 8 and comparative experiment D.
FIG. 5 is a support on TiO2Ru @ RuO of2And (5) a transmission electron microscope characterization image of the catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Referring to fig. 5, a fuel cell anode catalyst includes a carrier and an active material supported on the carrier; the active material comprises an inner core and a micropore selective permeation layer coated on the surface of the inner core, wherein the inner core is made of noble metal or alloy nano particles thereof, and the micropore selective permeation layer is made of oxide or hydroxide of the noble metal or alloy thereof. The micropore selective permeation layer is used for ensuring hydrogen to pass through and blocking carbon monoxide.
As a further improvement, the noble metal or alloy thereof nanoparticles are platinum, ruthenium, palladium or platinum-ruthenium alloy nanoparticles. Preferably, the noble metal or the alloy nanoparticles thereof are ruthenium nanoparticles, and the material of the microporous selective permeation layer is hydrated ruthenium oxide.
The material of the carrier is carbon, inorganic oxide, inorganic nitride or inorganic carbide. Preferably: inorganic oxides such as titanium dioxide.
The invention also provides a preparation method of the fuel cell anode catalyst, which comprises the following steps:
s1, dissolving a precursor of the noble metal or the alloy thereof in water, adding a carrier, mixing, adjusting the pH value to be neutral, and heating to 110-130 ℃ for reaction for 4-8 h;
s2, centrifugally washing after reaction, drying in vacuum, grinding, heating the prepared powder to 140-160 ℃, and continuously reacting for 4-8 hours to obtain carrier/hydrated metal oxide nanoparticles;
s3, performing electrochemical reduction on the prepared carrier/hydrated metal oxide nanoparticles, and controlling the reduction degree to obtain a target catalyst, wherein the target catalyst comprises a carrier and an active material loaded on the carrier; the active material comprises an inner core and a micropore selective permeation layer coated on the surface of the inner core, wherein the inner core is made of noble metal or alloy nano particles thereof, and the micropore selective permeation layer is made of oxide or hydroxide of the noble metal or alloy thereof.
In step S1, the precursor of the noble metal or the alloy thereof may be hydrated metal oxide nanoparticles of platinum, ruthenium, palladium or a platinum-ruthenium alloy. Preferably, the precursor of the noble metal or the alloy thereof is ruthenium trichloride hydrate. The material of the carrier is carbon, inorganic oxide, inorganic nitride or inorganic carbide. Preferably: inorganic oxides such as titanium dioxide.
In addition, preferably, the reaction is carried out for 5.5 to 6.5 hours by heating to 118 to 122 ℃. In this example, the reaction was carried out for 6 hours by heating to 120 ℃.
In step S2, the reaction is preferably continued for 5.5 to 6.5 hours by heating to 148 to 152 ℃. In this example, the reaction was carried out for 6 hours by heating to 150 ℃.
In step S3, the step of electrochemically reducing the prepared support/hydrated metal oxide nanoparticles comprises:
s31, preparing the prepared carrier/hydrated metal oxide nano particles into ink, and carrying out cyclic voltammetry scanning between 0-0.5V until the curve is stable, wherein the ink comprises 5mg of carrier/hydrated metal oxide nano particles, 0.1m L of 5 wt% nafion solution, and 0.5m L of solvent water and isopropanol respectively.
Example 1
Dispersing 50mg of ruthenium trichloride hydrate and 50mg of titanium dioxide nanoparticles in 20m L water, performing ultrasonic treatment for 3 hours, adjusting the pH value of the solution to 7, controlling the temperature to 120 ℃, reacting for 6 hours, then placing the obtained black precipitate in an air atmosphere, heating for 6 hours at 150 ℃ to obtain a prefabricated material, preparing the prefabricated material into ink, wherein the ink comprises the following components of 5mg of the prefabricated material, 0.1m L of 5 wt% nafion solution, and 0.5m L of solvent water and isopropanol respectively, performing ultrasonic treatment on the ink under the condition of ice water bath until the ink is uniformly dispersed, uniformly dropping the ink prepared by 20 mu L on a rotary disc electrode, performing cyclic voltammetry scanning at 0-0.5V until the curve is stable, and completing activation.
The hydrogen oxidation stability test for tolerance to carbon monoxide was then carried out in an atmosphere containing one percent carbon monoxide, with the potential controlled at 0.1V. The test was performed in a 0.5M sulfuric acid solution using a reversible hydrogen electrode as reference and a carbon plate as counter electrode.
Example 2
Dispersing 50mg of ruthenium trichloride hydrate and 50mg of titanium carbide nanoparticles in 20m L water, performing ultrasonic treatment for 3 hours, adjusting the pH value of the solution to 7, controlling the temperature to 120 ℃, reacting for 6 hours, then placing the obtained black precipitate in an air atmosphere, heating for 6 hours at 150 ℃ to obtain a prefabricated material, preparing the prefabricated material into ink, wherein the ink comprises the following components of 5mg of the prefabricated material, 0.1m L of 5 wt% nafion solution and 0.5m L of solvent water and isopropanol respectively, performing ultrasonic treatment on the ink under the condition of ice-water bath until the ink is uniformly dispersed, uniformly dropping the ink prepared by 20 mu L on a rotary disc electrode, performing cyclic voltammetry scanning at 0-0.5V until the curve is stable, and completing activation.
The hydrogen oxidation stability test for tolerance to carbon monoxide was then carried out in an atmosphere containing one percent carbon monoxide, with the potential controlled at 0.1V. The test was performed in a 0.5M sulfuric acid solution using a reversible hydrogen electrode as reference and a carbon plate as counter electrode.
Example 3
Dispersing 50mg of ruthenium trichloride hydrate and 20mg of titanium nitride in 20m L water, performing ultrasonic treatment for 3 hours, adjusting the pH value of the solution to 7, controlling the temperature to 120 ℃, reacting for 6 hours, then placing the obtained black precipitate in an air atmosphere, heating for 6 hours at 150 ℃ to obtain a prefabricated material, preparing the prefabricated material into ink, wherein the ink comprises the following components of 5mg of the prefabricated material, 0.1m L of 5 wt% nafion solution and 0.5m L of solvent water and isopropanol respectively, performing ultrasonic treatment on the ink under the condition of ice-water bath until the ink is uniformly dispersed, uniformly dropping the ink prepared by 20 mu L on a rotary disc electrode, performing cyclic voltammetry scanning at 0-0.5V until the curve is stable, and completing activation.
The hydrogen oxidation stability test for tolerance to carbon monoxide was then carried out in an atmosphere containing one percent carbon monoxide, with the potential controlled at 0.1V. The test was performed in a 0.5M sulfuric acid solution using a reversible hydrogen electrode as reference and a carbon plate as counter electrode.
Example 4
Dispersing 50mg of ruthenium trichloride hydrate and 20mg of C in 20m L water, performing ultrasonic treatment for 3 hours, adjusting the pH value of the solution to 7, controlling the temperature to 120 ℃, reacting for 6 hours, then placing the obtained black precipitate in an air atmosphere, heating for 6 hours at 150 ℃ to obtain a prefabricated material, preparing the prefabricated material into ink, wherein the ink comprises the following components of 5mg of the prefabricated material, 0.1m L of 5 wt% nafion solution, 0.5m L of solvent water and isopropanol respectively, performing ultrasonic treatment on the ink under the condition of ice-water bath until the ink is uniformly dispersed, uniformly dropping the ink prepared by 20 mu L on a rotary disc electrode, performing cyclic voltammetry scanning at 0-0.5V until the curve is stable, and completing activation.
The hydrogen oxidation stability test for tolerance to carbon monoxide was then carried out in an atmosphere containing one percent carbon monoxide, with the potential controlled at 0.1V. The test was performed in a 0.5M sulfuric acid solution using a reversible hydrogen electrode as reference and a carbon plate as counter electrode.
Example 5
Dispersing 50mg of ruthenium trichloride, 50mg of chloroplatinic acid and 20mg of C in 20m L water, performing ultrasonic treatment for 3 hours, adjusting the pH value of the solution to 7, controlling the temperature to 120 ℃, reacting for 6 hours, then placing the obtained black precipitate in an air atmosphere, heating at 150 ℃ for 6 hours to obtain a prefabricated material, preparing the prefabricated material into ink, wherein the ink comprises the following components of 5mg of the prefabricated material, 0.1m L of 5 wt% nafion solution and 0.5m L of solvent water and isopropanol respectively, performing ultrasonic treatment on the ink under the condition of ice-water bath until the ink is uniformly dispersed, uniformly dropping the ink prepared by 20 mu L on a rotary disc electrode, performing cyclic voltammetry scanning at 0-0.5V until the curve is stable, and completing activation.
The hydrogen oxidation stability test for tolerance to carbon monoxide was then carried out in an atmosphere containing one percent carbon monoxide, with the potential controlled at 0.1V. The test was performed in a 0.5M sulfuric acid solution using a reversible hydrogen electrode as reference and a carbon plate as counter electrode.
Example 6
Dispersing 50mg of chloroplatinic acid and 20mg of C in 20m L water, performing ultrasonic treatment for 3 hours, adjusting the pH value of a solution to 7, controlling the temperature to 120 ℃, reacting for 6 hours, then placing the obtained black precipitate in an air atmosphere, heating for 6 hours at 150 ℃ to obtain a prefabricated material, preparing the prefabricated material into ink, wherein the ink comprises the following components of 5mg of the prefabricated material, 0.1m L of 5 wt% nafion solution and 0.5m L of solvent water and isopropanol respectively, performing ultrasonic treatment on the ink under the condition of ice-water bath until the ink is uniformly dispersed, uniformly dropping the ink prepared by 20 mu L on a rotary disc electrode, performing cyclic voltammetry scanning at 0-0.5V until the curve is stable, and completing activation.
The hydrogen oxidation stability test for tolerance to carbon monoxide was then carried out in an atmosphere containing one percent carbon monoxide, with the potential controlled at 0.1V. The test was performed in a 0.5M sulfuric acid solution using a reversible hydrogen electrode as reference and a carbon plate as counter electrode.
Example 7
Dispersing 50mg of chloropalladate and 20mg of C in 20m L water, performing ultrasonic treatment for 3 hours, adjusting the pH value of a solution to 7, controlling the temperature to 120 ℃, reacting for 6 hours, then placing the obtained black precipitate in an air atmosphere, heating for 6 hours at 150 ℃ to obtain a prefabricated material, preparing the prefabricated material into ink, wherein the ink comprises the following components of 5mg of the prefabricated material, 0.1m L of 5 wt% nafion solution and 0.5m L of solvent water and isopropanol respectively, performing ultrasonic treatment on the ink under the condition of ice-water bath until the ink is uniformly dispersed, uniformly dropping the ink prepared by 20 mu L on a rotary disc electrode, performing cyclic voltammetry scanning at 0-0.5V until the curve is stable, and completing activation.
The hydrogen oxidation stability test for tolerance to carbon monoxide was then carried out in an atmosphere containing one percent carbon monoxide, with the potential controlled at 0.1V. The test was performed in a 0.5M sulfuric acid solution using a reversible hydrogen electrode as reference and a carbon plate as counter electrode.
Example 8
With Ru @ RuO2Carrying out battery test on the catalyst;
preparing a cathode gas diffusion electrode, wherein the ink comprises the following components: 20mg of Pt/C catalyst; 0.1ml of 5 wt% nafion solution; 1ml of solvent (isopropanol + water); placing the cathode ink under the ice-water bath condition for ultrasonic treatment for 10 min; and preparing a gas diffusion electrode (GDS) by adopting a dripping coating mode, wherein the loading capacity of the final cathode catalyst layer Pt is 2mg cm < -2 >.
The anode gas diffusion electrode was prepared in a similar manner to the cathode, with an ink composition of 20mg Ru @ RuO20.22m L of 5 wt% nafion solution, 0.2m L of deionized water and 0.4m L of isopropanol, placing the cathode ink under the condition of ice-water bath for 10min of ultrasound, preparing a gas diffusion electrode (GDS) by adopting a dropping coating mode, and finally loading the anode metal to 2mg cm-2；
Hot-pressing the prepared gas diffusion electrode and the nafion membrane to form a membrane electrode (the hot-pressing condition is 135 ℃, 3MPa and 2 min); and (3) carrying out single cell test on the prepared membrane electrode assembled battery under the following test conditions: oxidizing agent: non-humidified oxygen (100 sccm); fuel: h2Or H2100ppm CO balance gas (100 sccm); battery temperature: 60 ℃;
comparative experiment:
comparative experiment A
A commercial Pt/C catalyst purchased from Alfa aesar is prepared into ink for electrochemical test, wherein the ink comprises 1mg of catalyst, 0.1M L of 5 wt% nafion solution, L of solvent water and isopropanol which are 0.5M respectively, the ink is placed under the condition of ice-water bath and is subjected to ultrasonic treatment until the ink is uniformly dispersed, the ink prepared by 10 mu L is uniformly dripped on the surface of a rotating disk electrode to perform cyclic voltammetry scanning between 0 and 0.5V until the curve is stable and the activation is completed, then, the potential is controlled to be 0.1V in the atmosphere containing one percent of carbon monoxide to perform a hydrogen oxidation stability test for resisting the carbon monoxide, the test is performed in 0.5M sulfuric acid solution, a reversible hydrogen electrode is used as a reference, and a carbon sheet is used as a counter electrode.
Comparative experiment B
A commercial PtRu/C catalyst purchased from Alfa aesar is prepared into ink for electrochemical test, the ink comprises 1mg of catalyst, 0.1m L of 5 wt% nafion solution, L of solvent water and isopropanol, the ink is placed under the condition of ice-water bath and is subjected to ultrasonic treatment until the ink is uniformly dispersed, the ink prepared by 10 mu L is uniformly dropped on the surface of a rotating disk electrode to perform cyclic voltammetry scanning between 0 and 0.5V until the curve is stable, and the activation is completed.
The hydrogen oxidation stability test for tolerance to carbon monoxide was then carried out in an atmosphere containing one percent carbon monoxide, with the potential controlled at 0.1V. The test was performed in a 0.5M sulfuric acid solution using a reversible hydrogen electrode as reference and a carbon plate as counter electrode.
Comparative experiment C
A commercial Ru black catalyst purchased from Alfa aesar was formulated into an ink for electrochemical testing consisting of 1mg of catalyst, 0.1m L of 5 wt% nafion solution, L of solvent water and isopropyl alcohol each 0.5m, the ink was placed in an ice-water bath and sonicated until uniformly dispersed, 10 μ L of the resulting ink was dropped uniformly onto the surface of a rotating disk electrode and cyclic voltammetric scanning was performed between 0 and 0.5V until the curve stabilized, and activation was completed.
The hydrogen oxidation stability test for tolerance to carbon monoxide was then carried out in an atmosphere containing one percent carbon monoxide, with the potential controlled at 0.1V. The test was performed in a 0.5M sulfuric acid solution using a reversible hydrogen electrode as reference and a carbon plate as counter electrode.
Comparative experiment D
Commercial Pt/C anodes were used as cell test controls;
preparing a cathode gas diffusion electrode, wherein the ink comprises the following components: 20mg of Pt/C catalyst; 0.1ml of 5 wt% nafion solution; 1ml of solvent (isopropanol + water); placing the cathode ink under the ice-water bath condition for ultrasonic treatment for 10 min; preparing a gas diffusion electrode (GDS) by adopting a dripping coating mode, wherein the loading capacity of a cathode catalyst layer Pt is 2mg cm < -2 > finally;
the preparation method of the anode gas diffusion electrode is similar to that of the cathode, the ink composition is 20mg of Pt/C (40 wt% of Pt, Johnson Matthey), 0.22m L of 5 wt% nafion solution, 0.2m of deionized water L, 0.4m of isopropanol L, the cathode ink is placed under the condition of ice-water bath for ultrasonic treatment for 10min, the gas diffusion electrode (GDS) is prepared in a dropping coating mode, and the loading capacity of the final anode metal is 2mg cm-2；
Hot-pressing the prepared gas diffusion electrode and the nafion membrane to form a membrane electrode (the hot-pressing condition is 135 ℃, 3MPa and 2 min); and (3) carrying out single cell test on the prepared membrane electrode assembled battery under the following test conditions: oxidizing agent: non-humidified oxygen (100 sccm); fuel: h2Or H2100ppm CO balance gas (100 sccm); battery temperature: at 60 ℃.
And (3) analysis:
FIG. 1 is a schematic representation of the i-t curves of example 1 and comparative experiments A-C.
In the figure: curve 1 is the example 1, using a support on TiO2Ru @ RuO of21% CO/H corresponding to catalyst used as anode catalyst2The i-t curve diagram of the medium working stability test. Curve A is the 1% CO/H corresponding to using Pt/C as the anode catalyst2The i-t curve diagram of the medium working stability test. Curve B is the 1% CO/H corresponding to using PtRu/C as the anode catalyst2The i-t curve diagram of the medium working stability test. Curve C is 1% CO/H corresponding to the use of Ru black as anode catalyst2The i-t curve diagram of the medium working stability test. As can be seen from the figure, the catalyst of the present case can stably operate also in hydrogen gas containing CO at a high concentration.
FIG. 2 is a schematic representation of the i-t curves of examples 1-4. In the figure: curve 1 is the example 1, using a support on TiO2Ru @ RuO of21% CO/H corresponding to catalyst used as anode catalyst2Testing an i-t curve chart by using medium working stability; curve 2 is an example 2, using Ru @ RuO supported on TiC 21% CO/H corresponding to catalyst used as anode catalyst2Testing an i-t curve chart by using medium working stability; curve 3 is an example 3, using Ru @ RuO on TiN 21% CO/H corresponding to catalyst used as anode catalyst2Testing an i-t curve chart by using medium working stability; curve 4 is an example 4, using Ru @ RuO on C 21% CO/H corresponding to catalyst used as anode catalyst2The i-t curve diagram of the medium working stability test. As can be seen from the figure, the catalysts of examples 2-4 have slightly reduced tolerance in hydrogen containing a high concentration of CO.
FIG. 3 is a schematic representation of the i-t curves of examples 4-7. In the figure: curve 4 (example 4), using Ru @ RuO on C 21% CO/H corresponding to catalyst used as anode catalyst2Testing an i-t curve chart by using medium working stability; curve 5 (example 5), using PtRu @ RuO on C 21% CO/H corresponding to catalyst used as anode catalyst2Testing an i-t curve chart by using medium working stability; curve 6 (example 6), using Pt @ RuO on C 21% CO/H corresponding to catalyst used as anode catalyst2Testing an i-t curve chart by using medium working stability; curve 7 (example 7), using Pd @ RuO on C 21% CO/H corresponding as anode catalyst2The i-t curve diagram of the medium working stability test. It can be seen from the figure that the new strategy proposed by the scheme can have general poisoning resistance enhancement effect on different noble metal catalysts.
FIG. 4 is the PEMFC test i-t curve of example 8 and comparative experiment D.
In the figure: curve 8 (example 8), i-t plot of stability test operating in a PEMFC with 100ppm CO/H2 of anode fuel using a Ru @ RuO2 catalyst supported on TiO2 as anode catalyst; curve D (comparative experiment D), stability test i-t plot for operation in PEMFC with 100ppm CO/H2 for anode fuel using Pt/C catalyst as anode catalyst. It can be seen from the figure that the catalyst can be applied to a fuel cell system in practical application, and can maintain the activity of 80% even after co is introduced, and can keep the activity for 10 hours.
FIG. 5 is a transmission electron microscopy characterization of the Ru @ RuO2 catalyst supported on TiO2 showing the metal, surface oxide layer, support, and total three phases.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method of preparing a fuel cell anode catalyst, comprising the steps of:
s1, dissolving a precursor of the noble metal or the alloy thereof in water, adding a carrier, mixing, adjusting the pH value to be neutral, and heating to 110-130 ℃ for reaction for 4-8 h;
s2, centrifugally washing after reaction, drying in vacuum, grinding, heating the prepared powder to 140-160 ℃, and continuously reacting for 4-8 hours to obtain carrier/hydrated metal oxide nanoparticles;
s3, performing electrochemical reduction on the prepared carrier/hydrated metal oxide nanoparticles, and controlling the reduction degree to obtain a target catalyst, wherein the target catalyst comprises a carrier and an active material loaded on the carrier; the active material comprises an inner core and a micropore selective permeation layer coated on the surface of the inner core, wherein the inner core is made of noble metal or alloy nano particles thereof, and the micropore selective permeation layer is made of oxide or hydroxide of the noble metal or alloy thereof.
2. The method according to claim 1, wherein the precursor of the noble metal or the alloy thereof is a hydrated metal oxide nanoparticle of platinum, ruthenium, palladium or a platinum-ruthenium alloy.
3. The method according to claim 1, wherein the precursor of the noble metal or the alloy thereof is ruthenium trichloride hydrate.
4. The method of claim 3, wherein in step S3, the step of electrochemically reducing the prepared support/hydrated metal oxide nanoparticles comprises:
s31, preparing the prepared carrier/hydrated metal oxide nano particles into ink, and carrying out cyclic voltammetry scanning between 0-0.5V until the curve is stable, wherein the ink comprises 5mg of carrier/hydrated metal oxide nano particles, 0.1m L of 5 wt% nafion solution, and 0.5m L of solvent water and isopropanol respectively.
5. The method of claim 4, wherein in step S1, the reaction is carried out by heating to 118-122 ℃ for 5.5-6.5 h.
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| CN110354848B (en) * | 2019-05-24 | 2021-05-07 | 深圳欧赛技术有限公司 | PtRu catalyst and preparation method and application thereof |
| CN110600755B (en) * | 2019-09-06 | 2021-03-19 | 宁波柔创纳米科技有限公司 | Coating method of carbon carrier material loaded with metal catalyst and battery |
| CN111193043B (en) * | 2020-01-07 | 2021-06-01 | 北京化工大学 | Anode catalyst for proton exchange membrane fuel cell and synthetic method thereof |
| CN111628187A (en) * | 2020-05-05 | 2020-09-04 | 江苏大学 | Carbon-supported ruthenium oxide catalyst and preparation method thereof |
| CN114899427B (en) * | 2022-05-20 | 2024-02-27 | 厦门大学 | Fuel cell anode catalyst and preparation method and application thereof |
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