CN117476960A - Nano porous Pt film, preparation method thereof and application thereof in fuel cell electrode - Google Patents

Nano porous Pt film, preparation method thereof and application thereof in fuel cell electrode Download PDF

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CN117476960A
CN117476960A CN202311825766.9A CN202311825766A CN117476960A CN 117476960 A CN117476960 A CN 117476960A CN 202311825766 A CN202311825766 A CN 202311825766A CN 117476960 A CN117476960 A CN 117476960A
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film
nano porous
electrode
nanoporous
fuel cell
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CN117476960B (en
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姜在勇
何佳
王开丽
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Weifang University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/92Metals of platinum group
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605Porous electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1004Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The invention belongs to the technical field of application of electrode materials, and particularly relates to a nano porous Pt film, a preparation method thereof and application thereof in a fuel cell electrode. The preparation method of the nano porous Pt film comprises the following steps: adopting an electrochemical displacement method, taking Ag foil as an initial raw material, and placing the Ag foil into a precursor Pt solution for reaction to prepare an AgPt alloy film attached with silver chloride; placing the AgPt alloy film attached with the silver chloride crystal into an electrolyte accelerator for impregnation to obtain an AgPt alloy film; placing the AgPt alloy film in a dilute nitric acid solution for dealloying treatment; and then placing the porous Pt film in a tubular furnace which is communicated with a reducing atmosphere for heat treatment, thus obtaining the nano porous Pt film. The preparation method of the nano porous Pt film provided by the invention has mild conditions; the prepared Pt film has the advantages of easily-adjusted aperture, low cost and high electrocatalytic activity; the high-performance high-power high-performance fuel cell is applied to the fuel cell electrode, and the output power and the performance stability output of the cell are improved.

Description

Nano porous Pt film, preparation method thereof and application thereof in fuel cell electrode
Technical Field
The invention belongs to the technical field of application of electrode materials, and particularly relates to a nano porous Pt film, a preparation method thereof and application thereof in a fuel cell electrode.
Background
The proton exchange membrane fuel cell technology is a rapidly developed green energy technology, and has been applied to the aspects of automobiles, heavy engineering machinery, distributed power stations and the like at present. However, during the preparation process, the noble metal Pt catalyst has high catalytic performance but at the same time causes high cost of the proton exchange membrane fuel cell system, which is more than twice that of the internal combustion engine. Therefore, reducing Pt loading and developing metal films for use in proton exchange membrane fuel cell electrodes are key technological approaches to improve their cost competitiveness.
The nano porous metal film is a self-supporting metal material with a nano porous structure, and has extremely high specific surface area, so that the nano porous metal film has huge application prospect in the technical fields of electrocatalysis, biosensing, surface Raman enhancement and the like. In recent years, the research of application of nano porous metal as an electrocatalyst in fuel cells has become a new leading field. Compared to conventional carbon supported catalytic layers, nanoporous metal thin film electrodes have demonstrated dramatic structural and performance advantages: firstly, the interior of the nano porous metal is provided with a large number of three-dimensional mutually communicated nanoscale pores and frameworks, so that the nano porous metal has the characteristics of conductivity, ductility and the like of the metal, has the characteristics of nano materials such as small-size effect, surface effect, quantum size effect, quantum tunneling effect and the like, is not only an excellent electrode material, but also can be used as a surface functionalized electrode carrier to customize a composite functional material so as to adapt to different electrocatalytic reactions; secondly, as a non-carbon supported electrode material without a binder, the catalyst sites on the clean surface are combined with the carrier by virtue of strong metal bonds, so that the conductivity of the catalyst in the membrane electrode is greatly improved and the structural stability is enhanced; thirdly, the interconnected catalyst framework and the open-ended adjustable pore structure provide effective channels for proton conduction and oxygen and water transmission in the fuel cell, respectively, and provide abundant possibility for construction of high-performance membrane electrodes.
The nano porous gold film and Pt atoms are compounded to form a 'core-shell' structure, so that the nano porous gold film has a good application prospect on a fuel cell membrane electrode. The prior art mainly adopts a chemical reduction method and an electrochemical deposition method to prepare the low Pt nano porous film electrode taking gold as a substrate. The chemical reduction method is to prepare the nano porous Pt film electrode by controlling a certain reaction temperature and time to generate oxidation-reduction reaction by using the standard electrode potential difference between the substrate atoms and the Pt metal ions as driving force. For example, CN106816614a discloses a dense platinum monoatomic layer catalytic electrode for catalyzing a fuel cell electrode reaction and a preparation method thereof, firstly, a dealloying method is adopted to obtain a nano porous gold film, then the nano porous gold film is transferred to one side of a glassy carbon electrode or a Nafion film, and Pt atoms are deposited on the surface of the nano porous gold film by combining electrochemical and chemical reduction methods with the nano porous gold film as a substrate, so that a nano porous gold film electrode covered by a surface dense Pt monolayer is formed, and compared with a commercial Pt/C catalyst, the nano porous gold film electrode shows higher activity in an oxygen reduction test, but citric acid is adopted as a surfactant, which causes the problems of pore structure blockage of the nano porous film and organic matter pollution on the surface of the catalyst in the preparation process.
The method of combining electrochemical deposition with displacement reaction can prepare uniform Pt atomic layer catalytic electrode, but the preparation process needs to be performed finely, because the copper monoatomic layer is easily oxidized in the electrode transfer process, the Pt monoatomic layer is incomplete, and the catalytic activity and the structural stability of the catalyst electrode are further affected. For example, CN101332425a discloses a preparation method for uniformly depositing Pt monoatomic layer on the inner surface of a nano porous gold film by using under-potential deposition, and dealloying the AuAg alloy film by using concentrated nitric acid to obtain the nano porous gold film; in a three-electrode system, a nano-porous gold film is used as a working electrode, a carbon rod is used as a counter electrode, saturated calomel is used as a reference electrode, and a layer of copper atoms is uniformly deposited on the surface of the nano-porous gold under the action of underpotential in an electrolyte which is saturated by nitrogen and contains copper ion solution; and then the working electrode deposited with copper atoms is transferred to Pt metal salt with a certain concentration for free replacement, so that a thin film electrode with a monolayer of Pt atoms covered on the surface of the nano-porous gold is obtained, but the prepared nano-porous composite electrode is only suitable for operation in a three-electrode system and is not suitable for large-area thin film preparation, gold is used as a nuclear substrate, the price is high, the electrode cost is greatly increased, and the gold catalyst has very low electrocatalytic reaction activity or basically has no activity on most fuel cells.
Therefore, development of a nanoporous metal thin film material having high activity and low cost is urgent to promote further development of the nanoporous metal material in the field of fuel cell electrodes.
Disclosure of Invention
The invention aims to solve the technical problems of low electrocatalytic activity, poor stability and high substrate cost caused by small amount of supported active catalyst when the nano porous metal film is applied to a self-supporting electrode of a fuel cell due to the limitation of a metal substrate in the prior art, and provides a preparation method of the nano porous Pt film, which has the advantages of mild condition, simple flow and wide application range; the prepared nano porous Pt film has uniform thickness, easily-adjusted pore diameter, good stability, low cost and high electrocatalytic activity; the method is applied to the fuel cell electrode, and improves the output power of the cell and the stable output of the performance.
The preparation method of the nano porous Pt film comprises the following steps:
(1) Adopting an electrochemical displacement method, taking Ag foil as an initial raw material, placing the Ag foil into a precursor Pt solution for reaction to prepare an AgPt alloy film attached with silver chloride crystals, wherein the Pt loading capacity is 50 mu gcm -2 -100μgcm -2
(2) Placing the AgPt alloy film attached with the silver chloride crystal into an electrolyte accelerator for impregnation to obtain an AgPt alloy film;
(3) The AgPt alloy film is placed in a dilute nitric acid solution for dealloying treatment, and a nano Pt film with the atomic number ratio of Pt/Ag of 60/40-90/10 is obtained;
(4) And (3) placing the nano Pt film obtained in the step (3) in a tube furnace with a reducing atmosphere for heat treatment to obtain the nano porous Pt film.
The reaction temperature in the step (1) is 0-25 ℃ and the reaction time is 1-12h.
The precursor Pt solution in the step (1) is chloroplatinic acid solution or chloroplatinic acid solution, and the concentration of the precursor Pt solution is 1-30mmolL -1
The electrolyte accelerator in the step (2) is saturated NaCl solution, and the soaking time is 1-12h.
During the dealloying treatment of the step (3), the concentration of the dilute nitric acid solution is 10-50mmolL -1 The treatment temperature is 20-40 ℃ and the treatment time is 6-12h.
The reducing atmosphere in the step (4) is 5%H 2 /N 2 (volume ratio), the temperature of the heat treatment is 200-400 ℃ and the time is 2-10h.
A nano porous Pt film is prepared by the preparation method of the nano porous Pt film.
Use of a nanoporous Pt film in a fuel cell electrode: and (3) transferring the nano porous Pt film onto the Nafion film by a transfer printing method to form a self-supporting film electrode, and assembling the self-supporting film electrode into a fuel cell clamp.
Transferring the nano porous Pt film to a mica sheet or a PET substrate, and transferring the nano porous Pt film from the surface of the substrate to the surface of the Nafion film by adopting a hot pressing method.
The pressure applied by the hot pressing method is 2-15MPa, the temperature is 50-200 ℃ and the time is 0.5-10min.
Specifically, the preparation method of the nano porous Pt film comprises the following steps:
(1) Cutting Ag foil into small pieces, electrochemical displacement method, using standard electrode potential difference between Ag atom and Pt metal ion as driving force, using Ag foil as initial raw material, and placing in 1-30mmolL -1 The AgPt alloy film with silver chloride crystal attached is prepared by reacting the solution of chloroplatinic acid or the solution of chloroplatinic acid for 1 to 12 hours at the temperature of 0 to 25 ℃, and the Pt loading is 50 mu gcm -2 -100μgcm -2
(2) And (3) immersing the AgPt alloy film attached with the silver chloride crystals in a saturated NaCl solution for 1-12 hours, and gently removing the AgCl crystals generated on the surface of the film to obtain the AgPt alloy film which is completely free of impurities.
(3) Placing AgPt alloy film at 10-50mmolL -1 Dealloying is carried out for 6-12h at 20-40 ℃ in the dilute nitric acid solution to obtain the nano Pt film with the atomic number ratio of Pt/Ag of 60/40-90/10.
(4) Placing the nano Pt film obtained in the step (3) in a general 5%H way 2 /N 2 Heat treatment is carried out for 2-10h in a tube furnace of the reducing atmosphere at 200-400 ℃ to obtain the nano porous Pt film.
The prepared nano porous Pt film is subjected to electrochemical test: and (3) placing the nano porous Pt film in water, putting the glassy carbon electrode with the clean surface into the water to scoop the nano porous Pt film floating on the water surface, removing film materials around the glassy carbon electrode, drying the surface of the electrode coated with the film by blowing nitrogen, dripping Nafion film solution with the concentration of 0.05wt% to fix the film, and then performing three-dimensional electrochemical test. The electrochemical test can be directly applied to the battery after being qualified.
Specifically, the application of the nano porous Pt film in the fuel cell electrode: transferring the nano porous Pt film onto a mica sheet or a PET substrate, adopting a hot pressing method, applying pressure of 2-15MPa, temperature of 50-200 ℃ and time of 0.5-10min, transferring the nano porous Pt film from the substrate surface to the Nafion film surface, and assembling into a fuel cell clamp.
The nano porous Pt film of the invention adopts an electrochemical displacement method, utilizes the metal activity sequence difference of Ag and Pt to make two or four silver atoms and one Pt metal ion undergo a chemical displacement reaction to form a nano porous AgPt alloy film, and generates silver chloride crystals which are attached to the surface of the film, then uses saturated sodium chloride as electrolyte accelerator and excessive Cl - The ions and AgCl crystals form a complex, the solubility of AgCl is increased, so that forward decomposition of AgCl is accelerated, the AgCl crystals on the surface are thoroughly removed, the complex is placed in a dilute nitric acid solution for dealloying treatment, the Ag doping amount in an alloy film is controlled, a nano porous Pt film doped with a small amount of Ag atoms is obtained, and finally the complex is placed in a reducing atmosphere for heat treatment, so that the nano porous Pt film material with adjustable pore diameters is prepared.
Compared with the prior art, the invention has the following beneficial effects:
(1) The nano porous Pt film prepared by the method has the advantages of controllable Pt load capacity, uniform thickness, easily-adjusted pore diameter, strong binding force with a substrate, difficult falling, and capability of meeting the direct application requirement of the electrode of a fuel cell, and the nano porous Pt film serving as the electrode has an area size which can be customized according to the requirement.
(2) According to the preparation method of the nano porous Pt film, the pure Ag foil film is used as a substrate, and the three-dimensional nano porous Pt film with open pores is prepared by a method combining a chemical reduction method and a dealloying method, so that the preparation method has the characteristics of low cost, environment friendliness, simple steps and mild preparation conditions.
(3) The nano porous Pt film prepared by the invention is not only suitable for electrochemical catalytic half reaction, but also can be directly applied to a fuel cell membrane electrode, and can be used as a self-supporting electrode to improve the output power and stable performance output of a cell.
Drawings
FIG. 1 is a total Pt/Ag atomic ratio profile of the nano Pt film prepared in the step (3) of example 1.
Fig. 2 is a transmission electron microscope image of the nano Pt thin film prepared in step (3) of example 1.
FIG. 3 is a transmission electron microscopy image of the nanoporous Pt film after heat treatment in step (4) of example 1.
FIG. 4 is a cross-sectional scanning electron microscope image of the nanoporous Pt film after the heat treatment in step (4) of example 1.
Figure 5 is an XRD pattern of the product obtained in each of the four steps of example 1.
Fig. 6 is a cyclic voltammogram of the nanoporous Pt films prepared in example 1 and comparative example 1 in electrochemical tests.
FIG. 7 is an I-V plot of the nanoporous Pt film prepared in example 1 applied at 0.5bar and 1.5bar in a fuel cell.
Detailed Description
The invention will be further illustrated with reference to specific examples.
The reagents used in the following examples and comparative examples were all commercially available products. The purity of the adopted Ag foil is 99.9%, and the thickness is 100nm-120nm.
Example 1
The preparation method of the nano porous Pt film comprises the following steps:
(1) Cutting Ag foil into 2cm×2cm pieces, electrochemical displacement, washing with absolute ethanol at room temperature, drying at room temperature for 12 hr, and standing at 5mmolL -1 The solution is reacted for 2 hours at 0 ℃, the film is fished out and cleaned by clear water, and the solution is put into an ultrapure water tank to prepare the AgPt alloy film attached with silver chloride crystals, wherein the Pt loading capacity is 50 mu gcm -2
(2) And (3) immersing the AgPt alloy film attached with the silver chloride crystals in a saturated NaCl solution for 12 hours, gently removing the AgCl crystals generated on the surface of the film, and changing the surface of the film into black after the reaction is completed to obtain the AgPt alloy film.
(3) Placing AgPt alloy film at 10mmolL -1 Dealloying treatment is carried out for 6 hours at 30 ℃ to obtain the nano Pt film with the Pt/Ag atomic ratio of 65/35, the aperture is 2nm-5nm, the total spectrum diagram of the surface scanning of Pt and Ag elements is shown in figure 1, and the transmission electron microscope diagram is shown in figure 2.
(4) In order to regulate the aperture of the nano Pt film, the nano Pt film obtained in the step (3) is placed in a general 5%H way 2 /N 2 Heat treatment is carried out for 10 hours at 200 ℃ in a tube furnace of the reducing atmosphere, the pore diameter of the obtained nano porous Pt film is 5nm-10nm, and the transmission electron microscope diagram is shown in figure 3; the thickness is 70nm-80nm as shown in FIG. 4.
As shown in FIG. 5, from bottom to top, the XRD patterns of the Ag foil, the film after the replacement in the step (2), the film after the dilute nitric acid corrosion in the step (3) and the nano porous Pt film finally prepared in the step (4) are sequentially shown, and as can be seen from FIG. 5, the nano porous Pt film is successfully prepared by a chemical reduction method and a dealloying method, and the nano porous Pt film after the heat treatment can be analyzed to form the nano porous Pt film doped with a small amount of Ag atoms, and the nano porous Pt film has a three-dimensional continuous through hole structure, a porous framework is clear, the pore diameter is in the range of 5-20nm, and the size and the distribution are uniform.
Example 2
The preparation method of the nano porous Pt film comprises the following steps:
(1) Cutting Ag foil into 2.5cm×2.5cm pieces, electrochemical displacement, washing with absolute ethanol at room temperature, drying at room temperature for 12 hr, and standing at 10mmolL -1 The solution is reacted for 2 hours at 25 ℃, the film is fished out and cleaned by clear water and put into an ultrapure water tank to prepare the AgPt alloy film attached with silver chloride crystal, and the Pt loading capacity is 60 mu gcm -2
(2) And (3) immersing the AgPt alloy film attached with the silver chloride crystals in saturated NaCl solution for 10 hours, and gently removing the AgCl crystals generated on the surface of the film to obtain the AgPt alloy film which is complete and free of impurities.
(3) Placing AgPt alloy film at 20mmolL -1 Dealloying treatment is carried out for 8 hours at 30 ℃ to obtain the nano Pt film with the Pt/Ag atomic ratio of 80/20 and the aperture of 3nm-6nm.
(4) In order to regulate the aperture of the nano Pt film, the nano Pt film obtained in the step (3) is placed in a general 5%H way 2 /N 2 Heat treatment is carried out for 2 hours at 300 ℃ in a tube furnace of the reducing atmosphere to obtain the nano porous Pt film with the aperture of 5-10nm and the thickness of 75-85 nm.
Example 3
The preparation method of the nano porous Pt film comprises the following steps:
(1) Cutting Ag foil into 3cm×3cm pieces, electrochemical displacement, washing with absolute ethanol at room temperature, drying at room temperature for 12 hr, and standing at 30mmolL -1 The solution is reacted for 12 hours at 5 ℃, the film is fished out and cleaned by clear water and put into an ultrapure water tank, and the AgPt alloy film with silver chloride crystals attached is prepared with the Pt load of 100 mu gcm -2
(2) And (3) immersing the AgPt alloy film attached with the silver chloride crystals in a saturated NaCl solution for 8 hours, and gently removing the AgCl crystals generated on the surface of the film to obtain the AgPt alloy film which is complete and free of impurities.
(3) Placing AgPt alloy film at 50mmolL -1 Dealloying at 40deg.C for 12 hr to obtain a Pt/Ag atomic ratio of 90/10The aperture of the nano Pt film is 5nm-10nm.
(4) In order to regulate the aperture of the nano Pt film, the nano Pt film obtained in the step (3) is placed in a general 5%H way 2 /N 2 Heat treatment is carried out for 5 hours at 400 ℃ in a tube furnace of the reducing atmosphere to obtain the nano porous Pt film with the aperture of 15-20nm and the thickness of 85-95 nm.
Example 4
The preparation method of the nano porous Pt film comprises the following steps:
(1) Cutting Ag foil into 5cm×5cm pieces, electrochemical displacement, washing with absolute ethanol at room temperature, drying at room temperature for 12 hr, and standing at 1mmolL -1 The solution is reacted for 10 hours at 25 ℃, the film is fished out and cleaned by clear water, and the solution is put into an ultrapure water tank to prepare the AgPt alloy film attached with silver chloride crystal, wherein the Pt loading capacity is 50 mu gcm -2
(2) And (3) immersing the AgPt alloy film attached with the silver chloride crystals in a saturated NaCl solution for 1h, and gently removing the AgCl crystals generated on the surface of the film to obtain the AgPt alloy film which is complete and free of impurities.
(3) Placing AgPt alloy film at 30mmolL -1 Dealloying is carried out for 12 hours at 20 ℃ to obtain the nano Pt film with the Pt/Ag atomic ratio of 65/35 and the aperture of 2nm-5nm.
(4) In order to regulate the aperture of the nano Pt film, the nano Pt film obtained in the step (3) is placed in a general 5%H way 2 /N 2 Heat treatment is carried out for 3 hours at 350 ℃ in a tube furnace of the reducing atmosphere to obtain the nano porous Pt film with the aperture of 10-15nm and the thickness of 70-80 nm.
Comparative example 1
This comparative example was identical to the preparation method in steps (1), (2) and (4) in example 1, but the dissolution process of nitric acid to dissolve Ag atoms in step (3) was removed, and a nanoporous Pt film was obtained having a pore diameter of 1nm to 5nm and a thickness of 90nm to 100nm.
Comparative example 2
This comparative example was identical to the preparation in example 2, but step (1) was followedIs placed at 10mmolL -1 The reaction temperature in the chloroplatinic acid solution is replaced by 60 ℃, and the obtained nano porous Pt film has the aperture of 1nm-5nm and the thickness of 90nm-100nm.
Comparative example 3
The AgPt alloy film prepared by the prior art is used in a battery membrane electrode, and the specific preparation method comprises the following steps:
cutting Ag foil into 3cm×3cm pieces, electrochemical displacement, washing with absolute ethanol at room temperature, drying at room temperature for 12 hr, transferring Ag foil onto proton exchange membrane by hot pressing to obtain membrane electrode, directly serving as working electrode, and placing the electrode at 30mmolL -1 Chloroplatinic acid of (C) and 10mmol -1 In a three-electrode system (a prepared membrane electrode is a working electrode, a carbon rod is a counter electrode, and a saturated calomel electrode is a reference electrode) at the temperature of 5 ℃ in a potential interval of-0.2V to 0.6V, cyclic voltammetry scanning is used, and the scanning speed is 25mVs -1 And (3) Pt atoms are replaced, after the reaction is completed, the film is fished out and cleaned by clean water, and the film is put into an ultra-pure water tank for standby.
The electrochemical cyclic voltammetry replacement technology based on a three-electrode system is adopted in the comparative example, a nano porous Pt film can be obtained on a glassy carbon electrode, but the Ag foil on a proton exchange membrane cannot be subjected to replacement of Pt atoms, as can be seen from Table 1, an electronic path for connection cannot be formed between the electrode of comparative example 3 and the Ag foil, and electrochemical replacement cannot be performed, so that the preparation of the nano porous Pt film electrode cannot be realized by the method, and an applicable AgPt alloy film cannot be formed on the film electrode.
Application 1:
electrochemical tests were performed using the nanoporous Pt films prepared in example 1 and comparative example 1: performing cyclic voltammetry characterization, using a glassy carbon electrode of a nano porous Pt film as a working electrode, a saturated calomel electrode as a reference electrode and a carbon rod electrode as a counter electrode to form a three-electrode system, wherein N is used as 2 Saturated 0.1mol L -1 HClO of (a) 4 For electrolyte solution, the electrochemical workstation is connected to select cyclic voltammetry, and the potential range is-0.24-0.9 VvsSCE, and the potential range is 50mVs -1 Is of (1)The cyclic scan test is performed at a drawing speed, and the result is shown in fig. 6, wherein a is a curve of comparative example 1, B is a curve of example 1, and the comparative example 1 does not scan out a hydrogen zone, because the displaced Pt atoms are wrapped by a large amount of Ag atoms, so that Pt cannot perform hydrogen absorption/desorption during cyclic voltammetry scanning, example 1 shows a typical cyclic voltammetry curve of Pt catalyst in the interval-0.2-0.1 vvscsce, the experimental result of example 1 has a significant hydrogen absorption/desorption peak, and the experimental result shows a significant Pt oxidation and PtO reduction peak in the interval-0.4-0.9 vvscsce, demonstrating that a large amount of Ag atoms are removed, forming a nanoporous structure, thereby forming a nanoporous Pt film mainly comprising a Pt skeleton.
Application 2:
the application of the nano porous Pt film prepared in the embodiment 1 in the fuel cell electrode is carried out to test the performance of an oxyhydrogen fuel cell, the nano porous Pt film material is transferred to a mica sheet or a PET substrate, and is transferred to a Nafion211 film through hot pressing, and is placed between the prepared cathode and anode electrodes to form a sandwich structure, and the sandwich structure is hot pressed on a hot press at 135 ℃ under the pressure of 5MPa, and the hot pressing adopts positive pressure and back pressure, and each pressure is 90 seconds to obtain the anode and cathode anode electrode with the area of 2cm 2 The anode electrode was 0.1mg commercially available as MEA of (C) Pt cm -2 In the single cell performance test, after the membrane electrode is connected with the gas pipeline and the pressure device, the humidified high-purity N is firstly introduced into the anode and the cathode of the cell 2 To discharge the impurity gases in the battery, the flow rates of the gases are all 200mLmin -1 Continuously introducing the battery for 50min, applying a battery test to the battery, wherein the back pressure required by the anode and the cathode is 0.5bar and 1.5bar respectively during the test, and then introducing humidified high-purity H to the two sides of the anode and the cathode respectively 2 And O 2 The flow rate is 200mLmin -1 The test of the cell performance I-V curve is completed by using the fuel cell test system, as shown in FIG. 7, wherein a is an I-V curve of 1.5bar, b is an I-V curve of 0.5bar, and as can be seen from FIG. 7, the normal open circuit voltage is 0.93V. The test strip of FIG. 7Piece and result: the peak power density reaches 450mWcm under the conditions of 80 ℃ and 0.5bar back pressure -2 The peak power density was from 450mWcm when the cathode back pressure was increased to 1.5bar -2 Up to about 650mWcm -2 The performance is improved by 44%, and the overall performance of the hydrogen fuel cell is better.
The Pt thin films prepared in examples 1 to 4 and comparative examples 1 to 2 were applied to a battery membrane electrode, the nanoporous Pt thin film was transferred to a mica sheet or a PET substrate, a hot pressing method was used, the applied pressure was 10MPa, the temperature was 80 ℃, the time was 5min, the nanoporous Pt thin film was transferred from the substrate surface to the Nafion membrane surface, assembled into a fuel cell jig, the initial battery power density thereof and the battery power density after 10000 cycles of 0.6 to 1V cycle scan were detected, and the power density retention rate was calculated, as shown in table 1, the membrane electrode area corresponds to the Ag foil size.
TABLE 1 detection results
As can be seen from the detection results of the above examples and comparative examples, comparison of example 1 and comparative example 1 shows that Ag atoms of the AgPt alloy thin film that was not subjected to nitric acid treatment cannot be removed from the alloy under the same other conditions, so that a large pore structure cannot be formed, and poor battery power density is exhibited in the battery performance test. Comparison of example 2 and comparative example 2 shows that after the replacement temperature of the precursor Pt is increased, the kinetics of the replacement reaction of Pt ions and Ag atoms is dramatically improved, the ordered replacement of Ag and Pt atoms cannot be performed under mild conditions, and the rapid AgCl dissolution forms larger silver chloride crystals attached to the film surface, so that the film structure is damaged, resulting in poor battery performance. Comparison of example 3 and comparative example 3 shows that nanoporous Pt membrane electrodes could not be successfully prepared using electrochemical cyclic voltammetry based on a three electrode system and applied to battery membrane electrodes.

Claims (10)

1. A preparation method of a nano porous Pt film is characterized by comprising the following steps: the method comprises the following steps:
(1) Adopting an electrochemical displacement method, taking Ag foil as an initial raw material, placing the Ag foil into a precursor Pt solution for reaction to prepare an AgPt alloy film attached with silver chloride crystals, wherein the Pt loading capacity is 50 mu gcm -2 -100μgcm -2
(2) Placing the AgPt alloy film attached with the silver chloride crystal into an electrolyte accelerator for impregnation to obtain an AgPt alloy film;
(3) The AgPt alloy film is placed in a dilute nitric acid solution for dealloying treatment, and a nano Pt film with the atomic number ratio of Pt/Ag of 60/40-90/10 is obtained;
(4) And (3) placing the nano Pt film obtained in the step (3) in a tube furnace with a reducing atmosphere for heat treatment to obtain the nano porous Pt film.
2. The method for preparing a nanoporous Pt film according to claim 1, wherein: the reaction temperature in the step (1) is 0-25 ℃ and the reaction time is 1-12h.
3. The method for preparing a nanoporous Pt film according to claim 1, wherein: the precursor Pt solution in the step (1) is chloroplatinic acid solution or chloroplatinic acid solution, and the concentration of the precursor Pt solution is 1-30mmolL -1
4. The method for preparing a nanoporous Pt film according to claim 1, wherein: the electrolyte accelerator in the step (2) is saturated NaCl solution, and the soaking time is 1-12h.
5. The method for preparing a nanoporous Pt film according to claim 1, wherein: during the dealloying treatment of the step (3), the concentration of the dilute nitric acid solution is 10-50mmolL -1 The treatment temperature is 20-40 ℃ and the treatment time is 6-12h.
6. The method for preparing a nanoporous Pt film according to claim 1, wherein: step (4)The reducing atmosphere is H 2 /N 2 The heat treatment temperature is 200-400 deg.C, and the heat treatment time is 2-10h.
7. A nanoporous Pt film characterized by: is produced by the method for producing a nanoporous Pt film according to any one of claims 1 to 6.
8. Use of the nanoporous Pt film of claim 7 in a fuel cell electrode, characterized by: and (3) transferring the nano porous Pt film onto the Nafion film by a transfer printing method to form a self-supporting film electrode, and assembling the self-supporting film electrode into a fuel cell clamp.
9. The use of a nanoporous Pt film according to claim 8 in a fuel cell electrode, wherein: transferring the nano porous Pt film to a mica sheet or a PET substrate, and transferring the nano porous Pt film from the surface of the substrate to the surface of the Nafion film by adopting a hot pressing method.
10. The use of a nanoporous Pt film according to claim 9 in a fuel cell electrode, characterized in that: the pressure applied by the hot pressing method is 2-15MPa, the temperature is 50-200 ℃ and the time is 0.5-10min.
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CN101332438A (en) * 2008-08-04 2008-12-31 山东大学 Method for coating noble metal on nano porous gold and prepared catalyst
CN106757214A (en) * 2016-11-23 2017-05-31 昆明理工大学 The method that nanoporous noble metal film is prepared in eutectic type ionic liquid
CN110512229A (en) * 2019-09-17 2019-11-29 王选明 A kind of preparation method of water electrolysis analysis oxygen electrode
CN111916773A (en) * 2020-06-28 2020-11-10 中南大学 Integrated PtCu/nano carbon fiber catalyst layer, preparation method thereof and application thereof in fuel cell
CN114525511A (en) * 2022-03-01 2022-05-24 天津理工大学 Preparation method of nano porous metal electrode material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101332438A (en) * 2008-08-04 2008-12-31 山东大学 Method for coating noble metal on nano porous gold and prepared catalyst
CN106757214A (en) * 2016-11-23 2017-05-31 昆明理工大学 The method that nanoporous noble metal film is prepared in eutectic type ionic liquid
CN110512229A (en) * 2019-09-17 2019-11-29 王选明 A kind of preparation method of water electrolysis analysis oxygen electrode
CN111916773A (en) * 2020-06-28 2020-11-10 中南大学 Integrated PtCu/nano carbon fiber catalyst layer, preparation method thereof and application thereof in fuel cell
CN114525511A (en) * 2022-03-01 2022-05-24 天津理工大学 Preparation method of nano porous metal electrode material

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