CN110875480A - Platinum carbon nanofiber electrode and preparation method thereof - Google Patents
Platinum carbon nanofiber electrode and preparation method thereof Download PDFInfo
- Publication number
- CN110875480A CN110875480A CN201811018447.6A CN201811018447A CN110875480A CN 110875480 A CN110875480 A CN 110875480A CN 201811018447 A CN201811018447 A CN 201811018447A CN 110875480 A CN110875480 A CN 110875480A
- Authority
- CN
- China
- Prior art keywords
- electrode
- carbon
- nanofiber
- gas diffusion
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to a platinum carbon nanofiber electrode and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a carbon carrier, a Nafion solution and a binder to prepare spinning slurry; spinning the spinning slurry to obtain a nanofiber catalyst layer; transferring the nanofiber catalyst layer to the surface of a gas diffusion layer coated with carbon powder and polytetrafluoroethylene to obtain a gas diffusion electrode; and depositing platinum nano particles on the gas diffusion electrode in a three-electrode system by using the gas diffusion electrode as a working electrode and a solution containing chloroplatinic acid and sulfuric acid as an electrolyte by adopting a pulse electrodeposition technology to prepare the platinum-carbon nanofiber electrode. The platinum carbon nanofiber electrode and the preparation method thereof can improve the utilization rate of the catalyst Pt and the performance stability of the battery.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a platinum carbon nanofiber electrode and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of high power density, high energy conversion efficiency, low-temperature starting, environmental friendliness, and the like, and are considered as ideal power sources for stationary power stations, electric vehicles, and portable power sources. However, successful commercialization is mainly faced with both cost and lifetime issues. In a fuel cell assembly, the cost of the catalyst accounts for nearly half, reducing the catalyst loading is the most direct way to reduce the cost of the fuel cell, and the stability of the catalyst also has an extremely important effect on the fuel cell. Therefore, the preparation process of the electrode is optimized, the utilization rate and the stability of the catalyst in the electrode are improved, and the fuel cell still has higher activity and longer service life when the Pt (platinum) loading is lower, so that the method is a preoccupation in the current low-temperature fuel cell research, and has very important practical significance for reducing the cost of the PEMFC and accelerating the commercialization process of the PEMFC. The traditional method for preparing the electrode mainly sprays or coats catalyst slurry on a proton exchange membrane or a gas diffusion layer, and has the main defects of low Pt utilization rate and unstable battery performance. Researchers adopt an electrostatic spinning technology to prepare a Pd/C nanofiber layer and then prepare an electrode in a Pt deposition mode, the utilization rate of Pt is improved, but the situation that noble metal Pd particles are coated by macromolecules and Pt cannot be deposited exists, and the utilization rate of Pd is reduced; meanwhile, the Pd nanoparticles are difficult to be completely coated by the electro-deposited Pt, the exposed Pd nanoparticles are easy to dissolve in the operating environment of the fuel cell, and the dissolved Pd has a poisoning effect on the proton exchange membrane and is not beneficial to further prolonging the service life of the fuel cell.
Disclosure of Invention
Based on the above, it is necessary to provide a platinum carbon nanofiber electrode capable of improving the utilization rate of noble metals and the stability of a battery, and a preparation method thereof.
A preparation method of a platinum carbon nanofiber electrode comprises the following steps:
mixing a carbon carrier, a Nafion solution and a binder to prepare spinning slurry;
spinning the spinning slurry to obtain a nanofiber catalyst layer;
transferring the nanofiber catalyst layer to the surface of a gas diffusion layer coated with carbon powder and polytetrafluoroethylene to obtain a gas diffusion electrode;
and depositing platinum nano particles on the gas diffusion electrode in a three-electrode system by using the gas diffusion electrode as a working electrode and a solution containing chloroplatinic acid and sulfuric acid as an electrolyte by adopting a pulse electrodeposition technology to prepare a platinum-carbon nanofiber electrode (marked as Pt @ C nanofiber electrode).
In one embodiment, the pulse electrodeposition current is (25-300) mA-cm-2The current supply time is 0.1-2 ms, the current off time is 1.5-16 ms, and the pulse electrodeposition time is 200-3600 s.
In one embodiment, the pulse electrodeposition current is (115-235) mA-cm-2The current supply time is 0.8-1.2 ms, the current off time is 1.8-4 ms, and the pulse electrodeposition time is 400-1200 s.
In one embodiment, the mass ratio of the carbon carrier to the solid content of the Nafion solution to the binder is 20 (6-20) to (5-10).
In one embodiment, the raw material of the spinning slurry further comprises polytetrafluoroethylene, and the polytetrafluoroethylene, the carbon carrier, the Nafion solution and the binder are mixed to obtain the spinning slurry.
In one embodiment, the mass ratio of the polytetrafluoroethylene to the carbon carrier in the spinning slurry is (1-5): 20.
In one embodiment, the carbon carrier is supported in an amount of (0.2 to 2.0) mg-cm-2。
In one embodiment, the method further comprises a step of preparing the gas diffusion layer coated with carbon powder and polytetrafluoroethylene: mixing carbon powder and 4-22 wt% of polytetrafluoroethylene slurry according to the mass ratio of 10 (0.1-5) to obtain coating slurry, blade-coating the coating slurry on the surface of carbon paper, and controlling the blade-coating thickness to be 35-250 microns.
In one embodiment, the spinning step adopts electrostatic spinning, and the liquid flow rate of the electrostatic spinning is (0.4-1.2) mL-h-1The distance between the needle point and the receiving plate is (5-25) cm, the voltage is (8-22) KV, and the receiving time is (1.5-6.5) h.
The platinum carbon nanofiber electrode prepared by the preparation method.
According to the platinum carbon nanofiber electrode and the preparation method thereof, the nanofiber catalyst layer is formed by adopting a spinning technology, and the network with the nanofiber structure is beneficial to improving the H proton conductivity. The C and the Nafion are uniformly dispersed on the surface of the nanofiber of the binder, so that the Pt is favorably deposited on the contact interface of the carbon carrier and the Nafion, the condition that the catalyst Pt is not in contact with the Nafion or is completely coated by the Nafion is avoided, the three-phase reaction interface of proton, electron and gas is optimized, and the utilization rate of the catalyst Pt is improved. In addition, the Pt nano particles deposited by the pulse deposition technology are irregular spheres, the average diameter is about 15nm, and the activity of the Pt catalyst is improved; meanwhile, the deposited Pt has larger grain size, which is beneficial to mass transfer, and further can improve the stability of the Pt catalyst and the battery performance.
Drawings
Fig. 1 is a scanning electron microscope image of a nanofiber catalyst layer prepared in example 1 of the present invention;
FIG. 2 is a transmission electron micrograph of a Pt @ C nanofiber electrode prepared in example 1 of the present invention;
FIG. 3 is a graph of the discharge performance of a Pt @ C nanofiber electrode made in accordance with example 1 of the present invention and a conventional electrode made in accordance with comparative example 1;
FIG. 4 is a graph of stability testing curves for Pt @ C nanofiber electrodes made according to example 1 of the present invention and for conventional electrodes made according to comparative example 1.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The inventor researches and discovers that the traditional electrode preparation method is mainly to spray or coat catalyst slurry on a proton exchange membrane or a gas diffusion layer, and because the uniformity of components of a carbon-supported Pt catalyst and an electrolyte in the catalyst slurry is poor, the problem that part of the carbon-supported Pt catalyst is not contacted with a Nafion membrane or part of the carbon-supported Pt catalyst is completely coated by Nafion exists after the catalyst slurry is coated, a three-phase reaction interface of proton, electron and gas cannot be effectively constructed, and the improvement of the utilization rate of Pt is not facilitated; and the electrode formed by coating is compact and not beneficial to mass transfer, so that the battery performance is not high when the Pt loading is low. The Pt @ Pd/C nanofiber electrode is prepared by scientific researchers in a mode of depositing Pt behind Pd/C nanofibers, the utilization rate of Pt is improved, but the cost of Pd is high, the utilization rate of Pd needs to be improved, and meanwhile, the risk that Pd poisons a proton exchange membrane exists.
Based on this, the invention provides a platinum carbon nanofiber electrode of an embodiment and a preparation method thereof. The preparation method comprises the following steps of S1-S4.
Step S1: and mixing the carbon carrier, the Nafion solution and the binder to prepare spinning slurry.
The carbon carrier is used as a carrier of Pt, and the Nafion solution is a perfluorosulfonic acid type polymer solution and is used for supporting an electrode; nafion and a binder are mixed, a nanofiber structure is formed through subsequent spinning, and the network of the nanofiber structure is beneficial to improving the H proton conductivity. And the C and the Nafion are uniformly dispersed on the surface of the nanofiber of the binder, so that the subsequent deposition of Pt on the contact interface of the carbon carrier and the Nafion is facilitated, the condition that the catalyst Pt is not in contact with the Nafion or is completely coated by the Nafion is avoided, the three-phase reaction interface of proton, electron and gas is optimized, and the utilization rate of the catalyst Pt is improved.
In one embodiment, the loading amount of the carbon carrier is (0.2-2.0) mg-cm-2。
Preferably, the binder is at least one of polyacrylic acid, polyacrylonitrile and polyvinylpyrrolidone. These binders are soluble in at least one of isopropanol and water, and the binders may be dissolved in at least one of isopropanol and water to form a solution, which is added to the spinning dope in the form of a binder solution. Specifically, the mass content of the binder solution is 8-15%.
In one embodiment, the mass content of the Nafion solution is 3% -9%, and the mass ratio of the carbon carrier, the Nafion solution and the binder is 20 (6-20) to 5-10. Preferably, the mass ratio of the carbon carrier, the Nafion solution and the binder is 20 (15-20) to (5-10).
In one embodiment, the raw material of the spinning slurry also comprises polytetrafluoroethylene, and the spinning slurry is prepared by mixing the polytetrafluoroethylene, a carbon carrier, a Nafion solution and a binder. The inventor finds that the polytetrafluoroethylene is added into the spinning slurry, so that the hydrophobicity of the prepared nanofiber catalyst layer is favorably improved. Preferably, the mass ratio of the polytetrafluoroethylene to the carbon carrier in the spinning slurry is (1-5): 20.
Preferably, in the step S1, ultrasonic treatment is adopted for 2 to 4 hours, and then stirring is carried out for 18 to 40 hours.
Step S2: and spinning the spinning slurry to obtain the nanofiber catalyst layer.
The nanofiber catalyst layer prepared in step S2 has a nanofiber structure, and the average diameter of the fibers is 250 μm. C and Nafion are uniformly dispersed on the surface of the nano-fiber of the binder, so that the utilization rate of the catalyst Pt is improved.
In one embodiment, the spinning step adopts electrostatic spinning, and the liquid flow rate of the electrostatic spinning is (0.4-1.2) mL.h-1The distance between the needle point and the receiving plate is (5-25) cm, the voltage is (8-22) KV, and the receiving time is (1.5-6.5) h.
Step S3: and transferring the nanofiber catalyst layer to the surface of a Gas Diffusion Layer (GDL) coated with carbon powder and polytetrafluoroethylene to obtain the gas diffusion electrode.
The main function of the gas diffusion layer in the gas diffusion electrode is to allow the reactant gases to pass smoothly and to supply the reactive layer with the gases required for the corresponding reaction. The nanofiber catalyst layer is a place where a reduction reaction of oxygen occurs, and the gas delivered from the gas diffusion layer forms an electrochemical reaction activation point together with a catalyst and an electrolyte therein, thereby reducing the reaction gas.
In one embodiment, the method further comprises the step of preparing the gas diffusion layer coated with carbon powder and polytetrafluoroethylene: mixing carbon powder and 4-22 wt% of polytetrafluoroethylene slurry according to the mass ratio of 10 (0.1-5) to obtain coating slurry, blade-coating the coating slurry on the surface of the carbon paper, and controlling the blade-coating thickness to be 35-250 microns.
The transfer printing step can adopt a hot pressing method for transfer printing, the hot pressing pressure of the transfer printing is (0.25-1) MPa, the time is 1-5 min, and the hot pressing temperature is 135-142 ℃. Preferably, the hot pressing pressure of the transfer printing is (0.25-0.5) MPa, the time is 3-4 min, and the hot pressing temperature is 139-141 ℃.
Step S4: the platinum carbon nanofiber electrode is prepared by depositing platinum nanoparticles on a gas diffusion electrode in a three-electrode system by using a pulse electrodeposition technology and taking the gas diffusion electrode as a working electrode and a solution containing chloroplatinic acid and sulfuric acid as an electrolyte.
Specifically, a saturated calomel electrode can be used as a reference electrode, a graphite electrode can be used as a counter electrode, and a solution of chloroplatinic acid and sulfuric acid can be used as an electrolyte.
Step S4 is to deposit Pt on the gas diffusion electrode by using a pulse electrodeposition technique, where the Pt is deposited at the interface where the carbon carrier and the proton conductor Nafion contact, so as to avoid the situation that the catalyst Pt is not in contact with Nafion or is completely coated by Nafion, optimize the three-phase reaction interface of proton, electron and gas, and improve the utilization rate of the catalyst Pt. In addition, the deposited Pt nano particles are in irregular spherical shapes, the average diameter is about 15nm, and the activity of the Pt catalyst is improved; meanwhile, the deposited Pt has larger grain size, which is beneficial to mass transfer and improves the stability of the Pt catalyst.
In one embodiment, the pulse electrodeposition current is (25-300) mA-cm-2The current supply time is 0.1-2 ms, the current off time is 1.5-16 ms, and the pulse electrodeposition time is 200-3600 s.
Preferably, the current of the pulse electrodeposition is (115-235) mA-cm-2The current supply time is 0.8-1.2 ms, the current off time is 1.8-4 ms, and the pulse electrodeposition time is 400-1200 s.
In the electrolyte, the concentration of chloroplatinic acid is (0.1-60) mmol/L, and the concentration of sulfuric acid is (0.1-2) mol/L.
According to the platinum-carbon nanofiber electrode and the preparation method thereof, the nanofiber catalyst layer is formed by adopting a spinning technology, the gas diffusion electrode is formed by transfer printing, and then the catalyst Pt is deposited by adopting a pulse deposition technology. Therefore, the condition that the catalyst Pt is not contacted with Nafion or is completely coated by Nafion is avoided, the three-phase reaction interface of proton, electron and gas is optimized, and the utilization rate of the catalyst Pt is improved; the deposited Pt nano particles are irregular spheres, the average diameter is about 15nm, and the activity of the Pt catalyst is improved; meanwhile, the deposited Pt has larger grain size, which is beneficial to mass transfer, and further can improve the stability of the Pt catalyst and the battery performance.
In addition, the carbon carrier without the metal catalyst is adopted, so that the problem of low utilization rate caused by coating of the catalyst by Nafion in the step S1 can be further avoided, and the problem of instability of the Nafion membrane caused by degradation of the Nafion membrane by adopting a Pd catalyst is avoided by adopting a pulse deposition technology to deposit the catalyst Pt in the step S4, so that the utilization rate of the catalyst and the stability of the performance of the battery are improved.
The structure of the prepared platinum carbon nanofiber electrode is as follows: a nanofiber catalyst layer is formed on the gas diffusion layer coated with carbon powder and polytetrafluoroethylene on the surface, and a catalyst Pt is deposited on the nanofiber catalyst layer. The nanofiber catalyst layer has a nanofiber structure, the average diameter of the fibers is 250 microns, and C and Nafion are uniformly dispersed on the surface of the nanofiber of the binder; pt is deposited at the contact interface of the carbon carrier and the proton conductor Nafion, and the deposited Pt nano particles are in an irregular spherical shape and have an average diameter of about 15 nm.
Furthermore, the Pt content of the prepared platinum-carbon nanofiber electrode is (0.03-0.4) mg-cm-2. The Pt has larger grain size and is beneficial to mass transfer, so the battery performance is still excellent when the Pt loading is lower, and the stability of the Pt catalyst is improved.
The following are specific examples.
Example 1
(1) 1g of polyacrylic acid as a binder was weighed, dissolved in a mixed solvent of 6g of isopropyl alcohol and 1g of water, and stirred for 24 hours to prepare a 12.5 wt% binder solution. 0.05g of Vulcan XC-72 carbon carrier, 0.75g of Nafion solution (5 wt%) and 0.003g of PTFE powder are weighed and mixed uniformly, ultrasonic treatment is carried out for 3h, then 0.1g of binder solution is added, and stirring is carried out for 24h, thus obtaining spinning slurry. Wherein the loading amount of Vulcan XC-72 carbon carrier is 0.27mg cm-2。
(2) Then preparing a catalyst layer by adopting an electrostatic spinning technology, wrapping an aluminum foil on the surface of a roller collector, and carrying out electrostatic spinning to obtain a nanofiber catalyst layer, wherein the electrostatic spinning condition parameters are as follows: the liquid flow rate is 0.6mL h-1The distance between the needle tip and the receiving plate is 12cm, the voltage is 10KV, and the receiving time is 1h, so that the nanofiber catalyst layer is obtained.
(3) Carbon powder XC-72 and 5 wt% polytetrafluoroethylene slurry (commercially available) were mixed to obtain a coating slurry, and the coating slurry was drawn down to one side of carbon paper to prepare a gas diffusion layer, with a thickness of 50 μm. Wherein the carbon paper is available from Toray, japan. And finally, transferring the prepared nanofiber catalyst layer to one side of the gas diffusion layer coated by carbon powder and polytetrafluoroethylene in a scraping manner through hot pressing to obtain the gas diffusion electrode.
(4) The method comprises electrodepositing platinum by pulse electrodeposition with gas diffusion electrode as working electrode, saturated calomel electrode as reference electrode, graphite electrode as counter electrode, chloroplatinic acid and sulfuric acid solution as electrolyte, and deposition current of 125mA cm-2Time of current supply1.0ms, current off time of 4.0ms, pulse electrodeposition time of 750s, and Pt content of 0.1 mg/cm-2The platinum carbon nanofiber electrode (denoted as Pt @ C nanofiber electrode).
Example 2
The same as example 1 except that: changing the pulse electrodeposition parameters (deposition current of 150mA cm) in the step (4)-2Current supply time of 0.8ms, current off time of 3.8ms, pulse electrodeposition time of 200-500 s), and Pt content of 0.03-0.05 mg/cm-2Pt @ C nanofiber electrode of (1).
Example 3
The same as example 1 except that: the blade coating thickness in the step (3) is 250 mu m; the deposition current of the pulse electrodeposition in the step (4) is 300mA cm-2The current supply time was 0.1ms, the current off time was 16ms, and the pulse electrodeposition time was 3600 s.
Example 4
The same as example 1 except that: preparing a nano-fiber catalyst layer with the mass ratio of the solid content in the Nafion solution to the carbon carrier being 0.5.
Example 5
The same as example 1 except that: 1g of 5 wt% Nafion solution and 0.0125g of PTFE powder in the spinning slurry are uniformly mixed, and the mass of the binder solution is 0.2g, wherein the mass ratio of the carbon carrier in the spinning slurry to the solid content in the Nafion solution to the binder to the PTFE powder is 20:20:10: 5.
Example 6
The same as example 1 except that: no PTFE powder was added to the spinning dope.
Comparative example 1
The traditional electrode preparation method comprises the following steps: a commercial 40 wt% Pt/C catalyst was sprayed onto the surface of the gas diffusion layer to prepare a single-sided gas diffusion electrode as the cathode.
The following are performance tests.
The nanofiber catalyst layer prepared in example 1 was subjected to a scanning electron microscope test, and the obtained scanning electron microscope image is shown in fig. 1. As can be seen from fig. 1, the nanofiber catalyst layer prepared by the electrospinning technique in example 1 has a nanofiber structure, and the average diameter of the fibers is 250 μm.
The Pt @ C nanofiber electrode prepared in example 1 was subjected to a transmission electron microscope test, and the obtained transmission electron microscope image is shown in FIG. 2. As can be seen from fig. 2, the Pt catalyst deposited on the nanofiber catalytic layer had an irregular spherical shape with an average diameter of 15 nm.
The electrodes obtained in example 1 and comparative example 1 were used as cathodes, respectively, to prepare membrane electrodes, and performance tests were performed. Wherein the Pt supported amount of the Pt @ C nanofiber electrode prepared in example 1 was 0.1mg cm-2(ii) a The conventional electrode obtained in comparative example 1 had a Pt content of 0.18mg cm-2。
Specifically, the electrodes obtained in example 1 and comparative example 1 were used as cathodes, respectively; a commercial 40 wt% Pt/C catalyst was sprayed as an anode on one side of a Nafion membrane using a conventional preparation method with a Pt loading of 0.2mg cm-2(ii) a And finally, carrying out hot pressing on the prepared cathode and anode to form a film electrode, and carrying out electrochemical performance evaluation on a single cell evaluation device, wherein the electrochemical performance evaluation comprises discharge performance and battery stability tests.
FIG. 3 is a plot of the discharge performance of a Pt @ C nanofiber electrode made according to example 1 of the present invention versus a conventional electrode made according to comparative example 1. The battery operating conditions for the discharge performance test were: battery temperature: 65 ℃; degree of gas wettability: 80 percent; h2Flow rate: 100 mL/min-1(ii) a Air flow rate: 500 mL/min-1。
As can be seen from fig. 3: compared with the electrode prepared by the traditional spraying method in the comparative example 1, the Pt @ C nanofiber electrode prepared in the example 1 of the invention has better initial activity. The Pt supported amount of the Pt @ C nanofiber electrode prepared in example 1 of the invention is 0.1mg cm-2When the power density reaches 0.65W cm-2The amount of Pt supported on the platinum is 0.18 mg/cm-2Performance of conventional Pt/C electrode (0.66W cm)-2) And (4) the equivalent. That is, the embodiment of the present invention improves the utilization rate of Pt.
In FIG. 4 (a) and (b) are respectively Pt @ C nanofiber electrode prepared in example 1 of the present invention and a comparative example1 stability test curve of the conventional electrode prepared. The accelerated decay test conditions for the stability test were: the voltage range is 0.6-1.2V; scanning speed 0.1 V.s-1. The battery operating conditions were: battery temperature: 65 ℃; degree of gas wettability: 100 percent; h2Flow rate: 100 mL/min-1(ii) a Air flow rate: 500 mL/min-1。
As can be seen from fig. 4: the Pt @ C nanofiber electrode prepared in example 1 of the present invention had better stability than the electrode prepared by the conventional spray coating method of comparative example 1. After 3000 circles of accelerated attenuation, the highest power density is only attenuated by 9.1%, and the highest power density of the traditional Pt/C electrode is attenuated by 24.3%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a platinum carbon nanofiber electrode is characterized by comprising the following steps:
mixing a carbon carrier, a Nafion solution and a binder to prepare spinning slurry;
spinning the spinning slurry to obtain a nanofiber catalyst layer;
transferring the nanofiber catalyst layer to the surface of a gas diffusion layer coated with carbon powder and polytetrafluoroethylene to obtain a gas diffusion electrode;
and depositing platinum nano particles on the gas diffusion electrode in a three-electrode system by using the gas diffusion electrode as a working electrode and a solution containing chloroplatinic acid and sulfuric acid as an electrolyte by adopting a pulse electrodeposition technology to prepare the platinum-carbon nanofiber electrode.
2. The method according to claim 1, wherein the pulse electrodeposition current is (25 to 300) mA-cm-2The current supply time is 0.1-2 ms, the current off time is 1.5-16 ms, and the pulse electrodeposition time is 200-3600 s.
3. The method according to claim 2, wherein the pulse electrodeposition current is (115 to 235) mA-cm-2The current supply time is 0.8-1.2 ms, the current off time is 1.8-4 ms, and the pulse electrodeposition time is 400-1200 s.
4. The method according to claim 1, wherein the mass ratio of the carbon carrier to the solid content of the Nafion solution to the binder is 20 (6-20) to (5-10).
5. The method according to any one of claims 1 to 4, wherein the raw material of the spinning dope further comprises polytetrafluoroethylene, and the spinning dope is prepared by mixing the polytetrafluoroethylene, the carbon support, the Nafion solution, and the binder.
6. The preparation method according to claim 5, wherein the mass ratio of the polytetrafluoroethylene to the carbon carrier in the spinning slurry is (1-5): 20.
7. The method according to any one of claims 1 to 4, wherein the amount of the carbon carrier supported is (0.2 to 2.0) mg-cm-2。
8. The method according to any one of claims 1 to 4, further comprising a step of preparing the gas diffusion layer coated with carbon powder and polytetrafluoroethylene on the surface: mixing carbon powder and 4-22 wt% of polytetrafluoroethylene slurry according to the mass ratio of 10 (0.1-5) to obtain coating slurry, blade-coating the coating slurry on the surface of carbon paper, and controlling the blade-coating thickness to be 35-250 microns to obtain the carbon paper.
9. The method according to any one of claims 1 to 4, wherein the spinning step is electrospinning at a liquid flow rate of (0.4 to 1.2) mL-h-1The distance between the needle point and the receiving plate is (5-25) cm, the voltage is (8-22) KV, and the receiving time is (1.5-6.5) h.
10. The platinum-carbon nanofiber electrode prepared by the preparation method as set forth in any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811018447.6A CN110875480A (en) | 2018-09-03 | 2018-09-03 | Platinum carbon nanofiber electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811018447.6A CN110875480A (en) | 2018-09-03 | 2018-09-03 | Platinum carbon nanofiber electrode and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110875480A true CN110875480A (en) | 2020-03-10 |
Family
ID=69716509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811018447.6A Pending CN110875480A (en) | 2018-09-03 | 2018-09-03 | Platinum carbon nanofiber electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110875480A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113604843B (en) * | 2021-07-02 | 2023-04-21 | 北京化工大学 | Low-load Pt/C catalyst hydrogen diffusion anode and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441287A (en) * | 2013-08-09 | 2013-12-11 | 中国科学院上海高等研究院 | Preparation method of membrane electrode of direct methanol fuel cell |
| CN108110284A (en) * | 2016-11-18 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method for directly preparing fuel cell Pt nanocrystal nucleocapsid Catalytic Layer |
-
2018
- 2018-09-03 CN CN201811018447.6A patent/CN110875480A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441287A (en) * | 2013-08-09 | 2013-12-11 | 中国科学院上海高等研究院 | Preparation method of membrane electrode of direct methanol fuel cell |
| CN108110284A (en) * | 2016-11-18 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method for directly preparing fuel cell Pt nanocrystal nucleocapsid Catalytic Layer |
Non-Patent Citations (1)
| Title |
|---|
| SHAOJING HONG等: "High-Performance Low-Platinum Electrode for Proton Exchange Membrane Fuel Cells: Pulse Electrodeposition of Pt on Pd/C Nanofiber Mat", 《CHEMELECTROCHEM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113604843B (en) * | 2021-07-02 | 2023-04-21 | 北京化工大学 | Low-load Pt/C catalyst hydrogen diffusion anode and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Waldrop et al. | Application of electrospinning for the fabrication of proton-exchange membrane fuel cell electrodes | |
| CN103441287B (en) | The preparation method of a kind of direct methanol fuel cell membrane electrode | |
| CN110336049B (en) | Nitrogen-cobalt-doped hollow carbon nanofiber, preparation method and application thereof, and metal-air battery | |
| JP5055788B2 (en) | Electrocatalyst | |
| JP5648785B2 (en) | Fuel cell electrode | |
| US20090142647A1 (en) | Carbon fiber, porous support-carbon fiber composite and method for producing the same as well as catalyst structure, electrode for solid polymer fuel cell and solid polymer fuel cell | |
| CN105261767A (en) | Nano carbon-doped porous fiber single electrode, membrane electrode and preparation method | |
| CN104716348A (en) | Nanofiber network structure electrode, preparation method and application thereof | |
| CN108539206B (en) | Catalysis layer full-order fuel cell electrode and membrane electrode | |
| US20220140354A1 (en) | Fuel cell electrode with catalysts grown in situ on ordered structure microporous layer and method for preparing membrane electrode assembly | |
| CN111370717A (en) | Cathode catalyst slurry, cathode catalyst layer, membrane electrode and fuel cell | |
| CN112382767B (en) | Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer | |
| CN108110284B (en) | Method for directly preparing platinum nanocrystalline core-shell catalyst layer for fuel cell | |
| US20190036129A1 (en) | Carbon nanofiber catalyst substrate production process | |
| CN110875480A (en) | Platinum carbon nanofiber electrode and preparation method thereof | |
| CN111952599B (en) | Preparation method and application of nanofiber electrode of proton exchange membrane fuel cell | |
| Brodt et al. | Nanofiber fuel cell electrodes I. Fabrication and performance with commercial Pt/C catalysts | |
| CN111584879A (en) | Gas diffusion layer, method for producing same, and corresponding membrane electrode assembly and fuel cell | |
| CN100506373C (en) | Improved pemfc electrocatalyst based on mixed carbon supports | |
| KR20180062091A (en) | Method for preparing membrane-electrode assembly, membrane-electrode assembly prepared therefrom ans fuel cell comprising the same | |
| WO2021114317A1 (en) | Electrode material having fiber structure, and preparation and application thereof | |
| CN113675411B (en) | Fuel cell electrode and preparation method and application thereof | |
| CN114628718B (en) | Gas diffusion layer for fuel cell electrode, method for producing the same and use thereof | |
| CN116581308B (en) | Dry membrane electrode preparation method of membrane fuel cell | |
| JP7310855B2 (en) | catalyst layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200310 |
|
| RJ01 | Rejection of invention patent application after publication |