CN115939417A - Membrane electrode for proton exchange membrane fuel cell and preparation method thereof - Google Patents
Membrane electrode for proton exchange membrane fuel cell and preparation method thereof Download PDFInfo
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- 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
Abstract
The invention provides a membrane electrode for a proton exchange membrane fuel cell and a preparation method thereof, belonging to the field of membrane electrode preparation, wherein the method comprises the steps of mixing water, a Nation solution, a fluorinated multi-walled carbon nanotube additive, a Pt/C catalyst and isopropanol, and then carrying out ultrasonic treatment to obtain cathode catalyst layer slurry; mixing water, nafion solution, pt/C catalyst and isopropanol, and then carrying out ultrasonic treatment to obtain anode catalyst layer slurry; and S2, respectively spraying the cathode catalyst slurry and the anode catalyst slurry on two sides of the proton exchange membrane through ultrasonic spraying to obtain the membrane electrode. The membrane electrode prepared by the invention has the advantages that the assembly form of the ionomer of the cathode catalytic layer is adjusted, the porosity of the catalytic layer is optimized, the flooding resistance of the catalytic layer is enhanced, the accessibility of oxygen to platinum sites is increased, and the utilization rate of the platinum-based catalyst is improved.
Description
Technical Field
The invention belongs to the technical field of membrane electrode preparation, and particularly relates to a membrane electrode for a proton exchange membrane fuel cell and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are one of the key technologies in hydrogen energy systems. One of the biggest challenges in large scale pem fuel cell applications is the high demand and hence high cost of the noble metal platinum catalyst in the membrane electrode. To realize large-scale commercialization of PEMFC-powered vehicles, the amount of platinum must be reduced to improve the utilization of platinum. It is clearly one of the more practical approaches to improve Pt utilization by optimizing the structure and properties of the Catalyst Layer (CL) as compared to finding a platinum-based catalyst with high specific activity.
In the PEMFC cathode catalytic layer, an oxygen reduction reaction is performed at a three-phase interface composed of oxygen, a catalyst active site (e.g., platinum atom Pt), and a sulfonic acid group of an ionomer. The ionomer phase acts as a binder for the carbon/catalyst particles and provides a pathway for proton transport. The ionomer film covering the catalyst particles may create a large transport resistance to oxygen, thereby reducing its accessibility to the catalyst active sites. Sulfonic acid groups in commercial perfluorosulfonic acid (PFSA) ionomers can adsorb strongly on the Pt surface, poisoning the active sites, and efforts should be made to reduce ionomer coverage. However, the formation of an effective three-phase interface in the catalytic layer is again dependent on intimate contact of the catalyst with the ionomer. Therefore, adjusting the ionomer distribution allows a balance to be achieved between these factors, which is of great significance in improving the availability and utilization of platinum. Gasteiger et al aminate a carbon support with an ionomer and-NH x + The ionic interaction between the groups to achieve a more uniform distribution of the ionomer will promote a delicate balance between oxygen and proton transport (J Electrochem S)oc,2017, 164 (4): F418-F26). Strasser et al ammonolyze sp at high temperature 2 Pyridine N groups are introduced into the carbon matrix, which also can interact beneficially with the ionomer chains (Nat Mater,2020, 19 (1): 77-85).
In addition, the membrane electrode assembly operates in such a manner that a hydrogen oxidation reaction occurs in the anode catalyst layer to generate protons (H) to hydrate the protons 3 O + ) Is passed through a Proton Exchange Membrane (PEM) so that part of the water on the anode side is continuously transported with the protons across the membrane to the cathode side, a process known as Electro-osmotic drag (EOD). The cathode undergoes an oxygen reduction reaction to combine with protons from the anode to produce water. The cathode water is excessive due to the anode water and the cathode reaction product water caused by the electric dragging effect, and flooding is easily caused. The water flooding greatly increases the transmission resistance of oxygen on the cathode catalyst layer, influences the formation of an effective three-phase interface, and objectively reduces the utilization rate of the platinum-based catalyst. The hydrophobic modification is carried out on the cathode catalyst layer of the catalyst layer, and the method is an effective means for relieving cathode flooding. Avcioglu et al enhanced their hydrophobicity by adding polytetrafluoroethylene to the cathode catalytic layer (Int J Hydrog Energy,2018, 43 (40): 18632-41); dowd et al obtained a hydrophobic ionomer interface on the catalyst layer by heat treatment under specific conditions (J Appl Electrochem,2020, 50 (10): 993-1006); xue et al added cage polysilsesquioxane to the catalytic layer to hydrophobically modify the cathode catalytic layer (J Power Sources,2021, 487. However, these cathode catalyzed hydrophobic modification techniques still do not facilitate the performance improvement of membrane electrodes at different humidities.
Disclosure of Invention
The membrane electrode prepared by the invention has the adjusted assembly form of the ionomer of the cathode catalytic layer, can optimize the porosity of the catalytic layer, enhance the flooding resistance of the catalytic layer, increase the accessibility of oxygen to platinum sites, and improve the utilization rate and performance expression of the platinum-based catalyst, thereby realizing stronger adaptability of the membrane electrode to humidity change and being beneficial to practical application.
The invention provides a preparation method of a membrane electrode for a proton exchange membrane fuel cell, which comprises the following steps:
s1, mixing a Nation solution, a fluorinated multi-walled carbon nanotube additive, a Pt/C catalyst and a first solvent, and then carrying out ultrasonic treatment to obtain cathode catalyst layer slurry;
mixing the Nation solution, the Pt/C catalyst and a second solvent, and then carrying out ultrasonic treatment to obtain anode catalyst layer slurry;
and S2, respectively spraying the cathode catalyst layer slurry and the anode catalyst layer slurry on two sides of the proton exchange membrane through ultrasonic spraying to obtain the membrane electrode.
In an embodiment of the present invention, the fluorinated multi-walled carbon nanotube additive is obtained in the following manner: oxidizing the multi-walled carbon nano-tube by a chemical method, and fluorinating the oxidized multi-walled carbon nano-tube by using a fluorinating agent to obtain the fluorinated multi-walled carbon nano-tube additive.
In an embodiment of the invention, the chemical method is Hummers method; the fluorinating agent is one or two of sodium fluoride and ammonium fluoride.
In the embodiment of the invention, the mass ratio of the fluorinating agent to the multi-wall carbon nano-tubes subjected to oxidation treatment is 1:10-1:12; the fluorination treatment is heat treatment at 900-950 ℃.
In an embodiment of the present invention, the first solvent and the second solvent are independently selected from one or more of water, alcohol solvent; in the cathode catalyst layer slurry, the mass ratio of the fluorinated multi-walled carbon nanotube additive to the Pt/C catalyst carbon matrix is 1:5-1:10.
In an embodiment of the present invention, the first solvent and the second solvent are both a mixture of water and isopropanol; in the cathode catalyst layer slurry, the mass ratio of the water, the Nation solution, the fluorinated multi-walled carbon nanotube additive, the Pt/C catalyst and the isopropanol is 200:15:0.1:2-3:150-160.
In an embodiment of the present invention, the ultrasonic spraying specifically includes: and (2) placing the proton exchange membrane on an electric hot plate at 70-90 ℃, fixing by using negative pressure, and then respectively spraying the cathode catalyst layer slurry and the anode catalyst layer slurry by using ultrasonic spraying equipment, wherein the discharge flow rate is 0.1-0.5mL/s.
In the embodiment of the invention, the proton exchange membrane is a perfluorosulfonic acid Nation membrane, and the thickness of the membrane is 50-200 microns.
The invention provides a membrane electrode for a proton exchange membrane fuel cell obtained by the preparation method.
In the embodiment of the present invention, the membrane electrode is suitable for 50% RH-180% RH change in humidity.
Compared with the prior art, the preparation method of the membrane electrode can mix the hydrophobic fluorinated multi-walled carbon nanotube (F-MCNT) with the solvent and the Nation solution, perform ultrasonic treatment until the mixture is uniformly dispersed, then add the commercial platinum-based cathode catalyst, perform ultrasonic treatment until the mixture is uniformly dispersed, and prepare cathode catalyst layer slurry; the anode catalysis layer slurry preparation process is similar, but F-MCNT is not added; then, the prepared cathode catalyst layer slurry and anode catalyst layer slurry are respectively ultrasonically sprayed on two sides of a proton exchange membrane, so that the membrane electrode is obtained. The method mainly utilizes the fluorinated multi-walled carbon nanotube as an additive of the cathode catalyst layer slurry, adjusts the assembly form of the ionomer of the cathode catalyst layer, optimizes the porosity of the catalyst layer, enhances the flooding resistance of the catalyst layer, and increases the accessibility of oxygen to platinum sites. The method of preparing the membrane electrode of the present invention is simple and easy to implement, and achieves a greater adaptability of the membrane electrode to changes in humidity (50% RH-180% RH), which is the greatest advantage of the present application.
Drawings
FIG. 1 is a frozen TEM image of a cathode catalyst layer slurry in example 1 of the present invention;
FIG. 2 is H for membrane electrode application of example 1 and comparative example 2 -O 2 Graph comparing the performance of the fuel cell at 180% RH;
FIG. 3 is H for membrane electrode application of example 1 and comparative example 2 -a graph comparing the performance of Air fuel cells at 180% RH;
FIG. 4 is H for membrane electrode application of example 1 and comparative example 2 -O 2 The fuel cell has a relative humidity of 100% RHThe graphs can be compared;
FIG. 5 is H for membrane electrode application of example 1 and comparative example 2 -Air fuel cell performance at 100% rh vs. graph;
FIG. 6 is H for membrane electrode application of example 1 and comparative example 2 -O 2 Graph comparing the performance of the fuel cell at 50% RH;
FIG. 7 is H for membrane electrode application of example 1 and comparative example 2 -Air fuel cell performance comparison graph at 50% RH.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The invention provides a preparation method of a membrane electrode for a proton exchange membrane fuel cell, which comprises the following steps:
s1, mixing a Nation solution, a fluorinated multi-walled carbon nanotube additive, a Pt/C catalyst and a first solvent, and then carrying out ultrasonic treatment to obtain cathode catalyst layer slurry;
mixing the Nation solution, the Pt/C catalyst and a second solvent, and then carrying out ultrasonic treatment to obtain anode catalyst layer slurry;
and S2, respectively spraying the cathode catalyst layer slurry and the anode catalyst layer slurry on two sides of the proton exchange membrane through ultrasonic spraying to obtain the membrane electrode.
The membrane electrode prepared by the invention can enhance the flooding resistance of the catalyst layer, increase the accessibility of oxygen to platinum sites and improve the utilization rate and performance expression of the platinum-based catalyst, thereby realizing stronger adaptability of the membrane electrode to humidity change and being beneficial to the practical application of proton exchange membrane fuel cells.
In the embodiment of the invention, hydrophobic fluorinated multi-walled carbon nanotubes (F-MCNT) are used as a cathode catalyst layer additive, mixed with a solvent and a Nation solution, ultrasonically treated until the mixture is uniformly dispersed, then a commercial platinum-based cathode catalyst is added, and ultrasonically treated until the mixture is uniformly dispersed, so that cathode catalyst layer slurry is prepared.
In the embodiment of the invention, the fluorinated multi-wall carbon nanotube additive has certain hydrophobicity; commercially available products can be used, but are preferably obtained in the following manner:
oxidizing the multi-walled carbon nano-tubes by a chemical method, and fluorinating the oxidized multi-walled carbon nano-tubes by using a fluorinating agent to obtain the fluorinated multi-walled carbon nano-tube additive.
The invention preferably utilizes a chemical method to carry out oxidation treatment on the multi-walled carbon nano-tube, thereby facilitating the subsequent fluorination. The surface of the multi-wall carbon nano-tube (MWCNTs) is combined with a large number of surface groups such as carboxyl and the like, and the tube diameter is generally 2-100nm; preferably, the invention adopts Hummers method to carry out higher degree oxidation, the Hummers method includes oxidation-stripping-reduction process, specifically, multiwall carbon nanotube and concentrated sulfuric acid in a certain proportion are mixed, then sodium nitrate and potassium permanganate are added, the obtained mixture is added with water and hydrogen peroxide solution for treatment, finally water washing is carried out, and vacuum drying is carried out, so as to obtain oxidized multiwall carbon nanotube (can be recorded as O-MCNT).
After the oxidation treatment, the oxidized multi-walled carbon nanotubes obtained in the present example were subjected to a fluorination treatment using a fluorinating agent. Weighing a certain amount of oxidized multi-walled carbon nanotubes and a fluorinating agent, mixing the oxidized multi-walled carbon nanotubes and the fluorinating agent in methanol, ultrasonically dispersing, and then heating for fluorination treatment to combine the multi-walled carbon nanotubes with fluorine atoms to obtain the fluorinated multi-walled carbon nanotubes (which can be recorded as F-MCNT).
Wherein, the fluorinating agent is preferably one or two of sodium fluoride and ammonium fluoride. The mass ratio of the fluorinating agent to the multi-wall carbon nano-tube subjected to oxidation treatment is preferably 1:10-1:12; preferably, the amount of methanol mixed is 50-60mL. The invention is preferably dispersed uniformly by ultrasonic, and the ultrasonic time is preferably 15-20min. The fluorination treatment is preferably carried out at 900-950 ℃, and the heat treatment time is preferably 1-1.5 h; the temperature rise rate can be set to be 5 ℃ for min -1 The heat treatment is performed under the protection of an atmosphere such as nitrogen. The embodiment of the invention can also use the obtained solid productWashing with hydrofluoric acid and water (usually deionized water), wherein the preferred concentration of hydrofluoric acid is 20-30%, which is beneficial to removing unstable substances; drying to obtain the fluorinated multi-walled carbon nanotube additive.
In the embodiment of the invention, the solvent, the Nafion solution and the obtained fluorinated multi-walled carbon nanotube additive are mixed firstly and treated by ultrasonic treatment, and the ultrasonic time is preferably 15-20min; then adding a Pt/C catalyst, mixing, and then carrying out ultrasonic treatment to uniformly disperse the mixture, wherein the ultrasonic time is preferably 30-60 min; finally obtaining the cathode catalyst layer slurry.
For the sake of convenience, the solvent in the cathode catalyst layer slurry is referred to as a first solvent, and the solvent in the anode catalyst layer slurry is referred to as a second solvent. In an embodiment of the present invention, the first solvent and the second solvent are independently selected from one or more of water, alcohol solvents, preferably both water and isopropanol. The invention adopts a Nation solution (with a concentration of 5 wt%) to further form Nafion ionomer of perfluorosulfonic acid. The Pt/C catalyst is a commonly used commercial platinum-based catalyst, involving a carbon substrate or support, and the Pt content by mass may be 60%. In the cathode catalyst layer slurry, the mass ratio of the fluorinated multi-walled carbon nanotube additive to the Pt/C catalyst carbon matrix is 1:5-1:10. More preferably, the mass ratio of the water, the Nation solution, the fluorinated multi-walled carbon nanotube additive, the Pt/C catalyst and the isopropanol is 200:15:0.1:2-3:150-160, and more preferably 200:15:0.1: 2.4: 157.
In the embodiment of the invention, F-MCNT is not added in the preparation process of the anode catalytic layer slurry, and the preparation process is similar to that of the cathode catalytic layer slurry. Preferably, water, nafion solution, pt/C catalyst and isopropyl alcohol are mixed and then subjected to ultrasonic treatment to uniformly disperse the mixture, thereby obtaining anode catalyst layer slurry. The action and parameters of the Nafion solution, pt/C catalyst involved therein are as described previously, for example: the Nafion solution was 5% in concentration and was purchased from Aldrich Chemical company.
In the anode catalyst layer slurry according to the preferred embodiment of the present invention, the mass ratio of the water, the Nafion solution, the Pt/C catalyst and the isopropyl alcohol is preferably 300: 3-4: 1-1.5: 230-240, and more preferably 300: 3.7: 1.2: 236.
In the embodiment of the invention, the prepared cathode catalyst layer slurry and anode catalyst layer slurry are sprayed on two sides of the proton exchange membrane in sequence by ultrasonic spraying, so that the membrane electrode is obtained. The ultrasonic spraying specifically comprises: the proton exchange membrane is placed on an electric hot plate at 70-90 ℃, the proton exchange membrane is fixed by using the negative pressure of an air compressor, then an ultrasonic spraying device is used, the discharging flow rate can be 0.1-0.5mL/s, preferably 0.2-0.3mL/s, and the cathode catalyst layer slurry and the anode catalyst layer slurry are respectively and uniformly sprayed on the proton exchange membrane. In the embodiment of the invention, the proton exchange membrane is a Nafion membrane of perfluorosulfonic acid, and the thickness of the Nafion membrane is 50-200 microns; more preferably 5X 5cm 2 N212 type proton exchange membrane.
The core technology of the embodiment of the invention is to adopt the hydrophobic fluorinated multi-walled carbon nanotube as the additive of the cathode catalyst layer, more specifically to realize the pre-dispersion and pre-anchoring of the ionomer in the slurry, reduce the coverage of the ionomer in the catalyst layer structure to platinum sites, improve the accessibility of oxygen and weaken the poisoning of ionomer sulfonic acid groups to platinum. Meanwhile, the additive also improves the hydrophobicity of the cathode catalyst layer, adjusts the porosity and is beneficial to the transmission of oxygen. In addition, the method for preparing the membrane electrode is simple and convenient and is easy to implement.
The invention provides a membrane electrode for a proton exchange membrane fuel cell obtained by the preparation method; the membrane layer structure is composed of an anode catalyst layer, a proton exchange membrane and a cathode catalyst layer which are sequentially compounded. Some exemplary membrane electrode specifications have a proton exchange membrane thickness of about 60 μm, an anode catalytic layer thickness of about 6 μm, and a cathode catalytic layer thickness of about 25 μm; the diffusion layer is 220 μm thick in a single piece; conventional cathode catalyst layer pore diameter ranges are for example: 3.1-192.1 nm, and the change is 3.4-283.8 nm after the carbon fluoride tube is introduced.
In the membrane electrode provided by the embodiment of the invention, the assembly form of the ionomer of the cathode catalytic layer is adjusted, the porosity of the catalytic layer is optimized, the flooding resistance of the catalytic layer is enhanced, the accessibility of oxygen to platinum sites is increased, and the utilization rate and performance expression of the platinum-based catalyst are improved. In addition, the invention also provides the following productsThe membrane electrode is applied to a proton exchange membrane fuel cell; the membrane electrode can be applied as H 2 -Air fuel cell, H 2 -O 2 The fuel cell has a high resistance to a change in humidity, and is suitable for a change in humidity in the range of 50% RH to 180% RH, for example, and is useful for practical use in proton exchange membrane fuel cells.
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention. The reagents and materials described in the following examples are commercially available, unless otherwise specified. Among these, the key specifications for MWCNTs: external diameter of 10-20nm, length less than 2 μm, purity greater than 97%, gray level less than 3%, and specific surface area of 100-160m 2 g-1。
Example 1
(1) 2g of multi-walled carbon nanotubes and 46mL of concentrated sulfuric acid were added to a beaker and mixed thoroughly with magnetic stirring for 24 hours. Next, 200mg of sodium nitrate was added. After a little stirring, 2g of potassium permanganate were slowly added to the mixture using a spatula.
(2) The resulting mixture was stirred for about 30 minutes, then 6mL of deionized water was added dropwise with a dropper, 6mL of deionized water was added dropwise after stirring for 5 minutes, and 80mL of deionized water was slowly added after stirring for 5 minutes. After 15 minutes, 280mL of deionized water and 20mL of 30% hydrogen peroxide solution were added.
(3) Stirring the obtained mixture at room temperature for 5 minutes, repeatedly washing the mixture by deionized water, and performing vacuum drying to obtain oxidized multi-walled carbon nanotubes (O-MCNT); the oxidation degree was shown by the oxygen content obtained from XPS test, specifically 17at%.
(4) 100mg of the O-MCNT obtained and 1.2g of ammonium fluoride were added to a plastic beaker, and 50mL of methanol were added and dispersed uniformly by sonication. The methanol was then evaporated to dryness with constant stirring in an oil bath at 60 ℃.
(5) The obtained mixture was transferred to a corundum boat and then placed in a corundum tube furnace. Setting the heating rate at 5 ℃ for min -1 And carrying out heat treatment at 900 ℃ for one hour under the protection of nitrogen.
(6) Diluting 40% hydrofluoric acid solution into 20% hydrofluoric acid solution in advance, washing the heat-treated product with 20% hydrofluoric acid solution to remove unstable substances, performing solid-liquid separation by suction filtration, and washing the solid with a large amount of water. Finally, drying the washed solid in a vacuum drying oven to obtain a fluorinated multi-walled carbon nanotube (F-MCNT); the degree of fluorination was 1.01at% based on the fluorine content obtained by XPS test.
(7) 2mL of deionized water, 84. Mu.L of a 5wt% Nation solution (available from Aldrich Chemical Co.) and 1mg of the resulting F-MCNT were mixed and sonicated for 20min. 24mg of a commercial 60% Pt/C catalyst and 2mL of isopropyl alcohol were added, and ultrasonic treatment was performed for 60min to obtain a cathode catalytic layer slurry.
(8) 1.5mL of deionized water, 21. Mu.L of 5wt% Nation were mixed uniformly, and 6mg of a commercial 60% Pt/C catalyst and 1.5mL of isopropyl alcohol were added, followed by ultrasonic treatment for 60min to obtain an anode catalyst layer slurry.
(9) The commercial proton exchange membrane was placed on an electric hot plate at 80 ℃ and fixed by the negative pressure of an air compressor. The slurry of the cathode and anode catalytic layers is ultrasonically sprayed on an N212 proton exchange membrane (5 multiplied by 5 cm) by utilizing an ultrasonic automatic spraying device at the discharge flow rate of 0.2mL/s 2 ) On both sides, a membrane electrode (which may be designated as F-MEA) was obtained.
The composition specification of the membrane electrode F-MEA is as follows: anode platinum loading 0.1mg cm -2 Cathode platinum loading 0.4mg cm -2 H23C2 gas diffusion layer with electrode area of 2.1X 2.1cm 2 。
In addition, this example characterizes the actual microscopic morphology of the cathode catalyst slurry used to make p-CCM (pure catalyst coated membrane) and F-CCM (catalyst coated membrane with F-MCNTs) using Cryo-electron microscopy, see comparison of Cryo-TEM photographs in FIG. 1.
FIG. 1 (a) shows a cryo-electron microscope image of a mixture of 5wt% Nation solution, deionized water and isopropanol; in a mixture of deionized water and isopropanol, the Nation exists in the form of spherical micelles with a diameter of 10-20 nm. After a certain proportion of F-MCNTs is added, as shown in figure 1 (b), the spherical micelles of the Nation ionomer are changed and are attached to the surface of the F-MCNTs to form a cross-linked structure. This phenomenon can be explained by the fact that F-MCNTs destabilize the spherical micelles of Nafion ionomer, causing them to disperse. Cryoelectron microscopy images of p-CCM and F-CCM cathode slurries are shown in FIGS. 1 (c) and (d); by careful observation of cryo-electron microscope images, it was found that there were still significant free-Nation ionomer spherical micelles at 10-20nm in fig. 1 (c), but not in fig. 1 (d). This indicates that in the cathode slurry for F-CCM preparation, almost all Nafion ionomers are adsorbed on F-MCNTs first, and then bound to catalyst particles, and there are no free micelles. This shows that the membrane electrode of the present invention improves the uniformity of ionomer distribution, reduces platinum coverage by ionomer, and promotes the formation of three-phase interface.
(10) Using a H23C2 type gas diffusion layer, the electrode area was 2.1X 2.1cm 2 . After the cell was assembled, the cell performance was tested at 80 ℃. The cathode and the anode are fed with air according to the stoichiometric ratio.
Referring to fig. 2 to 7, the right axis is Voltage (Voltage), the left axis is Power Density (Power Density), and the abscissa axis is Current Density (Current Density). The experimental results showed that, at a back pressure of 2atm, when the humidity was 180% RH, H 2 -O 2 The power density of the fuel cell at 0.6V is 1.81Wcm -2 ，H 2 Air fuel cell power density at 0.6V of 1.04Wcm -2 (ii) a When the humidity is 100% RH, H 2 -O 2 The power density of the fuel cell at 0.6V is 1.60Wcm -2 ，H 2 -Air fuel cell power density at 0.6V of 1.16Wcm -2 (ii) a When the humidity is 50% RH, H 2 -O 2 The power density of the fuel cell at 0.6V is 1.49Wcm -2 ，H 2 Air fuel cell power density at 0.6V of 0.66Wcm -2 。
Comparative example
(1) 2mL of deionized water and 84. Mu.L of a 5wt% Nafion solution were taken and mixed uniformly, and 24mg of a commercial 60% Pt/C catalyst and 2mL of isopropyl alcohol were added and subjected to ultrasonic treatment for 60min to obtain a cathode catalyst layer slurry.
(2) 1.5mL of deionized water and 21. Mu.L of a 5wt% Nafion solution were mixed uniformly, and 6mg of a commercial 60% Pt/C catalyst and 1.5mL of isopropyl alcohol were added thereto, followed by ultrasonic treatment for 60min to obtain an anode catalyst layer slurry.
(3) According to the super in example 1And in the acoustic spraying mode, the cathode and anode catalytic layer slurry is sprayed on two sides of the N212 proton exchange membrane to obtain the membrane electrode. Anode platinum loading 0.1mg cm -2 Cathode platinum loading 0.4mg cm -2 。
(4) The electrode area was 2.1X 2.1cm2 using a H23C2 type gas diffusion layer. After the cell was assembled, the cell performance was tested at 80 ℃. The cathode and the anode are fed with air according to the stoichiometric ratio.
Referring to FIGS. 2 to 7, the experimental results show that H was determined when the humidity was 180% RH at a back pressure of 2atm 2 -O 2 The power density of the fuel cell at 0.6V is 1.15Wcm -2 ，H 2 Air fuel cell power density at 0.6V of 0.59Wcm -2 (ii) a When the humidity is 100% RH, H 2 -O 2 The power density of the fuel cell at 0.6V is 1.35Wcm -2 ，H 2 Air fuel cell power density at 0.6V of 0.91Wcm -2 (ii) a When the humidity is 50% RH, H 2 -O 2 The power density of the fuel cell at 0.6V is 0.83Wcm -2 ，H 2 -Air fuel cell power density at 0.6V of 0.50Wcm -2 。
From the comparison of the performances of FIGS. 2 to 7, it can be seen that the membrane electrode prepared according to the present invention has a stronger adaptability to changes in humidity (50% RH-180% RH).
Further, the following performance comparison results are obtained through CO in-situ electrochemical impedance spectroscopy test, so that the improved humidity adaptability of the membrane electrode is further illustrated.
TABLE 1F-MEA prepared according to the examples of the present invention having different changes in properties at different humidities
| 50 |
100％RH | 180％RH | |
| p-MEA-ΘPt | 33.7％ | 11.2％ | 8.6％ |
| F-MEA-ΘPt | 8.6％ | 4.6％ | 3.5％ |
Coverage of Pt-Nafion sulfonic acid group on platinum site
According to the embodiments, the method mainly utilizes the fluorinated multi-walled carbon nanotube as the additive of the cathode catalyst layer slurry, adjusts the assembly form of the ionomer of the cathode catalyst layer, optimizes the porosity of the catalyst layer, enhances the flooding resistance of the catalyst layer, and increases the accessibility of oxygen to the platinum site. The method for preparing the membrane electrode is simple and easy to implement, realizes stronger adaptability of the membrane electrode to humidity change (50 percent RH-180 percent RH), and is beneficial to application.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes may be made without departing from the principle of the present invention, and the technical features described above may be combined in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.
Claims (10)
1. A preparation method of a membrane electrode for a proton exchange membrane fuel cell is characterized by comprising the following steps:
s1, mixing a Nafion solution, a fluorinated multi-walled carbon nanotube additive, a Pt/C catalyst and a first solvent, and then carrying out ultrasonic treatment to obtain cathode catalyst layer slurry;
mixing the Nation solution, the Pt/C catalyst and a second solvent, and then carrying out ultrasonic treatment to obtain anode catalyst layer slurry;
and S2, respectively spraying the cathode catalyst layer slurry and the anode catalyst layer slurry on two sides of the proton exchange membrane through ultrasonic spraying to obtain the membrane electrode.
2. The method of preparing a membrane electrode according to claim 1, wherein the fluorinated multi-walled carbon nanotube additive is obtained by: oxidizing the multi-walled carbon nano-tubes by a chemical method, and fluorinating the oxidized multi-walled carbon nano-tubes by using a fluorinating agent to obtain the fluorinated multi-walled carbon nano-tube additive.
3. The method of preparing a membrane electrode according to claim 2, wherein the chemical method is Hummers method; the fluorinating agent is one or two of sodium fluoride and ammonium fluoride.
4. The method for producing a membrane electrode according to claim 3, wherein the mass ratio of the fluorinating agent to the oxidized multi-walled carbon nanotube is 1:10-1:12; the fluorination treatment is heat treatment at 900-950 ℃.
5. The method for preparing a membrane electrode according to any one of claims 1 to 4, wherein the first solvent and the second solvent are independently selected from one or more of water, alcohol solvents; in the cathode catalyst layer slurry, the mass ratio of the fluorinated multi-walled carbon nanotube additive to the Pt/C catalyst carbon substrate is 1:5-1:10.
6. the method of preparing a membrane electrode according to claim 5, wherein the first solvent and the second solvent are each a mixture of water and isopropyl alcohol; in the cathode catalyst layer slurry, the mass ratio of the water, the Nation solution, the fluorinated multi-walled carbon nanotube additive, the Pt/C catalyst and the isopropanol is 200:15:0.1:2-3:150-160.
7. The membrane electrode preparation method according to claim 5, wherein the ultrasonic spraying specifically comprises: and (2) placing the proton exchange membrane on an electric hot plate at 70-90 ℃, fixing by using negative pressure, and then respectively spraying the cathode catalyst layer slurry and the anode catalyst layer slurry by using ultrasonic spraying equipment, wherein the discharging flow rate is 0.1-0.5mL/s.
8. The method for preparing a membrane electrode according to claim 7, wherein the proton exchange membrane is a Nafion perfluorosulfonate membrane having a thickness of 50 to 200 μm.
9. A membrane electrode for a proton exchange membrane fuel cell obtained by the production method according to any one of claims 1 to 8.
10. The membrane electrode of claim 9, wherein said membrane electrode is adapted to address a humidity change of 50-180% rh.
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