CN113839049A - Fuel cell membrane electrode and preparation method thereof - Google Patents
Fuel cell membrane electrode and preparation method thereof Download PDFInfo
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- CN113839049A CN113839049A CN202111125137.6A CN202111125137A CN113839049A CN 113839049 A CN113839049 A CN 113839049A CN 202111125137 A CN202111125137 A CN 202111125137A CN 113839049 A CN113839049 A CN 113839049A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04664—Failure or abnormal function
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04828—Humidity; Water content
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a fuel cell membrane electrode which is of a five-layer structure and comprises two gas diffusion layers, two catalyst layers and an electrolyte membrane; the electrolyte membrane is positioned in the middle of the five-layer structure, and two catalytic layers are distributed on two sides of the electrolyte membrane respectively; and a gas diffusion layer is arranged outside each catalytic layer. The gas diffusion layer comprises a support layer and a microporous layer between the catalytic layer and the support layer; the supporting layer is made of carbon paper or carbon cloth; the microporous layer is deposited on the supporting layer and is connected with the supporting layer and the catalytic layer; the catalytic layer includes a catalyst and a binder. The invention improves the utilization rate of the catalyst and the output performance of the battery; by changing the material and preparation process of the microporous layer, the mass transfer is enhanced, and the output performance of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a fuel cell membrane electrode, a preparation method, a detection device, preparation equipment and a single fuel cell.
Background
The twenty-first century is a century of energy conservation, energy transition and environmental protection. The development of novel clean energy, the reasonable utilization of the existing energy and the coordinated development of environmental protection become the foundation of the economic development of the world in the century. At present, fossil energy such as petroleum, natural gas and coal, which human beings rely on for survival, is decreasing day by day, and hydrogen energy and renewable energy are used instead. Meanwhile, because of the inefficient combustion and use of petroleum, natural gas and coal, not only energy is wasted, but also the environment is seriously polluted. Therefore, saving energy and developing new energy, improving the utilization rate of fuel, and reducing pollution caused by fuel combustion become important problems to be solved in this century.
Fuel Cells (FC) are power generation devices that directly convert chemical energy into electrical energy without a combustion process, and the best Fuel is hydrogen, and fossil Fuel can be used, so that the FC has the outstanding advantages of high energy conversion efficiency, low pollution and environmental friendliness, is considered as the first choice of clean and efficient power generation technology in the 21 st century, and becomes the focus of research and development of governments and major corporations.
Proton Exchange Membrane Fuel Cells (PEMFCs) are a fifth generation of Fuel Cells that are being developed after Alkaline Fuel Cells (AFCs), phosphate Fuel Cells (PAFCs), Molten Carbonate Fuel Cells (MCFCs), and Solid Oxide Fuel Cells (SOFCs). Besides the common characteristics of other fuel cells, the fuel cell has the advantages of high specific power and specific energy, capability of being started quickly at room temperature, no electrolyte corrosion and overflow leakage, and the like, so the PEMFC has wide application prospect in the aspects of being used as a power source of an electric automobile, a mobile power source, a dispersed power station, and the like.
PEMFCs have been commercialized at the night since the technology thereof matured over several decades. However, in order to realize large-scale use of PEMFCs, breakthroughs in key technologies and key materials must be made to ensure stability and reliability of PEMFCs, and at the same time, cost of PEMFCs is greatly reduced. Membrane Electrode Assemblies (MEAs) are the core components of PEMFCs and are key factors affecting PEMFCs specific power density, energy density distribution, and their operating life. The current MEA studies show that the problems with MEA are mainly concentrated on: the mechanism of substance transport in the electrodes is not clear; the catalyst layer and the gas diffusion layer are unreasonable in structure, so that the catalyst utilization rate is low, the transfer resistance of reaction gas and liquid water is high, and the concentration polarization loss of a high current density area is large; the battery output performance is to be improved.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a fuel cell membrane electrode, a preparation method, a detection device, a preparation apparatus, and a single fuel cell, which solve the technical problems of low utilization rate and low output performance of the existing fuel cell.
The technical scheme adopted by the invention is as follows:
the invention provides a fuel cell membrane electrode which is of a five-layer structure and comprises two gas diffusion layers, two catalyst layers and an electrolyte membrane; the electrolyte membrane is positioned in the middle of the five-layer structure, and two catalytic layers are distributed on two sides of the electrolyte membrane respectively; a gas diffusion layer is arranged on the outer side of each catalytic layer;
the gas diffusion layer 3 includes a support layer 31 and a microporous layer 32, the microporous layer 32 being between the catalytic layer 2 and the support layer 31; the supporting layer is made of carbon paper or carbon cloth; the microporous layer is deposited on the supporting layer and is connected with the supporting layer and the catalytic layer;
the catalytic layer includes a catalyst and a binder.
Further, the microporous layer is a hydrophilic microporous layer and comprises a microporous material and a hydrophilic coating layer deposited on the microporous material, the hydrophilic coating layer is in contact with the supporting layer, and the microporous material is in contact with the catalytic layer;
the content of the hydrophilic coating is 2-8% of the total weight of the microporous layer, the hydrophilic coating comprises hydrophilic polymers, and the hydrophilic polymers comprise one or more of polyvinyl alcohol (PVA), polyvinyl pyridine (PVP), polyacrylic acid (PAA), polyacrylamide (polyacrylamide), polyallylamine (polyallyamine), polyethyleneimine (polyethylenimine), polyalkyloxazoline and polyalkylamine;
the thickness of the hydrophilic microporous layer is greater than 1.2 μm;
the specific surface area of the microporous material is more than 55m2/g；
The average particle size of the microporous material is more than 30 nm;
the microporous material is a carbon-based material and comprises one or more of carbon nano tubes, carbon nano fibers, activated carbon nano wires, activated carbon, carbon black and graphite.
Further, the catalytic layer adopts a double-layer structure, and the catalyst adopts Pt/C; firstly preparing 40 wt.% Pt/C catalytic layer and then preparing 20 wt.% Pt/C catalytic layer on the gas diffusion layer; in contact with the electrolyte membrane is 20 wt.% of a Pt/C catalytic layer; in contact with the gas diffusion layer was a catalytic layer of 40 wt.% Pt/C.
The present invention also provides a fuel cell membrane electrode detection apparatus, the fuel cell membrane electrode detection apparatus 100 including: a movement driver 110, a first humidifier 120, a pressure driver 130, a second humidifier 140, a control unit 150, and an electronic load 160;
the moving driver 110 is used for continuously moving the fuel cell membrane electrode 10, and two catalytic layers are respectively adhered to two sides of the electrolyte membrane 1, wherein one catalytic layer is an anode 12, and the other catalytic layer is a cathode 13;
the first humidifier 120, which is used for humidifying the fuel cell membrane electrode 10, includes a humidifier 121 mounted on the anode side and a humidifier 122 mounted on the cathode side;
the pressure driver 130 includes a conductive heating jig which is in contact with the fuel cell membrane electrode 10, and presses the conductive heating jig against the fuel cell membrane electrode 10 by moving the conductive heating jig; the conductive heating jig includes a first conductive heating jig 131 disposed on the anode 12 side and a second conductive heating jig 132 disposed on the cathode 13 side; the first conductive heating clamp 131 is provided with a first gas inlet and a first gas outlet; the second conductive heating clamp 132 is provided with a second gas inlet and a second gas outlet;
the second humidifier 140 supplies the fuel cell membrane electrode 10 with gas through the first gas inlet and the second gas inlet, respectively, the gas being humidified while passing through the first diffuser 141 and the second diffuser 142;
the control unit 150 is used to control the entire fuel cell membrane electrode detection apparatus 100 while detecting the temperatures of the first and second conductive heating jigs 131 and 132, and the flow rates of the supplied gases;
the electronic load 160 is used to control and measure the voltage or current between the anode 12 and the cathode 13, and the voltage or current between the first conductive heating jig 131 and the second conductive heating jig 132.
Further, the fuel cell membrane electrode detection apparatus 100 further includes:
a gasket 14, said gasket 14 being mounted on the fuel cell membrane electrode 10;
and the marking unit 170 is used for marking the grade or the activity of the fuel cell membrane electrode after detection.
Furthermore, the fuel cell membrane electrode detection device also comprises an alarm system, wherein the alarm system is connected with the control unit and comprises a first NAND gate, a second NAND gate, a key switch, a light emitting diode and an alarm; the cathode of the light emitting diode is connected with the output end of the first NAND gate and the input end of the second NAND gate, and the anode of the light emitting diode is connected with a power supply; the output end of the second NAND gate is sequentially connected with an NPN triode, an oscillator and an alarm;
when the fuel cell membrane electrode detection device works normally, the key switch is in a closed state, the first NAND gate outputs high level, the light-emitting diode does not emit light, the second NAND gate outputs low level, the oscillator does not work, and the alarm does not sound;
when the detector detects a dangerous factor, the detector outputs a negative pulse to the alarm circuit, the first NAND gate outputs a low level to enable the light emitting diode to be conducted and emit light, the second NAND gate outputs a high level to enable the oscillator to work, and the alarm gives an alarm;
after the dangerous factors are eliminated, the key switch is pressed down, and the acousto-optic alarm is stopped.
Further, the risk factors include hydrogen leakage, smoke, and the like.
The invention also provides a preparation method of the fuel cell membrane electrode, which comprises the following steps:
step S1, electrolyte membrane pretreatment, specifically including the steps of:
step S11, putting the electrolyte membrane into 6 wt.% hydrogen peroxide solution to boil for 1h, and removing organic and inorganic impurities in the electrolyte membrane; removing residual hydrogen peroxide solution on the surface by using deionized water;
step S12, placing the electrolyte membrane in 0.6 mol.L-1Boiling the sulfuric acid solution for 1h to ensure that the electrolyte membrane is re-protonated;
step S13, drying the processed electrolyte membrane in a vacuum drying oven;
step S2, preparing a gas diffusion layer, wherein the supporting layer is made of carbon paper, and the method specifically comprises the following steps:
step S21, soaking the carbon paper in a PTFE solution, and then drying the carbon paper;
step S22, carrying out ultrasonic dispersion on PTFE and carbon black in an ethanol solution to form a mixture;
step S23, uniformly spraying the mixture on the surface of one side of the carbon paper to form a microporous layer;
and step S24, sintering at 340 ℃ in a high-temperature furnace, melting the PTFE in the carbon paper and the PTFE in the microporous layer, and bonding the carbon paper and the PTFE together.
Step S3, preparing a catalytic layer, specifically including the steps of:
step S31, mixing PTFE, a catalyst and glycerol to form a primary mixture;
step S32, performing ultrasonic dispersion on the primary mixture in an ethanol solution to form a secondary mixture;
step S33, uniformly spraying the mixture on a gas diffusion layer, and drying to form a gas diffusion electrode;
step S34, sintering the gas diffusion electrode in a high temperature furnace at 340 ℃;
step S35, evenly spraying Nafion solution on the surface of the catalyst to finish the three-dimensional process of the gas diffusion electrode; after the Nafion solution is dried, the film is cast;
and step S4, cutting the gas diffusion electrodes into squares, hot-pressing the two cut gas diffusion electrodes and the pretreated electrolyte membrane, and taking out to finish the preparation of the membrane electrode of the fuel cell.
Further, in step S31, the catalyst includes one or more of platinum, palladium, iridium, ruthenium, vanadium, rhodium, gold, silver, cobalt, nickel, and iron, and the mass ratio of the catalyst to the PTFE is 1: 1 to 50: 1;
in the step S33, the drying temperature is between 40 ℃ and 50 ℃, and the drying time is between 40 minutes and 1 hour;
in the step S35, the drying time of the Nafion solution is between 3 hours and 5 hours;
in the step S4, the hot pressing temperature is between 120 and 250 ℃, and the hot pressing time is between 20 and 200 seconds.
The present invention also provides an apparatus for preparing a fuel cell membrane electrode, comprising:
two gas diffusion electrode supply rollers for conveying one gas diffusion electrode in one direction, respectively, the gas diffusion electrode including a gas diffusion layer and a catalytic layer bonded together;
an electrolyte membrane supply roller for conveying an electrolyte membrane between two gas diffusion electrodes;
a pair of upper and lower heat transfer rollers sandwiching the two gas diffusion electrodes and the electrolyte membrane therebetween for hot pressing;
a gas diffusion electrode supply roller is respectively arranged above the upper heat transfer roller and below the lower heat transfer roller;
each gas diffusion electrode supply roller is provided with a synchronous detection and control unit for detecting whether the two gas diffusion electrodes move synchronously or not, and if not, synchronizing the two gas diffusion electrodes.
The invention also provides a single fuel cell, which comprises a membrane electrode, a flow field plate and a flow collecting plate; the membrane electrode is positioned at the central position of the single fuel cell; the flow field plates are arranged on two sides of the membrane electrode and connected with the gas diffusion layer, and the flow field plates are made of graphite; and the current collecting plates are arranged on two sides of the flow field plate and are made of copper.
Compared with the prior art, the invention has the advantages of optimizing the structures of the catalyst layer and the gas diffusion layer, improving the utilization rate of the catalyst and the output performance of the cell, reducing the cost of MEA in the fuel cell, improving the performance of the MEA, and being beneficial to promoting the practicability of the fuel cell.
Drawings
FIG. 1 is a view showing the structure of a membrane electrode according to the present invention;
FIG. 2 is a schematic view of a gas diffusion layer according to the present invention;
FIG. 3 is a schematic diagram of a gas diffusion layer prepared by spraying according to the present invention;
FIG. 4 is a diagram illustrating a screen printing method for preparing a gas diffusion electrode catalyst layer according to the present invention;
FIG. 5 is a schematic view of the present invention showing a gas diffusion electrode formed by a dipping method;
FIG. 6 is a schematic view of the present invention showing a gas diffusion electrode formed by a brush coating method;
FIG. 7 shows a first embodiment of a structure for preparing a double hydrophilic catalyst layer according to the present invention;
FIG. 8 is a second embodiment of a dual hydrophilic catalytic layer fabrication structure according to the present invention;
FIG. 9 is a view showing the construction of a membrane electrode assembly according to the present invention;
fig. 10 is a diagram of the alarm system of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be further described with reference to the accompanying drawings and specific examples.
The first embodiment is as follows:
the present invention provides a fuel cell Membrane Electrode Assembly (MEA) as shown in fig. 1. The Membrane Electrode can divide the MEA of the PEMFC into a Gas Diffusion Electrode (GDE) and a catalytic Electrode Membrane (CCM) according to the difference of a Catalyst support layer (Backing/Substrate) in the Catalyst layer preparation process. The membrane electrode comprises three parts: a Gas Diffusion Layer (GDL)3, a catalyst layer 2, and an electrolyte membrane 1, which is a polymer electrolyte membrane, preferably a Proton Exchange Membrane (PEM). The polymer electrolyte membrane together with the catalytic layers 2 on both sides is called a three-layer membrane electrode; the two sides of the three-layer membrane electrode are respectively clamped by a gas diffusion layer, and the five-layer membrane electrode is formed after hot pressing. The microporous layer is preferably a mixture of carbon black and PTFE deposited on the support layer, connecting the support layer and the catalytic layer.
The polymer electrolyte membrane serves as a "separator" between the cathode and the anode, and must be capable of preventing the mutual permeation of reaction gases, conducting ions, and also have electronic insulation properties. In the specific embodiment, a perfluoro sulfonic acid type proton exchange membrane manufactured by DuPont, U.S. is preferably used, and has good stability and high proton conductivity, and the proton exchange membrane comprises Nafion112, Nafion115, Nafion117 and other brands.
The gas diffusion layer 3 is in direct contact with the fuel cell flow field plate. The gas diffusion layer is a key component for connecting the flow field plate and the catalytic layer, and is responsible for supporting the catalytic layer and collecting reaction current. The reaction gas flows through the gas diffusion layer and enters the catalyst layer, and the generated current is collected through the gas diffusion layer and then conducted to the flow field plate.
The gas diffusion layer 3 includes a support layer 31 and a microporous layer 32, as shown in fig. 2. The existing gas diffusion Layer has no Micro-Porous Layer (MPL), the catalyst Layer 2 is directly prepared on carbon paper or carbon cloth, and a part of catalyst powder directly falls into gaps of the carbon paper or the carbon cloth, so that a great deal of catalyst waste is caused. An important structural breakthrough in the gas diffusion layer 3 according to the invention is the introduction of a microporous layer, after which the carbon paper or carbon cloth is referred to as support layer 31. Before the catalyst layer is prepared, a mixture of carbon black and Polytetrafluoroethylene (PTFE) is prepared on the support layer in advance, so that the carbon paper or carbon cloth enters gaps to play a role in connecting carbon fibers with the catalyst layer, and the contact resistance is reduced while the catalyst consumption is reduced.
The gas diffusion layer 3 functions to support the catalytic layer 2, and thus carbon materials of the same material as the catalyst support are the first choice for the gas diffusion layer, such as carbon paper and carbon cloth. The supporting layer 31 of the present invention preferably uses carbon paper as the material of the supporting layer.
The catalyst layer 2 is a place where the reaction gas undergoes oxidation-reduction. The composition of the catalytic layer, in addition to the catalyst, also requires a binder to ensure the stability of the catalytic layer 2. The adhesive of the catalyst layer mainly adopts PTFE and Nafion, and the Gas Diffusion Electrode (GDE) can be divided into two types of hydrophobic hydrophilic type according to the physical property of the adhesive.
Example two:
the invention also provides a preparation method of the fuel cell membrane electrode, which comprises the following steps:
step S1, proton exchange membrane pretreatment, because the proton exchange membrane is stored for a long time before use, impurities in the proton exchange membrane are removed.
Step S1 specifically includes the following steps:
step S11, putting the proton exchange membrane into 6 wt.% hydrogen peroxide solution to boil for 1h, and removing organic and inorganic impurities in the proton exchange membrane; washing with deionized water for many times to remove residual hydrogen peroxide on the surface;
step S12, putting the proton exchange membrane into the reactor, wherein the proton exchange membrane is 0.6 mol.L-1Boiling the solution for 1h to re-protonate the proton exchange membrane;
and step S13, drying the treated proton exchange membrane in a vacuum drying oven for use.
The membrane electrode prepared by the invention preferably adopts a Nafion112 membrane as a polymer electrolyte membrane.
Step S2, preparing a gas diffusion layer, wherein the support layer is preferably carbon paper, and the microporous layer is a mixture of carbon black and PTFE.
Step S2 specifically includes the following steps:
step S21, soaking the carbon paper in 62.5 wt.% PTFE solution, and then drying the carbon paper;
step S22, carrying out ultrasonic dispersion on PTFE and carbon black in an ethanol solution to form a mixture;
step S23, uniformly spraying the mixture on the surface of one side of the carbon paper to form a microporous layer;
and step S24, sintering at 340 ℃ in a high-temperature furnace to make the gas diffusion layer have hydrophobicity. After the gas diffusion layer is sintered, the PTFE in the carbon paper and the PTFE in the microporous layer are mutually bonded after being melted, so that the gas diffusion layer is tightly bonded, and the stability of the electrode can be improved.
Fig. 3 is a schematic diagram of a gas diffusion layer prepared by spraying, in which a processing object is placed under a spray gun, and then the air inlet pressure is adjusted, so that the mixture in the medicine pool is sprayed out under a certain pressure, and is dispersed in a foggy manner and uniformly dispersed on a processing sample. The sprayed material is uniformly dispersed by adjusting the flow rate of the sprayed material and the moving speed of the spray gun.
Step S3, preparation of the catalytic layer,
the catalytic layer of the electrode comprises a hydrophobic electrode and a hydrophilic electrode. The preparation process is also different according to the difference of hydrophobicity and hydrophilicity. The hydrophobic electrode adopts PTFE as a binder of the Pt/C catalyst, so that the mass transfer resistance of gas in the catalytic layer is very small, and the electrode can be ensured to react under the condition of high humidity of reaction gas. Unlike hydrophobic electrodes, the hydrophilic catalyst layer uses Nafion as a binder, which has the function of proton channels in addition to the binding function.
The preparation process of the hydrophobic catalysis layer specifically comprises the following steps:
step S31, mixing PTFE, a catalyst and glycerol to form a primary mixture, wherein the catalyst adopts Pt/C, and PTFE is used as a binder of the Pt/C catalyst;
step S32, performing ultrasonic dispersion on the primary mixture in an ethanol solution to form a secondary mixture;
step S33, uniformly spraying the mixture on a gas diffusion layer, and drying to form a gas diffusion electrode;
step S34, sintering the gas diffusion electrode in a muffle furnace at 340 ℃;
step S35, evenly spraying Nafion solution on the surface of the catalyst to finish the three-dimensional process of the gas diffusion electrode; standby; this Nafion solution formed a recast film (recast film) after drying.
The preparation of hydrophilic catalyst layer and hydrophobic electrode only differs on the catalyst layer:
mixing Nafion, a catalyst and glycerol according to a certain proportion;
ultrasonically dispersing the mixture in an ethanol solution;
and uniformly spraying the mixture on the gas diffusion layer, and drying for later use.
From the preparation process, the hydrophobic electrode needs to be sprayed twice in the preparation stage of the catalyst layer, and the preparation process of the catalyst layer of the hydrophilic electrode only needs to be sprayed once. Obviously, from the preparation procedure, the catalytic layer of the hydrophilic electrode is more beneficial to the preparation of the membrane electrode. The GDE of the invention preferably adopts a hydrophilic catalytic layer structure, and the platinum loading in each GDE catalytic layer is 0.3 mg-cm-2。
And step S4, hot pressing the membrane electrode. The hot pressing device of the membrane electrode adopts a flat plate hot press. Cutting GDE into 5cm pieces with a blade2A square of size. And hot-pressing the two cut GDEs and the pretreated proton exchange membrane for a certain time at a certain temperature and under a certain pressure, and then taking out the GDEs and the pretreated proton exchange membrane to obtain the membrane electrode of the fuel cell.
In addition to the preparation of the catalytic layer, the catalytic layer may be prepared by a screen printing method, as shown in fig. 4, in addition to the above two spray coating methods. The screen printing method comprises the following specific steps: substances such as Pt/C catalyst, PTFE and glycerol are prepared into paste 21. The paste is then repeatedly squeezed by a squeegee so as to penetrate the mesh 23 and reach the surface of the gas diffusion layer 3. After a catalyst layer with a certain mass is uniformly formed, GDE is obtained.
Preferably, in order to improve the utilization rate of the hydrophobic electrode catalyst, a proton channel needs to be prepared to the inside of the catalytic layer. The proton channel has three preparation modes, and Nafion can enter the hydrophobic catalysis layer by dipping, brushing and spraying the surface of the hydrophobic electrode, so that a three-phase reaction zone in the catalysis layer is enlarged. This process is called three-dimensional formation of the electrodes. The concrete examples include three methods of dipping method, brushing method and spraying method
FIG. 5 is a schematic diagram of a gas diffusion electrode for making a hydrophobic electrode catalyst layer into a three-dimensional structure by dipping. The dipping method is to dip the side of the gas diffusion electrode 4 on which the catalyst layer is formed into a Nafion-containing solution 5 a plurality of times depending on the concentration of the solution. The Nafion hairs are attracted to the inside of the hydrophobic electrode catalyst layer by surface tension between the catalyst layer particles.
FIG. 6 is a schematic view showing a gas diffusion electrode of a water repellent electrode formed into a three-dimensional shape by a brush coating method. The gas diffusion electrode 4 was fixed on a table with the catalytic layer side up. A brush 6 is adopted to dip Nafion solution, and brush coating is repeatedly carried out on the surface of the catalyst layer until the Nafion is uniformly distributed and the required amount is achieved.
The schematic drawing of the spraying process gas diffusion electrode is shown in fig. 3. The same method as the spraying method for preparing the gas diffusion layer.
Preferably, membrane electrodes are made with different catalytic layer compositions, further looking at the reactive layer within the hydrophilic catalytic layer. The preparation structure of the double hydrophilic catalyst layer is shown in fig. 7 and fig. 8.
In fig. 7, a 20 wt.% Pt/C catalytic layer 221 was prepared on the gas diffusion layer 3, followed by a 40 wt.% Pt/C catalytic layer 222 of the same platinum loading. After the membrane-forming electrode is prepared, the Pt/C catalyst layer 222 is 40 wt.% in contact with the proton exchange membrane; and in contact with the GDL is 20 wt.% Pt/C catalytic layer 221.
The preparation process in fig. 8 is reversed from that in fig. 7. On top of the gas diffusion layer, first a 40 wt.% Pt/C catalytic layer 222 was prepared, and then a 20 wt.% Pt/C catalytic layer 221 with the same platinum content was prepared. After the membrane-forming electrode was prepared, a catalytic layer of 20 wt.% Pt/C was in contact with the proton exchange membrane, and a catalytic layer of 40 wt.% Pt/C was in contact with the gas diffusion layer. Since the total amount of catalyst used in the catalyst layers in fig. 7 and 8 is the same, the uniformity of the thickness of the catalyst layers between the proton exchange membrane and the gas diffusion layers is ensured.
The test results show that the discharge performance of fig. 8 is superior to that of fig. 7. The polarization current in fig. 8 is higher than the density in fig. 7 at the same potential in all ranges of the polarization curve. As the analysis indicated previously, the two membrane electrodes had the same thickness of catalyst layers, i.e., the same length of proton channels, and the shadow response to membrane electrode performance was mainly based on the distribution of the different Pt/C catalysts.
When the Pt/C catalyst on the side close to the gas diffusion layer is 20 wt.% in the hydrophilic catalytic layer, the polarization performance of the membrane electrode is lower than that of the Pt/C catalyst on the side close to the gas diffusion layer, which is 40 wt.% in the hydrophilic catalytic layer.
The reactive layer of fig. 7 is 20 wt.% Pt/C catalyst, and the electrochemical reaction preferentially proceeds during contact with the gas diffusion layer. The 20 wt.% Pt/C catalyst provides limited reactive sites, which affect the membrane electrode performance. The reactive layer of fig. 8, which is also the catalytic layer in contact with the gas diffusion layer, provides more reactive sites when the redox reaction is performed in the reactive layer, since the content of 40 wt.% of the catalytic platinum is twice that of the catalytic layer of fig. 7, and the contact area with Nafion is larger, and thus the performance of fig. 8 is significantly higher than that of fig. 7.
Example three:
the invention also provides a fuel cell membrane electrode detection device, as shown in fig. 9, for detecting the power generation performance, activity and grade of the membrane electrode. The fuel cell membrane electrode detection device 100 includes: a movement driver 110, a first humidifier 120, a pressure driver 130, a second humidifier 140, a control unit 150, an electronic load 160, and a marking unit 170.
The moving driver 110 is used for continuously moving the fuel cell membrane electrode 10, and two catalytic layers are respectively attached to two sides of the electrolyte membrane 1, wherein one catalytic layer is an anode 12, and the other catalytic layer is a cathode 13. The gasket 14 is continuously joined to the edge areas of both sides of the membrane electrode 10.
The first humidifier 120 hydrates electrolytes included in electrodes (an anode 12 and a cathode 13) at both sides of the polymer electrolyte membrane 1 and the membrane electrode 10, to which the gasket 14 is attached, thereby generating hydrogen gas during the reaction. The first humidifier 120 includes a humidifier 121 mounted on the anode side and a humidifier 122 mounted on the cathode side for humidifying the fuel cell membrane electrode 10. The humidifier 121 and the humidifier 122 may be moved by a moving mechanism. The humidifier in the embodiment of the present invention is a direct injection type humidifier in which moisture is directly supplied through an electromagnetic valve, but various types of humidifiers may be used.
The pressure driver 130 includes an electrically conductive heating jig which is in contact with the fuel cell membrane electrode 10 and which is pressed against the fuel cell membrane electrode 10 by moving the electrically conductive heating jig, and a gas inlet and outlet. The conductive heating jig includes a first conductive heating jig 131 provided on the anode 12 side and a second conductive heating jig 132 provided on the cathode 13 side, and can be lifted and lowered by a not-shown driving mechanism. The first conductive heating clamp 131 is provided with a first gas inlet and a first gas outlet; the second conductive heating jig 132 is provided with a second gas inlet and a second gas outlet.
The first and second conductive heating jigs 131 and 132 are stacked inside the first and second heating plates 131a and 132a, respectively, to supply fuel and discharge water generated by the reaction. The gas diffusion layer 3 includes a first gas diffusion layer 131c and a second gas diffusion layer 132c, the first gas diffusion layer 131c being laminated inside the first separator 131b, and the second gas diffusion layer 132c being laminated inside the second separator 132 b. The first sealing gasket 131d is laminated along the edge of the first gas diffusion layer 131c, and the second sealing gasket 132d is laminated along the edge of the second gas diffusion layer 132 c.
A first gas inlet and a first gas outlet for supplying hydrogen and nitrogen to the anode 12 of the membrane electrode 10 through the first heating plate 131a and the first separator 131b and discharging nitrogen from the anode 12. The second gas inlet and the second gas outlet are used to supply air (or oxygen) and nitrogen to the cathode 13 of the membrane electrode 10 through the second heating plate 132a and the second separator 132b, and to discharge nitrogen from the cathode 13.
The pressure of the membrane electrode output can be evaluated near the first gas outlet of the first conductive heating jig 131 and near the second gas outlet of the second conductive heating jig 132. The first conductive heating jig 131 is provided with a first control valve 131e in a pressurized state, and the second conductive heating jig 132 is provided with a second control valve 132e in a pressurized state. In addition, load cells for sensing a load are installed on the driving mechanism of the pressure driver 130 or the first conductive heating jig 131 and the first conductive heating jig 132 to adjust the pressurized states of the first conductive heating jig 131 and the first conductive heating jig 132.
The second humidifier 140 supplies the fuel cell membrane electrode 10 with gas through the first gas inlet and the second gas inlet, respectively, and the gas is humidified while passing through the first diffuser 141 and the second diffuser 142. The second humidifier 140 may have a structure humidified by a humidifying membrane method that supplies moisture to the flowing gas using a polymer separation membrane. The permselective membrane used in the wet membrane method is preferably a hollow fiber membrane having a large permeation area per unit volume.
The control unit 150 is used to control the entire fuel cell membrane electrode detection apparatus 100 while detecting the temperatures of the first and second conductive heating jigs 131 and 132, and the flow rates of the supplied gases.
The electronic load 160 is used to control and measure a voltage or current applied between the anode 12 and the cathode 13, and to control and measure a voltage or current between the first conductive heating jig 131 and the second conductive heating jig 132.
The marking unit 170 determines and marks the grade or activity of the membrane electrode 10 according to the power generation performance test or the activity test. The marking unit 170 marks the membrane electrode 10 in a manner recognizable by a printer, a punch, or the like.
The hydrogen originally belongs to flammable and explosive gas, and the hydrogen becomes more unstable due to high temperature and high pressure, so that the detection device further comprises alarm systems 180 for ensuring safety and preventing safety accidents caused by hydrogen leakage, as shown in fig. 10. Once hydrogen leakage is detected, the alarm system can immediately alarm and shut down the detection device. Meanwhile, in order to ensure the safety of detection personnel and all equipment and instruments, the alarm system can also monitor and alarm the memorability of dangerous factors such as smoke and fire.
The fuel cell membrane electrode detection device alarm system 180 is connected with the control unit 150, and comprises a first nand gate 1801, a second nand gate 1802, a key switch 1803, a light emitting diode 1804 and an alarm 1808; the cathode of the light emitting diode 1804 is connected with the output end of the first NAND gate 1801 and the input end of the second NAND gate 1802, and the anode of the light emitting diode 1804 is connected with the power supply 1809; the output end of the second nand gate 1802 is sequentially connected with an NPN triode 1805, an oscillator 1807 and an alarm 1808; the oscillator 1807 is composed of a transformer 1806 and a capacitor.
When the fuel cell membrane electrode detection device works normally, the key switch is in a closed state, the first NAND gate outputs high level, the light-emitting diode does not emit light, the second NAND gate outputs low level, the oscillator does not work, and the alarm does not sound;
when the detector detects a dangerous factor, the detector outputs a negative pulse to the alarm circuit, the first NAND gate outputs a low level to enable the light emitting diode to be conducted and emit light, the second NAND gate outputs a high level to enable the oscillator to work, and the alarm gives an alarm;
after the dangerous factors are eliminated, the key switch is pressed down, and the acousto-optic alarm is stopped.
Example four:
the present invention also provides an apparatus for preparing a fuel cell membrane electrode, comprising:
two gas diffusion electrode supply rollers for conveying one gas diffusion electrode in one direction, respectively, the gas diffusion electrode including a gas diffusion layer and a catalytic layer bonded together;
an electrolyte membrane supply roller for conveying an electrolyte membrane between two gas diffusion electrodes;
a pair of upper and lower heat transfer rollers sandwiching the two gas diffusion electrodes and the electrolyte membrane therebetween for hot pressing;
a gas diffusion electrode supply roller is respectively arranged above the upper heat transfer roller and below the lower heat transfer roller;
each gas diffusion electrode supply roller is provided with a synchronous detection and control unit for detecting whether the two gas diffusion electrodes move synchronously or not, and if not, synchronizing the two gas diffusion electrodes.
Example five:
the invention also provides a single fuel cell, which comprises a membrane electrode, a flow field plate and a flow collecting plate; the membrane electrode is positioned at the central position of the single fuel cell; the flow field plates are arranged on two sides of the membrane electrode and connected with the gas diffusion layer, and the flow field plates are made of graphite; and the current collecting plates are arranged on two sides of the flow field plate and are made of copper.
It should be noted that the foregoing is only illustrative and illustrative of the present invention, and that any modifications and alterations to the present invention are within the scope of the present invention as those skilled in the art will recognize.
Claims (10)
1. The fuel cell membrane electrode is characterized by having a five-layer structure and comprising two gas diffusion layers, two catalyst layers and an electrolyte membrane; the electrolyte membrane is positioned in the middle of the five-layer structure, and two catalytic layers are distributed on two sides of the electrolyte membrane respectively; a gas diffusion layer is arranged on the outer side of each catalytic layer;
the gas diffusion layer comprises a support layer and a microporous layer between the catalytic layer and the support layer; the supporting layer is made of carbon paper or carbon cloth; the microporous layer is deposited on the supporting layer and is connected with the supporting layer and the catalytic layer;
the catalytic layer includes a catalyst and a binder.
2. The fuel cell membrane electrode assembly according to claim 1 wherein said microporous layer is a hydrophilic microporous layer comprising a microporous material and a hydrophilic coating deposited on the microporous material, said hydrophilic coating being in contact with a support layer, said microporous material being in contact with a catalytic layer;
the content of the hydrophilic coating is 2-8% of the total weight of the microporous layer, the hydrophilic coating comprises hydrophilic polymers, and the hydrophilic polymers comprise one or more of polyvinyl alcohol, polyvinyl pyridine, polyacrylic acid, polyacrylamide, polyallylamine, polyethyleneimine, polyalkyloxazoline and polyalkylamine;
the thickness of the hydrophilic microporous layer is greater than 1.2 μm;
the specific surface area of the microporous material is more than 55m2/g；
The average particle size of the microporous material is more than 30 nm;
the microporous material is a carbon-based material and comprises one or more of carbon nano tubes, carbon nano fibers, activated carbon nano wires, activated carbon, carbon black and graphite.
3. The fuel cell membrane electrode assembly according to claim 1 wherein said catalyst layer is a double layer structure, and said catalyst is Pt/C; firstly preparing 40 wt.% Pt/C catalytic layer and then preparing 20 wt.% Pt/C catalytic layer on the gas diffusion layer; in contact with the electrolyte membrane is 20 wt.% of a Pt/C catalytic layer; in contact with the gas diffusion layer was a catalytic layer of 40 wt.% Pt/C.
4. A fuel cell membrane electrode test device for testing a fuel cell membrane electrode according to any one of claims 1 to 3, comprising: the humidifier comprises a moving driver, a first humidifier, a pressure driver, a second humidifier, a control unit and an electronic load;
the mobile driver is used for continuously moving the membrane electrode of the fuel cell, two catalytic layers are respectively stuck to two sides of the electrolyte membrane, wherein one catalytic layer is an anode, and the other catalytic layer is a cathode;
the first humidifier is used for humidifying the membrane electrode of the fuel cell and comprises a humidifier arranged on one side of the anode and a humidifier arranged on one side of the cathode;
the pressure driver comprises a conductive heating clamp contacted with the membrane electrode of the fuel cell, and the conductive heating clamp is pressed on the membrane electrode of the fuel cell by moving the conductive heating clamp; the conductive heating clamp comprises a first conductive heating clamp arranged on one side of the anode and a second conductive heating clamp arranged on one side of the cathode; the first conductive heating clamp is provided with a first gas inlet and a first gas outlet; a second gas inlet and a second gas outlet are formed in the second conductive heating clamp;
a second humidifier supplying gas to the fuel cell membrane electrode through the first gas inlet and the second gas inlet, respectively, the gas being humidified while passing through the first diffuser and the second diffuser;
the control unit is used for controlling the whole fuel cell membrane electrode detection device, and simultaneously detecting the temperatures of the first conductive heating clamp and the second conductive heating clamp and the flow rate of supplied gas;
an electronic load is used to control and measure the voltage or current between the anode and the cathode, and the voltage or current between the first and second electrically conductive heating clamps.
5. The fuel cell membrane electrode test device according to claim 4, further comprising:
a gasket mounted on a fuel cell membrane electrode;
and the marking unit is used for marking the grade or the activity of the fuel cell membrane electrode after detection.
6. The fuel cell membrane electrode detection device according to claim 5, further comprising an alarm system, wherein the alarm system is connected to the control unit, and comprises a first nand gate, a second nand gate, a key switch, a light emitting diode and an alarm; the cathode of the light emitting diode is connected with the output end of the first NAND gate and the input end of the second NAND gate, and the anode of the light emitting diode is connected with a power supply; the output end of the second NAND gate is sequentially connected with an NPN triode, an oscillator and an alarm;
when the fuel cell membrane electrode detection device works normally, the key switch is in a closed state, the first NAND gate outputs high level, the light-emitting diode does not emit light, the second NAND gate outputs low level, the oscillator does not work, and the alarm does not sound;
when the detector detects a dangerous factor, the detector outputs a negative pulse to the alarm circuit, the first NAND gate outputs a low level to enable the light emitting diode to be conducted and emit light, the second NAND gate outputs a high level to enable the oscillator to work, and the alarm gives an alarm;
after the dangerous factors are eliminated, the key switch is pressed down, and the acousto-optic alarm is stopped.
7. A method of making a fuel cell membrane electrode assembly according to claim 1, said method comprising the steps of:
step S1, electrolyte membrane pretreatment, specifically including the steps of:
step S11, boiling the electrolyte membrane in a 6 wt.% hydrogen peroxide solution for 1 hour to remove organic and inorganic impurities in the electrolyte membrane; removing residual hydrogen peroxide solution on the surface by using deionized water;
step S12, placing the electrolyte membrane in 0.6 mol.L-1Boiling the sulfuric acid solution for 1 hour to re-protonate the electrolyte membrane;
step S13, drying the processed electrolyte membrane in a vacuum drying oven;
step S2, preparing a gas diffusion layer, wherein the supporting layer is made of carbon paper, and the method specifically comprises the following steps:
step S21, soaking the carbon paper in a PTFE solution, and then drying the carbon paper;
step S22, carrying out ultrasonic dispersion on PTFE and carbon black in an ethanol solution to form a mixture;
step S23, uniformly spraying the mixture on the surface of one side of the carbon paper to form a microporous layer;
and step S24, sintering at 340 ℃ in a high-temperature furnace, melting the PTFE in the carbon paper and the PTFE in the microporous layer, and bonding the carbon paper and the PTFE together.
Step S3, preparing a catalytic layer, specifically including the steps of:
step S31, mixing PTFE, a catalyst and glycerol to form a primary mixture;
step S32, performing ultrasonic dispersion on the primary mixture in an ethanol solution to form a secondary mixture;
step S33, uniformly spraying the mixture on a gas diffusion layer, and drying to form a gas diffusion electrode;
step S34, sintering the gas diffusion electrode in a high temperature furnace at 340 ℃;
step S35, evenly spraying Nafion solution on the surface of the catalyst to finish the three-dimensional process of the gas diffusion electrode; after the Nafion solution is dried, the film is cast;
and step S4, cutting the gas diffusion electrodes into squares, hot-pressing the two cut gas diffusion electrodes and the pretreated electrolyte membrane, and taking out to finish the preparation of the membrane electrode of the fuel cell.
8. The method of manufacturing a fuel cell membrane electrode assembly according to claim 7, wherein in step S31, the catalyst includes one or more of platinum, palladium, iridium, ruthenium, vanadium, rhodium, gold, silver, cobalt, nickel, and iron, and the mass ratio of the catalyst to the PTFE is 1: 1 to 50: 1;
in the step S33, the drying temperature is between 40 ℃ and 50 ℃, and the drying time is between 40 minutes and 1 hour;
in the step S35, the drying time of the Nafion solution is between 3 hours and 5 hours;
in the step S4, the hot pressing temperature is between 120 and 250 ℃, and the hot pressing time is between 20 and 200 seconds.
9. An apparatus for preparing a fuel cell membrane electrode assembly according to claim 1 comprising:
two gas diffusion electrode supply rollers for conveying one gas diffusion electrode in one direction, respectively, the gas diffusion electrode including a gas diffusion layer and a catalytic layer bonded together;
an electrolyte membrane supply roller for conveying an electrolyte membrane between two gas diffusion electrodes;
a pair of upper and lower heat transfer rollers sandwiching the two gas diffusion electrodes and the electrolyte membrane therebetween for hot pressing;
a gas diffusion electrode supply roller is respectively arranged above the upper heat transfer roller and below the lower heat transfer roller;
each gas diffusion electrode supply roller is provided with a synchronous detection and control unit for detecting whether the two gas diffusion electrodes move synchronously or not, and if not, synchronizing the two gas diffusion electrodes.
10. A single fuel cell comprising the fuel cell membrane electrode according to any one of claims 1 to 3, and further comprising a flow field plate and a current collecting plate; the membrane electrode is positioned at the central position of the single fuel cell; the flow field plates are arranged on two sides of the membrane electrode and connected with the gas diffusion layer, and the flow field plates are made of graphite; and the current collecting plates are arranged on two sides of the flow field plate and are made of copper.
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| CN114430050A (en) * | 2022-01-18 | 2022-05-03 | 山东仁丰特种材料股份有限公司 | Gas diffusion layer for high-performance hydrogen fuel cell and preparation method thereof |
| CN117451756A (en) * | 2023-10-31 | 2024-01-26 | 天津大学 | Fuel cell membrane electrode degradation detection device and in-situ degradation detection system and method |
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