CN110970629B - Fuel cell membrane electrode CCM and preparation method and device thereof - Google Patents
Fuel cell membrane electrode CCM and preparation method and device thereof Download PDFInfo
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8817—Treatment of supports before application of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32082—Radio frequency generated discharge
- H01J37/32091—Radio frequency generated discharge the radio frequency energy being capacitively coupled to the plasma
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3402—Gas-filled discharge tubes operating with cathodic sputtering using supplementary magnetic fields
- H01J37/3405—Magnetron sputtering
- H01J37/3408—Planar magnetron sputtering
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8867—Vapour deposition
- H01M4/8871—Sputtering
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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]
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a membrane electrode CCM of a fuel cell, a preparation method and a device thereof, comprising the following steps: (1) the PEM film is placed in a low vacuum environment, and is treated by using plasma generated by organic amine capacitive coupling discharge; (2) and (2) placing the PEM film treated in the step (1) in a low vacuum environment, and depositing a catalyst Pt on the surface of the PEM film by adopting a vacuum sputtering deposition method to form the Pt film. The invention adopts the low-temperature plasma PEM surface modification and the vacuum sputtering deposition catalyst Pt film technology, so that the finally formed Pt film is a high-purity, ultrathin and ultrafine-grain Pt film, the thickness of the Pt film is less than 50nm, the Pt film has good uniformity, the Pt film is firmly combined with a substrate, the heat shock resistance is strong, the Pt film is not easy to peel off, the cost is low, and the service life is prolonged.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a membrane electrode CCM of a fuel cell, a preparation method and a device thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are high-efficiency energy conversion devices that can directly convert chemical energy stored in hydrogen fuel and an oxidant into electrical energy by means of electrochemical reaction, have the characteristics of environmental protection, high specific energy, low-temperature rapid start and high smooth operation, and are considered as ideal power sources for replacing internal combustion engines. In recent years, various governments and companies have been dedicated to promote the development of fuel cell electric vehicles, represented by japan, and 12 months 2014, yota released Mirai hydrogen fuel cell vehicles; in 2016, 3 months, Clarity Fuel cell vehicles were introduced by Honda. The domestic fuel cell automobile industry develops the automobile group as a representative, the development of the front and rear four-generation hydrogen fuel cell passenger cars is completed, and the large-scale verification is carried out on the Rongwei 950 automobile type. In 11 months of 2017, the Shangqi Datong formally released the Chinese first-style fuel cell wide-body light weight FCV80 at Guangzhou vehicle exhibition, and marked that the fuel cell commercial vehicle realizes industrialization.
The fuel cell technology is considered as a novel energy technology which is most likely to replace the existing energy technology on a large scale due to the important advantages of high energy conversion efficiency, small environmental disturbance (zero emission or low emission), rich and various fuel sources and the like, and is one of important technical means for solving the future energy problems and the serious environmental pollution problem caused by burning fossil energy. EMA, as a core component, greatly affects fuel cell performance.
A Membrane Electrode Assembly (MEA) is mainly composed of a Gas Diffusion Layer (GDL), a Catalyst Layer (CL), and a Proton Exchange Membrane (PEM). The MEA is a core component of the proton exchange membrane fuel cell, provides micro-channels for multi-phase substance transfer and electrochemical reaction sites for the PEMFC, and the performance of the MEA directly determines the performance of the PEMFC. The technical indexes of the MEA for the vehicle in 2020 are proposed by the United states department of energy (DOE) to be as follows: the cost is less than $ 14/kW; the durability reaches 5000 h; the power density reaches 1W/cm under rated power 2 . According to the requirement, the total dosage of the noble metal Pt is less than 0.125mg/cm 2 The current density at 0.9V should be 0.44A/mgPt. The MEA currently with the best performance is the nanostructured thin film (NSTF) electrode developed by 3M company, whose Pt content can be reduced to 0.125mg/cm 2 However, water flooding is easy to occur, and the problem of durability needs to be solved; there are not many enterprises which put out membrane electrode products and sell them to the outside in China, and there is a large gap between the technical level and the state. Therefore, the preparation of MEA with low price, high performance and good durability becomes a hot research topic of extensive attention of researchers in various countries around the world.
Although proton exchange membrane fuel cell technology is generally considered to be nearly mature, such fuel cells still suffer from high cost and short lifetimeProblems and Pt resource limitations. And these problems have become major factors that restrict the development and commercialization progress of fuel cell technologies. The key to solving this problem is the structure of Pt and PEM. DOE has established that the Pt loading of the cathode electrode catalyst of a 50kW PEM fuel cell stack is reduced to 0.05mg/cm 2 The following long-term goals. Therefore, the preparation of high-performance low-Pt-loading and even ultra-low-Pt-loading membrane electrodes by developing and developing high-efficiency catalysts and improving and developing new membrane electrode preparation technologies has a very important significance for effectively reducing the cost of proton exchange membrane fuel cells and promoting the development and commercialization process of proton exchange membrane fuel cell technologies.
Disclosure of Invention
In order to solve the above problems, the present invention provides a membrane electrode CCM for a fuel cell, a method for preparing the same, and an apparatus thereof, and particularly, a low temperature plasma PEM surface modification and vacuum sputtering deposition catalyst (Pt) thin film technology is adopted, which has only a few nanometers of action depth on the PEM surface and no high temperature action, thereby avoiding affecting the properties of the PEM material, and the finally formed Pt film is a high purity, ultrathin, ultrafine particle Pt thin film, which has a thickness of less than 50nm, good uniformity, firm combination with a substrate, strong thermal shock resistance, difficult peeling, corrosion resistance, low cost, and prolonged service life.
Plasma refers to a partially or completely ionized gas, which includes high-energy active components such as electrons, ions, excited molecules, radicals and photons, and the sum of positive and negative charges carried by the free electrons and the ions completely cancels out. The ion temperature (or gas temperature) of the low-temperature plasma is near room temperature, but the mass of electrons is far less than that of ions, so that the electron temperature can be between tens of thousands and hundreds of thousands of degrees and is far higher than the ion temperature, and the state is very favorable for performing modification treatment on the surface of the PEM and vacuum sputtering plating of the Pt thin film layer. The advantages are that: 1) the low-temperature plasma is a non-thermodynamic equilibrium plasma generated by discharging in a low-pressure gas; the electron temperature (1-10 eV) is about 1-2 orders of magnitude higher than the gas temperature and the ion temperature; up to 10 4 The electron temperature of K is such that the electrons are sufficientThe energy of the proton exchange membrane is used for exciting, decomposing and ionizing gas molecules through collision, so that the reaction activity is greatly improved, and a modified PEM with excellent quality can be obtained at a lower temperature; 2) the low-temperature plasma is generated by discharging in low-pressure gas under a vacuum background, the gas is simpler and is easy to accurately control, and the control on surface layer components can be realized; 3) the method has the advantages of stability in controlling the growth speed of the Pt layer and firm combination with the substrate material, and realizes continuous and repeatable growth of the process.
In a first aspect, the present invention provides a method for preparing a membrane electrode CCM of a fuel cell, comprising the following steps:
(1) the PEM film is placed in a low vacuum environment, and is treated by using plasma generated by organic amine capacitive coupling discharge;
(2) and (3) placing the PEM film treated by the plasma in the step (1) in a low vacuum environment again, and depositing a catalyst Pt on the surface of the PEM film by adopting a vacuum sputtering method.
In the invention, when the surface of the PEM is treated by plasma formed by organic amine capacitive coupling discharge, active groups such as amino groups and the like can be grafted on the surface of the PEM, so that the modification treatment of the PEM is realized, a favorable basis is provided for improving the peel strength of the PEM and a catalyst Pt layer, and then the metal Pt element is deposited on the surface of the PEM by a vacuum sputtering method. The compact Pt film prepared by the invention is less than 50nm, and the Pt loading capacity is less than 0.2mg/cm 2 The minimum can be 0.04mg/cm 2 Peel Strength of PEM from catalyst Pt layer>8.0N/cm, the cost is lower than 450 yuan/m 2 。
Preferably, the organic amine capacitive coupling discharge conditions are as follows: the body power density is more than 0.1W/cm 3 Electric field intensity (discharge voltage/electrode spacing)>5.0kV/m, and the air pressure range is 30 Pa-80 Pa. The plasma generated by the organic amine gas coupling discharge processes the PEM surface to realize the surface grafting of amino and the surface etching and roughening, and the above discharge conditions can effectively ensure the etching and grafting effects.
Preferably, the organic amine is a fatty amine, which is easier to graft amino groups on the PEM membrane surface than other types of organic amines. More preferably, the organic amine is methylamine, ethylamine, propylamine, butylamine, pentylamine or hexylamine, and isomers of the foregoing amines are also suitable for use in the present invention.
Preferably, the pressure of the background vacuum environment in step (1) is not greater than 10 Pa.
Preferably, the plasma treatment time in step (1) is 5 to 30 s.
Preferably, in step (1), after the plasma treatment is completed, the organic amine supply is stopped, the vacuum degree is pumped to be lower than 10Pa, the air is stopped to be in an atmospheric state, and the PEM film is taken out.
Preferably, in the step (2), the vacuum sputtering deposition conditions are as follows: the working gas is Ar gas with the purity of 99.999 percent, the sputtering plating time is 6-30s, the Ar gas flow is 10-50sccm, the working gas pressure is 0.2-2Pa, the radio frequency is 2-60MHz, and the radio frequency power is 50-300W.
Preferably, in the step (2), before performing vacuum sputtering deposition of the Pt film, the rf magnetron sputtering discharge chamber needs to be cleaned, and the cleaning method is as follows:
pumping the discharge chamber to background vacuum, then introducing Ar gas into the chamber, and realizing Ar gas discharge through radio frequency modulation; wherein the background vacuum is less than or equal to 1 x 10 -4 Pa, the purity of Ar gas is 99.999%, the flow rate of Ar is 10-50sccm, the cleaning time is 10-100s, the working pressure is 0.2-2Pa, the radio frequency is 2-60MHz, and the cleaning power is 50-300W.
Further preferably, in the step (2), after the radio frequency magnetron sputtering discharge chamber is cleaned, the discharge chamber is pumped to background vacuum again, Ar gas is introduced, and a Pt film is formed on the PEM film by sputtering through radio frequency modulation, wherein the specific process parameters are as follows: background vacuum is less than or equal to 1 x 10 -4 Pa, the purity of Ar gas is 99.999%, the sputtering plating time is 10-30s, the Ar gas flow is 25sccm, the working gas pressure is 0.3Pa, the radio frequency is 13.56MHz, and the radio frequency power is 150W.
The device for preparing the membrane electrode CCM of the fuel cell by using the preparation method is of a double-chamber structure and comprises a capacitive coupling discharge chamber and a radio frequency magnetron sputtering discharge chamber, wherein the power supply of the capacitive coupling discharge chamber is a medium-frequency pulse power supply, and the power supply of the radio frequency magnetron sputtering discharge chamber is a radio frequency power supply.
The invention adopts sectional plasma to carry out pretreatment modification on the surface of the PEM, greatly improves the reaction activity of the surface of the PEM, is convenient for the subsequent vacuum sputtering deposition of a Pt film, organically combines the surface modification of the matrix plasma with the vacuum sputtering coating and forms a uniform ultrafine particle catalyst Pt film on the surface of the PEM. The invention has the following technical effects:
(1) generating high-density active particles by using plasma, and simultaneously carrying out physical and chemical etching and surface grafting amino (amino is provided by organic amine) modification treatment on the surface of the PEM so as to improve the peel strength of the PEM and a catalyst Pt layer;
(2) the plasma-treated PEM material is sputtered with the Pt thin film, so that the prepared particles are smaller, the utilization rate of the Pt catalyst is higher, the larger surface area and the utilization rate can be improved, the preparation process is simpler, the expanded production is easy, the substrate is not limited, and the like.
In a second aspect, the present invention provides a fuel cell membrane electrode CCM produced by the method of producing any one of the fuel cell membrane electrode CCMs of the first aspect.
In a third aspect, the present invention provides a production apparatus to which the production method according to any one of the first aspect is applied.
Preferably, the preparation device comprises a capacitive coupling discharge chamber and a radio frequency magnetron sputtering discharge chamber, wherein a transmission device is arranged in each discharge chamber, an anode electrode and a cathode electrode are respectively arranged on two sides of the transmission device in the capacitive coupling discharge chamber, a magnetron sputtering target made of Pt is arranged on the outer side of the transmission device in the radio frequency magnetron sputtering discharge chamber, and the anode electrode, the cathode electrode and the magnetron sputtering target are all connected with an external power supply.
Preferably, the capacitive coupling discharge chamber and the radio frequency magnetron sputtering discharge chamber are communicated through a vacuum transition cavity, the two discharge chambers and a transmission device in the vacuum transition cavity are of an integral structure, an unreeling machine is arranged at one end of the transmission device, which is positioned in the capacitive coupling discharge chamber, and a reeling machine is arranged at one end of the transmission device, which is positioned in the radio frequency magnetron sputtering discharge chamber.
Compared with the prior art, the invention has the advantages that the action depth on the PEM surface is only a few nanometers, the maximum action is not more than 50nm, the whole process does not have high temperature action, the property of a matrix material can not be influenced, the surfaces of various shapes can be treated when the PEM surface is modified by adopting the plasma technology, the sputtering deposition film is firmly combined with the matrix, the barrier property of the thermal barrier is strong, the impact resistance is strong, the film is not easy to peel off and is corrosion-resistant, and the thickness of the film can be accurate to the nanometer level.
Drawings
FIG. 1 is a schematic structural diagram of a fuel cell membrane electrode CCM manufacturing device;
FIG. 2 is a Scanning Electron Microscope (SEM) surface view of a plasma modified PEM membrane used in the present invention;
FIG. 3 is a graph of X-ray photoelectron spectroscopy (XPS) N1s for a plasma modified PEM membrane used in the present invention;
FIG. 4 is an XRD pattern of sputter deposited Pt films of the present invention;
FIG. 5 is a graph showing the performance of a single cell of a CCM obtained by the preparation method of the present invention;
FIG. 6 is a LSV curve of a CCM obtained by the preparation method of the present invention.
Wherein, 1, CCM preparing device; 11. a capacitive coupling discharge chamber; 12. a PEM membrane; 13. an unreeling machine; 14. an anode electrode; 15. a cathode electrode; 16. a vacuum transition cavity; 17. a radio frequency magnetron sputtering discharge chamber; 18. a magnetron sputtering target; 19. and (7) a winding machine.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
When the CCM preparation method of the fuel cell membrane electrode provided by the invention is utilized, the CCM preparation device 1 used is of a double-chamber structure, as shown in figure 1, the CCM preparation device comprises a capacitive coupling discharge chamber 11 and a radio frequency magnetron sputtering discharge chamber 17, which are respectively used for generating plasma and sputtering coating, transmission devices are arranged in the two chambers, preferably, the transmission devices are horizontally arranged, one end of each transmission device is provided with an unreeling machine or a reeling machine, and the time of a PEM membrane passing between two electrodes and the time of sputtering coating can be controlled by controlling the rotating speed of the unreeling machine or the reeling machine; the upper side and the lower side of the transmission device in the capacitive coupling discharge chamber are respectively provided with an anode electrode 14 and a cathode electrode 15, and the transmission device can be arranged left and right or front and back, so long as the transmission device is positioned between the two electrodes, the outer side of the transmission device in the radio frequency magnetron sputtering discharge chamber 17 is provided with a magnetron sputtering target 18, the magnetron sputtering target is made of Pt, and the magnetron sputtering target can be positioned at any one of the upper, lower, left, right, front and back positions of the transmission device, preferably the upper position.
The capacitive coupling discharge chamber 11 and the radio frequency magnetron sputtering discharge chamber 17 can be adjacent or separated, and in order to improve the production efficiency and reduce the labor cost, the capacitive coupling discharge chamber 11 and the radio frequency magnetron sputtering discharge chamber 17 can be communicated through a vacuum transition cavity 16, and the vacuum transition cavity is preferably a long and narrow cavity. In order to improve the production efficiency, preferably, the two discharge chambers and the transmission device in the vacuum transition chamber are of an integrated structure, wherein one end of the transmission device, which is located in the capacitive coupling discharge chamber 11, is provided with an unreeling machine 13 for installing a PEM film roll, one end of the transmission device, which is located in the radio frequency magnetron sputtering discharge chamber 17, is provided with a reeling machine 19, the untreated PEM film roll is sleeved on a reel of the unreeling machine 13, the PEM film roll is slowly unreeled under the action of the unreeling machine 13, is spread on the surface of the transmission device, is sequentially subjected to discharge grafting of amino through the capacitive coupling discharge chamber 11, is subjected to sputtering plating of a Pt film through the radio frequency magnetron sputtering discharge chamber 17, and finally is formed into a film roll again under the action of the reeling machine 19, and the film at the moment can be used as a membrane electrode CCM and taken out of the radio frequency magnetron sputtering discharge chamber 17.
The power supply of the capacitive coupling discharge chamber is a medium-frequency pulse power supply and is connected with the anode electrode and the cathode electrode; the power supply of the radio frequency magnetron sputtering discharge chamber is a radio frequency power supply and is connected with a magnetron sputtering target, the radio frequency is 2-60MHz, specifically 4MHz, 9MHz, 13.56MHz, 18MHz, 23MHz, 31MHz, 37MHz, 45MHz, 51MHz, 55MHz and the like can be selected, in the embodiment of the invention, 13.56MHz is taken as an example for specific description, in the cavity, the magnetron sputtering target is a cathode electrode, and the cavity body is an anode electrode; the invention is suitable for PEM films with any thickness, and in the embodiment of the invention, a PEM film roll produced by DuPont in the United states is selected, and three specifications of 15 mu m, 50 mu m and 117 mu m are selected as examples for description.
Example 1
The method for preparing the membrane electrode CCM of the fuel cell by adopting the PEM film roll with the thickness of 15 mu m comprises the following steps:
(1) the method comprises the following steps of (1) placing a PEM film in a low vacuum environment, and treating the PEM film by using plasma generated by organic amine capacitive coupling discharge, wherein the specific steps are as follows:
(11) the film roll is arranged on an unreeling machine in a capacitive coupling discharge chamber 11, the film roll is vacuumized to be below 10Pa, plasma is generated through methylamine gas discharge to etch and graft amino treatment on the PEM film, the rotating speed of the unreeling machine is controlled, and the time of the PEM film passing through a plasma discharge area is 12 s. The bulk power density (power output/(electrode area. times. spacing between two electrodes)) of the plasma discharge was 0.15W/cm 3 The discharge voltage meets the requirement of the electric field intensity of the discharge area, and the electric field intensity (discharge voltage/electrode spacing) is 6.0 kV/m. In order to improve the etching efficiency of plasma, alkaline methylamine gas discharge is adopted to treat the non-alkaline PEM, and the discharge pressure is 30 Pa.
(12) Stopping the supply of methylamine, continuously pumping until the vacuum degree is lower than 10Pa, pumping out all methylamine, stopping pumping in air until the state of atmospheric pressure, taking out the PET film coil, carrying out sealed packaging, and then entering the next step of sputtering plating.
(2) Putting the PEM film treated by the plasma in the step (1) in a low vacuum environment again, and depositing a catalyst Pt on the surface of the PEM film by adopting a vacuum sputtering method, wherein the specific steps are as follows:
(21) putting a PEM membrane on a transmission device in a radio frequency magnetron sputtering discharge chamber, fixing, then pumping the chamber to a background vacuum, then introducing Ar gas into the chamber, realizing Ar gas discharge through radio frequency modulation to generate radio frequency capacitance coupling plasma CCP, cleaning a vacuum chamber and the transmission device, and preventing impurities from affecting the final CCP;
the specific process parameters are as follows: temperature at room temperature, background vacuum<1×10 -4 Pa, the working gas is Ar gas with the purity of 99.999 percent, the cleaning time is 1min, the flow rate of the Ar gas is 25sccm, the working gas pressure is 0.3Pa, the radio frequency is 13.56MHz, and the radio frequency power is 150W.
(22) After the vacuum chamber and the transmission device are cleaned, the vacuum chamber is pumped to the background vacuum<1×10 -4 Pa, introducing Ar gas again, bombarding the magnetron sputtering target by plasma generated by radio frequency modulation to carry out sputtering plating, and forming a nano Pt film on the PEM film;
the specific process parameters are as follows: temperature at room temperature, background vacuum<1×10 -4 Pa, the working gas is Ar gas with the purity of 99.999 percent, the time is 30s, the flow rate of the Ar gas is 25sccm, the working gas pressure is 0.3Pa, the radio frequency is 13.56MHz, and the radio frequency power is 150W.
(23) And after the sputtering plating process is finished, introducing Ar gas as protective gas to finally prepare the membrane electrode CCM of the fuel cell.
The cleaning process in the step (21) is only performed when the equipment is initially operated, that is, the first batch of CCM preparation process needs to be cleaned, and the subsequent preparation process may not be cleaned.
Example 2
The difference from example 1 is: this example uses a 50 μm thick roll of PEM film and the bulk power density of the plasma discharge in step (1) is 1.5W/cm 3 (ii) a In the step (2), the technological parameters of the sputtering plating process are as follows: the sputter plating time was 12 seconds.
Example 3
The difference from example 1 is: in this example, a 117 μm thick PEM film roll was used, and the bulk power density of the plasma discharge in step (1) was 1.5W/cm 3 (ii) a In the step (2), the technological parameters of the sputtering plating process are as follows: the sputter plating time was 6 seconds.
Example 4
The difference from example 1 is: in the step (1), the plasma treatment time was 30s, and the bulk power density of the plasma discharge was 2W/cm 3 The electric field intensity is 8.0kV/m, and the discharge air pressure is 80 Pa; in the step (2), the process parameters of the cleaning process are as follows: the flow rate of Ar is 50sccm, the cleaning time is 10s, the working pressure is 1.5Pa, and the cleaning power is 50W; the technological parameters of the sputtering plating process are as follows: the sputtering time is 20s, the Ar gas flow is 10sccm, the working gas pressure is 2Pa, and the radio frequency power is 50W.
Example 5
The difference from example 1 is: in the step (1), the plasma treatment time was 5s, and the bulk power density of the plasma discharge was 5W/cm 3 The electric field intensity is 13kV/m, and the discharge air pressure is 50 Pa; in the step (2), the process parameters of the cleaning process are as follows: the flow rate of Ar is 10sccm, the cleaning time is 100s, the working pressure is 3Pa, and the cleaning power is 300W; the technological parameters of the sputtering plating process are as follows: the sputtering time is 25s, the Ar gas flow is 10sccm, the working pressure is 3Pa, and the radio frequency power is 300W.
The performance metrics associated with CCMs prepared in examples 1-3 are as follows:
the method for measuring the peel strength specifically comprises the following steps: according to the test requirements of the national standard GB/T13555, the CCM sample strip is cut into the size of 25mm multiplied by 100mm, an electronic universal test tensile machine is adopted to carry out the peel strength test on the CCM sample strip, and the vertical displacement rate of a tensile module of the tensile machine is 10 mm/min.
The CCM prepared by the present invention not only has ultra-low Pt loading, ultra-thin Pt film, ultra-strong peel strength, and meets commercial requirements, as demonstrated by the test of example 3 below:
after scanning the prepared CCM by an electron microscope, as can be seen from figure 2, the PEM surface after plasma treatment becomes rough, so that the PEM is easily combined with Pt, and the firmness of the PEM and the Pt is improved.
After the obtained CCM is scanned by X-ray, N1s is mainly composed of amino groups, namely, the PEM surface is grafted with amino groups, as can be seen from an electron spectrum (XPS) N1s diagram in FIG. 3.
As can be seen from the XRD pattern of the Pt film sputter-deposited in fig. 4, the main crystal orientation of Pt is (111), and the calculation result by the scherrer equation shows that the grain size is about 10nm, i.e., the Pt thin film particles are smaller and more uniform, and can be accurate to the nanometer level.
As can be seen from the performance curve of the single cell of fig. 5, the open circuit voltage of the membrane electrode with the anode electrode made of CCM according to the present invention and the open circuit voltage of the cathode electrode made of commercial Pt/C was 1.026V (the open circuit voltage of commercial Pt/C was generally 0.9-1.0V), and thus it was found that the CCM made according to the present invention was normally commercially available.
As can be seen from the LSV curve of CCM in fig. 6, the hydrogen permeation current is 0.01A (commercial Pt/C is 0.04A), and the value is normal, i.e., the CCM prepared by the present invention is commercially available and has better effect than the existing commercial electrode.
The above embodiments only express various embodiments of the present invention, and the description thereof is more specific and detailed, but it should not be understood that the scope of the present invention is limited thereby. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention.
Claims (8)
1. A method for preparing a membrane electrode CCM of a fuel cell comprises the following steps:
(1) the PEM film is placed in a low vacuum environment with the pressure less than or equal to 10Pa, and is treated by plasma generated by organic amine capacitive coupling discharge for 5-30 s; the organic amine capacitive coupling discharge conditions are as follows: bulk power density>0.1W/cm 3 Electric field intensity>5.0kV/m, and the air pressure range is 30-80 Pa; after the plasma treatment is finished, stopping supplying the organic amine, pumping until the vacuum degree is lower than 10Pa, stopping the machine, introducing air to the atmospheric pressure state, and taking out the PEM film;
(2) placing the PEM film treated in the step (1) at a temperature of less than or equal to 1 x 10 -4 And depositing a catalyst Pt on the surface of the PEM film by a vacuum sputtering deposition method under a low-vacuum environment of Pa, wherein the sputtering deposition conditions are as follows: the working gas is Ar gas with the purity of 99.999 percent, the sputtering plating time is 6-30s, the Ar gas flow is 10-50sccm, the working gas pressure is 0.2-2Pa, the radio frequency is 2-60MHz, and the radio frequency power is 50-300W;
pt film thickness of membrane electrode CCM obtainedThe degree is 10nm-50nm, and the Pt loading capacity is 0.04-0.2mg/cm 2 Peel Strength of PEM film and catalyst Pt film>8.0N/cm。
2. The method for producing a fuel cell membrane electrode CCM according to claim 1, wherein in the step (1), the organic amine is an aliphatic amine.
3. The method for producing a fuel cell membrane electrode CCM according to claim 2, wherein in the step (1), the organic amine is methylamine, ethylamine, propylamine, butylamine, pentylamine, or hexylamine, and isomers thereof.
4. The method for preparing the membrane electrode CCM of the fuel cell according to claim 1, wherein in the step (2), before the Pt film is deposited by vacuum sputtering, the radio frequency magnetron sputtering discharge chamber needs to be cleaned, and the cleaning method comprises the following steps:
pumping the discharge chamber to a background vacuum, then introducing Ar gas into the discharge chamber, and realizing Ar gas discharge through radio frequency modulation; wherein the background vacuum is less than or equal to 1 x 10 -4 Pa, the purity of Ar gas is 99.999%, the flow rate of Ar is 10-50sccm, the cleaning time is 10-100s, the working pressure is 0.2-2Pa, the radio frequency is 2-60MHz, and the cleaning power is 50-300W.
5. The method for preparing a membrane electrode CCM for a fuel cell according to claim 4, wherein in the step (2), after the cleaning of the radio frequency magnetron sputtering discharge chamber is completed, the discharge chamber is pumped to background vacuum again, Ar gas is introduced, and a Pt film is formed on the PEM film by sputtering through radio frequency modulation, wherein the specific process parameters are as follows: background vacuum is less than or equal to 1 x 10 -4 Pa, the purity of Ar gas is 99.999%, the working time is 24s, the flow rate of Ar gas is 25sccm, the working pressure is 0.3Pa, the radio frequency is 13.56MHz, and the radio frequency power is 150W.
6. A fuel cell membrane electrode CCM prepared by the production method according to any one of claims 1 to 5.
7. A device for preparing a membrane electrode CCM (continuous current module) of a fuel cell by applying the preparation method of any one of claims 1 to 5, which is characterized by comprising a capacitive coupling discharge chamber (11) and a radio frequency magnetron sputtering discharge chamber (17), wherein a transmission device is arranged in each discharge chamber, an anode electrode (14) and a cathode electrode (15) are respectively arranged at two sides of the transmission device in the capacitive coupling discharge chamber, a magnetron sputtering target (18) made of Pt is arranged at the outer side of the transmission device in the radio frequency magnetron sputtering discharge chamber, and the anode electrode, the cathode electrode and the magnetron sputtering target are all connected with an external power supply.
8. The preparation device according to claim 7, wherein the capacitive coupling discharge chamber (11) and the radio frequency magnetron sputtering discharge chamber (17) are communicated through a vacuum transition cavity (16), the two discharge chambers and a transmission device in the vacuum transition cavity are of an integral structure, an unreeling machine (13) is arranged at one end of the transmission device in the capacitive coupling discharge chamber, and a reeling machine (19) is arranged at one end of the transmission device in the radio frequency magnetron sputtering discharge chamber.
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