CN212810360U - Proton exchange membrane and fuel cell - Google Patents
Proton exchange membrane and fuel cell Download PDFInfo
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- CN212810360U CN212810360U CN202021749021.0U CN202021749021U CN212810360U CN 212810360 U CN212810360 U CN 212810360U CN 202021749021 U CN202021749021 U CN 202021749021U CN 212810360 U CN212810360 U CN 212810360U
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The application provides a proton exchange membrane and a fuel cell. The proton exchange membrane comprises a body, which plays the roles of transferring protons and blocking gas; the graphene oxide sheets are arranged side by side with the body, and one side of each graphene oxide sheet is connected to the side face of the body. The graphene oxide sheet is arranged on the side face of the body, so that the PEM has a good oxidation-reduction function, oxygen is more easily generated on the surface of the graphene oxide sheet and water is generated with protons, and the self-humidifying performance of the PEM is further improved; the graphene oxide sheet can greatly reduce the internal resistance of the PEM, accelerate the water back diffusion coefficient of the membrane and accelerate the proton conduction rate.
Description
Technical Field
The application belongs to the technical field of proton exchange membrane fuel cells, and particularly relates to a proton exchange membrane and a fuel cell.
Background
With the increasing depletion of fossil fuels and the increasing environmental crisis caused by the combustion of fossil fuels, the development of new energy sources has attracted more and more attention. The use of petroleum fuel causes serious pollution to the environment, and the development of novel zero-pollution energy sources is more and more concerned by people. Proton Exchange Membrane Fuel Cells (PEMFCs) are an environmentally friendly energy conversion device without a Fuel combustion process, and are favored because of their advantages of zero emission, low noise, high energy conversion rate, large energy density, and capability of starting at low temperature, and are considered as the ultimate mode of energy.
Proton Exchange Membranes (PEM) are the core channels of the electrochemical reaction of fuel cells and play a role in transferring protons and blocking reaction gases. A good PEM should have: high proton conductivity, low gas permeability, good thermal stability, sufficient mechanical strength, chemical stability and suitable cost performance. Currently, commercially available PEMs are electro-polymer membranes produced by dupont, usa, and composite membranes produced by Gore, canada. Both of these films suffer from the inability to self-moisturize and insufficient water retention capacity, especially in high temperature environments. While the hydrogen ion or proton transport rate in the PEM is linear with the water content of the membrane. And the uniform hydration of the whole proton exchange membrane can prevent the local dehydration and the local heating of the membrane, and can avoid the performance reduction of the battery and the degradation of the membrane material caused by the local dehydration and the local heating of the membrane. That is, the cell performance of PEMFCs is largely dependent on the water content in the PEM.
Currently, the humidification mode of PEMFCs mainly includes two modes, namely external humidification and internal humidification. The external humidification is to humidify the gas entering the cell by using a gas humidifier, the method can realize the effective humidification of the PEM, but also makes the structure of the cell system more complicated, increases the energy consumption and reduces the net output power of the fuel cell. The internal humidification is mainly to humidify the PEM by utilizing water generated in the process of electrochemical reaction of the fuel cell during operation. The internal humidification mode can maintain the normal operation of the battery without external equipment.
The technology reports that an inorganic hydrophilic material with a moisture retention function is coated on one side of a diffusion layer, a constant moisture layer is formed on one side of the diffusion layer, a catalyst is coated on the constant moisture layer, and then the constant moisture layer is hot-pressed to two sides of a PEM (proton exchange membrane).
Disclosure of Invention
Therefore, an object of the present invention is to provide a proton exchange membrane, a method for preparing the same, and a fuel cell, which can improve conductivity.
In order to solve the above problems, the present application provides a proton exchange membrane comprising:
the body plays roles of transferring protons and blocking gas;
the graphene oxide sheets are arranged side by side with the body, and one side of each graphene oxide sheet is connected to the side face of the body.
Preferably, the body includes a uniformly distributed catalytically active component therein, the catalytically active component including at least one of platinum, gold, palladium or silver.
Preferably, the body comprises a polymer porous membrane, and the catalyst active ingredient is uniformly dispersed in the polymer porous membrane; the material of the polymer porous membrane comprises at least one of polytetrafluoroethylene, polypropylene, polyvinylidene fluoride and polypropylene.
Preferably, the proton exchange membrane further comprises an inorganic nanoparticle layer, and the inorganic nanoparticle layer is arranged on the other side of the graphene oxide sheet.
Preferably, the material of the inorganic nanoparticle layer comprises nano-SiO2Nano-sized TiO 22Nano-grade Zr (HPO)4)2And nano-sized ZrO2At least one of them.
Preferably, the thickness of the proton exchange membrane is 60-70 μm.
According to another aspect of the present application, there is provided a fuel cell comprising a proton exchange membrane as described above.
The application provides a proton exchange membrane, includes: the body plays roles of transferring protons and blocking gas; the graphene oxide sheets are arranged side by side with the body, and one side of each graphene oxide sheet is connected to the side face of the body. The graphene oxide sheet is arranged on the side face of the body, so that the PEM has a good oxidation-reduction function, oxygen is more easily generated on the surface of the graphene oxide sheet and water is generated with protons, and the self-humidifying performance of the PEM is further improved; the graphene oxide sheet can greatly reduce the internal resistance of the PEM, accelerate the water back diffusion coefficient of the membrane and accelerate the proton conduction rate.
Drawings
FIG. 1 is a schematic view of a proton exchange membrane according to an embodiment of the present disclosure;
fig. 2 is a graph comparing the performance test of the fuel cell of the example of the present application with the conventional performance test.
The reference numerals are represented as:
1. a body; 2. graphene oxide flakes; 3. an inorganic nanoparticle layer.
Detailed Description
Referring collectively to fig. 1, in accordance with an embodiment of the present application, a proton exchange membrane, comprises:
the body 1 plays roles of transferring protons and blocking gas;
and the graphene oxide sheets 2 are arranged side by side with the body 1, and one side of each graphene oxide sheet 2 is connected to the side surface of the body 1.
The structure of the graphene oxide sheet 2 is introduced into the side surface of the body 1, so that the thermal stability of the PEM can be improved, the PEM has a good oxidation-reduction function, the thickness of the PEM is greatly reduced, the internal resistance of the PEM is greatly reduced, the water back-diffusion coefficient of the PEM is accelerated, the proton conduction rate is accelerated, and the cell performance is improved. In addition, the cost of the PEM is effectively reduced, so that the PEM is more suitable for commercial popularization.
In some embodiments, the body 1 includes a uniform distribution of catalytically active components including at least one of platinum, gold, palladium, or silver.
The traditional proton exchange membrane has catalyst active components which are not uniformly dispersed, and local electronic channels are formed in the membrane electrode, so that the fuel cell has self-discharge phenomenon to cause the failure of the fuel cell. The present application provides uniform dispersion of catalyst active components such as at least one of platinum, gold, palladium, or silver within the bulk, which can simplify the gas flow field design of the fuel cell, increase the self-humidifying operational stability, and improve the cell performance of the PEMFC. Secondly, the design allows for interpenetration of H2And O2Water is generated under the catalytic action of active ingredients of the catalyst, and cathode back diffusion water in the battery humidifies the PEM together, so that the mixed potential of permeating gas generated on the electrode is effectively eliminated, the polarization of the oxygen electrode is obviously reduced, and the open-circuit voltage (OCV) of the battery is improved. Finally, the introduction of the catalyst active ingredient can prevent H2And O2Permeation and diffusion in the membrane, effective inhibition of HO2And oxidative radicals such as HO attack polymers to cause the risk of membrane degradation, and effectively eliminate mixed overpotential, thereby improving the open circuit voltage and the battery performance of the battery.
Noble metal Pt is introduced into the proton exchange membrane, the introduction amount of the Pt is in certain proportion to the mass of the proton exchange membrane resin, and the mass ratio of the Pt to the proton exchange membrane resin is 0.0003-0.02: 1.
In some embodiments, the body 1 includes a polymer porous membrane in which the catalyst active ingredient is uniformly dispersed; the material of the polymer porous membrane comprises at least one of polytetrafluoroethylene, polypropylene, polyvinylidene fluoride and polypropylene.
The body 1 adopts a high-molecular porous membrane structure, not only can play a role in enhancing the support, but also can play a role in uniformly dispersing the catalyst active ingredients in the porous membrane in the middle part of the membrane.
In some embodiments, the proton exchange membrane further comprises an inorganic nanoparticle layer 3, and the inorganic nanoparticle layer 3 is disposed on the other side of the graphene oxide sheet 2. Preferably, the material of the inorganic nanoparticle layer 3 includes nano-SiO2Nano-sized TiO 22Nano-grade Zr (HPO)4)2And nano-sized ZrO2At least one of them.
The inorganic nano particle layer 3 has the function of absorbing water, and the inorganic nano particles doped in the membrane can effectively lock water, prevent the membrane from drying up, effectively prevent the proton conductivity of the membrane from being reduced due to membrane dehydration at high temperature, and effectively improve the water retention performance of the proton exchange membrane at high temperature.
In some embodiments, the proton exchange membrane has a thickness of 60-70 μm.
The proton exchange membrane is thin, is beneficial to the back diffusion of water, accelerates the back diffusion rate, achieves the aim of wetting the membrane in time, and is beneficial to improving the battery performance of the PEMFC and adapting to the load which changes rapidly.
According to another aspect of the present application, there is provided a method for preparing the proton exchange membrane as described above, including:
and oxidizing the graphite flake to obtain a graphene oxide solution, and spraying the graphene oxide solution onto the side surface of the body.
The graphite flake is oxidized and then prepared into a solution state, and a casting or spraying method is adopted, so that the complex synthetic steps are not needed, the complex equipment requirements are not needed, and the operation is simple, convenient and quick.
Subsequently, the sprayed product is immersed in the nano-scale particles and the solid polymer electrolyte solution for 5-20 minutes, and then is dried and rolled.
In the early stage, the preparation method further comprises the process of manufacturing the body 1: dissolving a supported catalyst in a high-molecular solid electrolyte solution, and uniformly mixing to form a membrane casting solution; and casting or spraying the casting solution on a polymer porous membrane, and drying to obtain a body.
Example 1
1) The method comprises the following steps of (1) washing a high-molecular porous reinforced membrane for three times by using a high-molecular resin material as a composite reinforced material, and then fixing the high-molecular porous reinforced membrane on a mould plate;
the proton exchange membrane with the polymer resin structure is beneficial to the transmission of water and protons in the membrane, and the type of the proton exchange membrane comprises perfluorinated sulfonic acid resin (such as Nafion, Flemin, Aciplex or Dow resin), Sulfonated Polyarylethersulfone (SPSU), Sulfonated Polyetheretherketone (SPEEK), partially fluorinated Sulfonated Polystyrene (SPFS), partially sulfonated polyphenylether sulfone or partially sulfonated polyaryletherketone. The preferable proton exchange membrane resin material is perfluorinated sulfonic acid resin Nafion, and the aperture of the perfluorinated sulfonic acid resin Nafion is 0.2-0.7 mu m; the thickness is 5 to 155 μm; the porosity is 60-90%.
2) Dissolving the polymer solid electrolyte in an organic solution to prepare a uniform solution with the polymer content of 7-13%;
the polymer solid electrolyte is dissolved in a solvent with high boiling point to prepare the polymer solid electrolyte solution. The high-molecular solid electrolyte is proton exchange membrane resin, wherein the high-boiling point solvent is N-methyl-2-pyrrolidone, dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide.
3) Dissolving a supported catalyst in a polymer solid electrolyte solution, oscillating for 24 hours, ultrasonically treating for 0.5-6 hours, and stirring for 0.5-6 hours to form a membrane casting solution; the mass ratio of the supported catalyst to the polymer solid electrolyte in the membrane casting solution is 0.01:1-0.2: 0.01;
4) casting or spraying the casting solution obtained in the step 3) on a porous reinforced membrane by a casting and spraying method, and drying for 12-36 hours at 30-50 ℃ under vacuum to prepare a composite proton exchange membrane;
5) placing the composite proton exchange membrane prepared in the step 4) in Ar/N2Heating at 110 deg.C overnight;
6) putting the composite proton exchange membrane after the heat treatment in the step 5) in 3-5% H2O2Ultrasonic treating in solution for 1-3 hr, taking out, washing with deionized water, and placing in dilute H solution with pH of 0.3-0.82SO4Ultrasonic treating at normal temperature for 2-3 hr, and washing with deionized waterTo self-humidifying composite proton exchange membranes.
7) Adding graphite flake to H2SO4：H3PO44: to the 1 ratio of acidic mixture, potassium permanganate was then added and the mixture was stirred continuously for 3 days. Then 36% of H was added thereto2O2The reaction was stirred for 3 days. And after the reaction is finished, centrifuging and then washing with HCl and deionized water to obtain the graphene oxide.
8) Preparing the graphene oxide obtained in the step 7) into a graphene oxide solution, and spraying the graphene oxide solution on the self-humidifying composite proton exchange membrane prepared in the step 6) to obtain the final product, namely the ultrathin three-layer self-humidifying composite proton exchange membrane
9) Separately preparing nano SiO2With solid polyelectrolyte solution, nano TiO2With solid polyelectrolyte solution, nano Zr (HPO)4)2With solid polyelectrolyte solution, ZrO2With a solid polyelectrolyte solution;
10) and (3) immersing the three-layer self-humidifying composite proton exchange membrane obtained in the step (8) into the inorganic nano particle and solid polyelectrolyte solution obtained in the step (9), taking out the membrane after 5-20 minutes, horizontally placing the membrane on a heating plate for drying, rolling the membrane by using a rubber roller, and repeating the rolling for 5-8 times to obtain the self-humidifying water-retaining composite proton exchange membrane with self-humidifying and water-retaining properties.
Example 2
1) Dissolving high molecular resin and a catalyst in an organic solution, directly casting or spraying the solution on two sides of a porous reinforced membrane, placing the porous reinforced membrane in dry air at 60 ℃ for 10-12 hours, and drying the porous reinforced membrane in a vacuum drying oven at 60 ℃ overnight to prepare a multilayer self-humidifying composite membrane;
2) uniformly spraying the catalytic layer slurry on two sides of a proton exchange membrane by using a vacuum spraying method for the multilayer self-humidifying composite membrane, drying at 80 ℃ overnight, and forming catalytic layers on the two sides of the proton exchange membrane;
3) h is to be2SO4:H3PO4The acidic mixture was added to the graphite flake at a ratio of 4:1, followed by potassium permanganate and the mixture was stirred continuously for 3 days. Then adding 36% ofH2O2The reaction was stirred for 3 days. After the reaction is finished, centrifuging and then washing with HCl and deionized water to obtain graphene oxide;
4) preparing the graphene oxide obtained in the step 2) into a graphene oxide solution, and spraying the graphene oxide solution on the self-humidifying composite proton exchange membrane prepared in the step 2) to obtain a final product, namely the ultrathin three-layer self-humidifying composite proton exchange membrane.
5) Preparation of nano SiO2With solid polyelectrolyte solution, nano TiO2With solid polyelectrolyte solution, nano Zr (HPO)4)2With solid polyelectrolyte solution, ZrO2With a solid polyelectrolyte solution;
6) and (3) immersing the three-layer self-humidifying composite proton exchange membrane obtained in the step (4) into the inorganic nano particle and solid polyelectrolyte solution obtained in the step (5), taking out the membrane after 5-20 minutes, horizontally placing the membrane on a heating plate for drying, rolling the membrane by using a rubber roller, and repeating the rolling for 5 times to obtain the self-humidifying water-retaining composite proton exchange membrane with self-humidifying and water-retaining properties.
According to another aspect of the present application, there is provided a fuel cell comprising a proton exchange membrane as described above.
The performance of the fuel cell using the proton exchange membrane is tested, and compared with the conventional proton exchange membrane, the performance is obviously improved, and the result is shown in fig. 2, wherein RH ═ 0% is of the conventional proton exchange membrane, and RH ═ 100% is of the proton exchange membrane of the present application.
It is easily understood by those skilled in the art that the above embodiments can be freely combined and superimposed without conflict.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application. The foregoing is only a preferred embodiment of the present application, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present application, and these modifications and variations should also be considered as the protection scope of the present application.
Claims (6)
1. A proton exchange membrane, comprising:
the body (1) plays a role in transferring protons and blocking gas;
the graphene oxide sheet (2) is arranged side by side with the body (1), and one side of the graphene oxide sheet (2) is connected to the side face of the body (1).
2. The proton exchange membrane according to claim 1, wherein said body (1) comprises a homogeneous distribution of catalytically active components.
3. The proton exchange membrane according to claim 2, wherein the body (1) comprises a polymeric porous membrane, the catalytically active component being uniformly dispersed within the polymeric porous membrane.
4. The proton exchange membrane according to claim 1, 2 or 3, further comprising an inorganic nanoparticle layer (3), wherein the inorganic nanoparticle layer (3) is disposed on the other side of the graphene oxide sheet (2).
5. The proton exchange membrane according to claim 1, wherein the thickness of the proton exchange membrane is 60-70 μm.
6. A fuel cell comprising the proton exchange membrane according to any one of claims 1 to 5.
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