CN212366004U - Laminated structure of proton membrane and bearing membrane of fuel cell - Google Patents

Laminated structure of proton membrane and bearing membrane of fuel cell Download PDF

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Publication number
CN212366004U
CN212366004U CN202020818773.1U CN202020818773U CN212366004U CN 212366004 U CN212366004 U CN 212366004U CN 202020818773 U CN202020818773 U CN 202020818773U CN 212366004 U CN212366004 U CN 212366004U
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membrane
fuel cell
resin layer
polymer resin
cell proton
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苏璇
王静静
冯威
刘婧
李永哲
张栋梁
张永明
张恒
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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

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Abstract

The utility model belongs to the technical field of fuel cell, concretely relates to fuel cell proton membrane and laminated structure who bears membrane, including fuel cell proton membrane and bear membrane, fuel cell proton membrane includes polymer resin layer, reinforcing material and lower polymer resin layer, goes up the polymer resin layer and coats reinforcing material's upper and lower both sides respectively with lower polymer resin layer, and the bear membrane includes transparent or translucent polymer membrane be equipped with the surface modification layer on the transparent or translucent polymer membrane, polymer resin layer and bear membrane surface modification layer laminate under the fuel cell proton membrane form laminated structure. The utility model discloses a set up the surface modification layer on the carrier film, can make perfluorosulfonic acid resin solution evenly spread in the fuel cell proton membrane, satisfy the large-scale stable production condition of fuel cell proton membrane, can make to have appropriate peel strength between carrier film and the fuel cell proton membrane simultaneously, can satisfy CCM volume to volume serialization steady production.

Description

Laminated structure of proton membrane and bearing membrane of fuel cell
Technical Field
The utility model belongs to the technical field of fuel cell, concretely relates to fuel cell proton membrane and laminated structure who bears membrane.
Background
The automobile using petrochemical fuel as power consumes a large amount of non-renewable resources, which not only causes the emission of greenhouse gases, but also causes environmental problems such as haze, photochemical smog and the like, so that the sustainable development of the human society is threatened, and the development of new energy automobiles is imminent. The fuel cell automobile technology takes a proton exchange membrane fuel cell (called a fuel cell for short) as an engine, can directly convert chemical energy in hydrogen into electric energy for pushing an automobile to run without a combustion process, has the advantages of high safety, long endurance, short fuel filling time, high energy conversion efficiency, zero emission and the like, and is considered as an ultimate target of a new energy automobile by the industry.
The proton membrane of the fuel cell plays a central role in conducting protons, supporting an electrocatalyst, and isolating the cathode and anode reaction gases in the fuel cell, and is not only a core component of the engine of the fuel cell vehicle, but also a key material for supporting the fuel cell and the fuel cell vehicle industry. The carrier film is a key material for continuously producing the fuel cell film, and the carrier film is required to have the properties of high surface energy, proper peel strength, better mechanical property, high temperature resistance, low water absorption, good creep resistance, stable chemical property and the like in actual production and use of downstream customers. The higher surface energy of the carrier film is beneficial to the spreading of the perfluorosulfonic acid resin solution; the peel strength between the fuel cell membrane and the carrier membrane refers to the maximum force required for peeling the fuel cell membrane from the carrier membrane in unit width, and the peel strength between the fuel cell proton membrane and the carrier membrane is an important property and determines whether to match the roll-to-roll processing technology of the downstream customer of the fuel cell proton membrane for producing CCM (continuous CCM); continuous production of fuel cell membranes firstly requires excellent mechanical properties, high temperature resistance, low water absorption and creep resistance of the carrier membrane, and the carrier membrane has stable chemical properties and can resist corrosion of perfluorosulfonic acid resin.
The Nafion membrane is most widely used in the market at present, but with the development of hydrogen fuel cells, the production level of membrane electrodes is improved, the cost is reduced, and the like, so that the production process of CCM is gradually converted into a roll-to-roll process, which requires that the peeling strength between the fuel cell membrane and the carrier membrane is controlled within a proper range, and neither the fuel cell membrane wrinkles in the roll-to-roll CCM production process because of the low peeling strength nor the fuel cell membrane cannot be peeled from the carrier membrane because of the too high peeling strength.
SUMMERY OF THE UTILITY MODEL
The to-be-solved technical problem of the utility model is: the defects of the prior art are overcome, and a laminated structure of the proton membrane and the carrier membrane of the fuel cell is provided, so that the peeling strength between the proton membrane and the carrier membrane of the fuel cell can be controlled in a proper range, and the large-scale stable production condition of the proton membrane of the fuel cell is met.
The utility model discloses an adopt following technical scheme to realize:
the laminated structure of the fuel cell proton membrane and the bearing membrane comprises the fuel cell proton membrane and the bearing membrane, wherein the fuel cell proton membrane comprises an upper polymer resin layer, a reinforcing material and a lower polymer resin layer, the upper polymer resin layer and the lower polymer resin layer are respectively coated on the upper side and the lower side of the reinforcing material, the bearing membrane comprises a transparent or semitransparent polymer membrane, a surface modification layer is arranged on the transparent or semitransparent polymer membrane, and the polymer resin layer under the fuel cell proton membrane and the surface modification layer of the bearing membrane are laminated to form a laminated structure.
The thickness of the proton membrane of the fuel cell is 6-25 um.
The upper polymer resin layer and the lower polymer resin layer are all perfluorinated sulfonic acid resin.
The upper polymer resin layer and the lower polymer resin layer are completely the same.
The reinforcing material is an e-PTFE porous membrane, the thickness of the e-PTFE porous membrane is 5-20um, and the porosity of the e-PTFE porous membrane is 70-90%. The mechanical property of the proton membrane of the fuel cell can be improved, and the swelling ratio of the proton membrane of the fuel cell can be reduced.
Preferably, the transparent or translucent polymer film is a polymethylpentene film, a polyethylene terephthalate film, a polystyrene film, a polycarbonate film, a polyethylene film, a polyvinyl chloride film, a polyvinylidene fluoride film or a polyimide film, and has the properties of good mechanical property, high temperature resistance, low water absorption, good creep resistance, stable chemical property and the like.
The thickness of the transparent or semitransparent polymer film is 50-200 um.
The thickness of the surface modification layer is 1-100nm, and the surface energy is more than or equal to 35 dyn/m. The surface modified layer is prepared by carrying out plasma grafting modification or surface modification by corona treatment on a transparent or semitransparent polymer film. Wherein, in the plasma grafting modification, Ar is adopted as the activating gas, the activating time is 3-10min, and C is adopted3F6Grafting gas for 10-30 min; the power used during corona treatment is 3-6 KW.
Compared with the prior art, the beneficial effects of the utility model are as follows:
1. the utility model discloses a set up the surface modification layer on the carrier film, can make perfluorosulfonic acid resin solution evenly spread in the fuel cell proton membrane, ensure the thickness homogeneity of polymer resin layer, satisfy and use the large-scale stable production condition of coating mode to the fuel cell proton membrane.
2. The utility model discloses can make and have appropriate peel strength between carrier film and the fuel cell proton membrane, can satisfy CCM volume to volume serialization stable production.
Drawings
Fig. 1 is a schematic structural view of the present invention;
in the figure: 1. a carrier film; 101. a transparent or translucent polymeric film; 102. a surface modification layer; 2. a fuel cell proton membrane; 201. a lower polymer resin layer; 202. a reinforcing material; 203. and (3) coating a polymer resin layer.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples.
Example 1
As shown in fig. 1, the laminated structure of the fuel cell proton membrane and the carrier membrane comprises a fuel cell proton membrane 2 and a carrier membrane 1, wherein the fuel cell proton membrane 2 comprises an upper polymer resin layer 203, a reinforcing material 202 and a lower polymer resin layer 201, the upper polymer resin layer 203 and the lower polymer resin layer 201 are respectively coated on the upper side and the lower side of the reinforcing material 202, the carrier membrane 1 comprises a transparent or semitransparent polymer membrane 101, a surface modification layer 102 is arranged on the transparent or semitransparent polymer membrane 101, and the lower polymer resin layer 201 of the fuel cell proton membrane 2 and the surface modification layer 102 of the carrier membrane 1 are laminated to form a laminated structure.
The thickness of the fuel cell proton membrane 2 is 6-25um, the thickness of the transparent or semitransparent polymer membrane 101 is 50-200um, the thickness of the surface modification layer 102 is 1-100nm, and the surface energy is more than or equal to 35 dyn/m.
The upper polymer resin layer 203 and the lower polymer resin layer 201 are completely the same and are all perfluorosulfonic acid resins.
The reinforced material 202 is an e-PTFE porous membrane, the thickness of which is 5-20um, and the porosity of which is 70-90%.
In the preparation, a transparent or translucent polymer film 101 is selected from polyethylene terephthalate film, a pressure of 30Pa and a power of 100W are selected by a plasma processor, and Ar gas is usedActivating the polyethylene terephthalate film for 5min, and then introducing C3F6The gas is used for 30min to graft and modify the surface of the substrate to form a surface modified layer 102. And then, uniformly coating a perfluorinated sulfonic acid resin solution with the solid content of 10 wt% on two sides of the e-PTFE membrane, then covering a wet membrane on the surface modification layer 102 of the carrier membrane 1, and drying at 100 ℃ for 2h to form a membrane, thus preparing the proton membrane 2 of the fuel cell.
Example 2
As shown in fig. 1, the laminated structure of the fuel cell proton membrane and the carrier membrane comprises a fuel cell proton membrane 2 and a carrier membrane 1, wherein the fuel cell proton membrane 2 comprises an upper polymer resin layer 203, a reinforcing material 202 and a lower polymer resin layer 201, the upper polymer resin layer 203 and the lower polymer resin layer 201 are respectively coated on the upper side and the lower side of the reinforcing material 202, the carrier membrane 1 comprises a transparent or semitransparent polymer membrane 101, a surface modification layer 102 is arranged on the transparent or semitransparent polymer membrane 101, and the lower polymer resin layer 201 of the fuel cell proton membrane 2 and the surface modification layer 102 of the carrier membrane 1 are laminated to form a laminated structure.
The thickness of the fuel cell proton membrane 2 is 6-25um, the thickness of the transparent or semitransparent polymer membrane 101 is 50-200um, the thickness of the surface modification layer 102 is 1-100nm, and the surface energy is more than or equal to 35 dyn/m.
The upper polymer resin layer 203 and the lower polymer resin layer 201 are completely the same and are all perfluorosulfonic acid resins.
The reinforced material 202 is an e-PTFE porous membrane, the thickness of which is 5-20um, and the porosity of which is 70-90%.
During preparation, a transparent or semitransparent polymer film 101 is selected and a polycarbonate film is adopted, and the surface of the polycarbonate is modified through corona treatment with the power of 3KW to form a surface modified layer 102. And then, uniformly coating a perfluorinated sulfonic acid resin solution with the solid content of 10 wt% on two sides of the e-PTFE membrane, then covering a wet membrane on the surface modification layer 102 of the carrier membrane 1, and drying at 120 ℃ for 2h to form a membrane, thus preparing the proton membrane 2 of the fuel cell.
Example 3
As shown in fig. 1, the laminated structure of the fuel cell proton membrane and the carrier membrane comprises a fuel cell proton membrane 2 and a carrier membrane 1, wherein the fuel cell proton membrane 2 comprises an upper polymer resin layer 203, a reinforcing material 202 and a lower polymer resin layer 201, the upper polymer resin layer 203 and the lower polymer resin layer 201 are respectively coated on the upper side and the lower side of the reinforcing material 202, the carrier membrane 1 comprises a transparent or semitransparent polymer membrane 101, a surface modification layer 102 is arranged on the transparent or semitransparent polymer membrane 101, and the lower polymer resin layer 201 of the fuel cell proton membrane 2 and the surface modification layer 102 of the carrier membrane 1 are laminated to form a laminated structure.
The thickness of the fuel cell proton membrane 2 is 6-25um, the thickness of the transparent or semitransparent polymer membrane 101 is 50-200um, the thickness of the surface modification layer 102 is 1-100nm, and the surface energy is more than or equal to 35 dyn/m.
The upper polymer resin layer 203 and the lower polymer resin layer 201 are completely the same and are all perfluorosulfonic acid resins.
The reinforced material 202 is an e-PTFE porous membrane, the thickness of which is 5-20um, and the porosity of which is 70-90%.
During preparation, a transparent or semitransparent polymer film 101 is selected and a polymethylpentene film is adopted, and the surface of the polymethylpentene film is modified through corona treatment with the power of 6KW to form a surface modified layer 102. And then, uniformly coating a perfluorinated sulfonic acid resin solution with the solid content of 10 wt% on two sides of the e-PTFE membrane, then covering a wet membrane on the surface modification layer 102 of the carrier membrane 1, and drying at 150 ℃ for 2h to form a membrane, thus preparing the proton membrane 2 of the fuel cell.
Of course, the above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and the technical field of the present invention is equivalent to the changes and improvements made in the actual range of the present invention, which should be attributed to the patent coverage of the present invention.

Claims (8)

1. A fuel cell proton membrane and carrier membrane laminate structure, comprising: the fuel cell proton membrane comprises a fuel cell proton membrane (2) and a carrier membrane (1), wherein the fuel cell proton membrane (2) comprises an upper polymer resin layer (203), a reinforcing material (202) and a lower polymer resin layer (201), the upper polymer resin layer (203) and the lower polymer resin layer (201) are respectively coated on the upper side and the lower side of the reinforcing material (202), the carrier membrane (1) comprises a transparent or semitransparent polymer membrane (101), a surface modification layer (102) is arranged on the transparent or semitransparent polymer membrane (101), and the lower polymer resin layer (201) of the fuel cell proton membrane (2) and the surface modification layer (102) of the carrier membrane (1) are laminated to form a laminated body structure.
2. The fuel cell proton membrane and carrier membrane laminate structure of claim 1 wherein: the thickness of the fuel cell proton membrane (2) is 6-25 um.
3. The fuel cell proton membrane and carrier membrane laminate structure of claim 1 wherein: the upper polymer resin layer (203) and the lower polymer resin layer (201) are all perfluorinated sulfonic acid resin.
4. The fuel cell proton membrane and carrier membrane laminate structure of claim 1 wherein: the upper polymer resin layer (203) and the lower polymer resin layer (201) are completely the same.
5. The fuel cell proton membrane and carrier membrane laminate structure of claim 1 wherein: the reinforcing material (202) is an e-PTFE porous membrane, the thickness of the e-PTFE porous membrane is 5-20um, and the porosity of the e-PTFE porous membrane is 70-90%.
6. The fuel cell proton membrane and carrier membrane laminate structure of claim 1 wherein: the transparent or semitransparent polymer film (101) is a polymethylpentene film, a polyethylene terephthalate film, a polystyrene film, a polycarbonate film, a polyethylene film, a polyvinyl chloride film, a polyvinylidene fluoride film or a polyimide film.
7. The fuel cell proton membrane and carrier membrane laminate structure of claim 1 wherein: the transparent or translucent polymer film (101) has a thickness of 50-200 um.
8. The fuel cell proton membrane and carrier membrane laminate structure of claim 1 wherein: the thickness of the surface modification layer (102) is 1-100nm, and the surface energy is more than or equal to 35 dyn/m.
CN202020818773.1U 2020-05-15 2020-05-15 Laminated structure of proton membrane and bearing membrane of fuel cell Active CN212366004U (en)

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Application Number Priority Date Filing Date Title
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Publications (1)

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