CN112952137A - Sealing structure of membrane electrode protective film of fuel cell - Google Patents
Sealing structure of membrane electrode protective film of fuel cell Download PDFInfo
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- CN112952137A CN112952137A CN201911266798.3A CN201911266798A CN112952137A CN 112952137 A CN112952137 A CN 112952137A CN 201911266798 A CN201911266798 A CN 201911266798A CN 112952137 A CN112952137 A CN 112952137A
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- protective film
- membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 87
- 230000001681 protective effect Effects 0.000 title claims abstract description 51
- 239000000446 fuel Substances 0.000 title claims abstract description 36
- 238000007789 sealing Methods 0.000 title claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 51
- 210000000170 cell membrane Anatomy 0.000 claims abstract description 9
- 238000009792 diffusion process Methods 0.000 claims description 80
- 210000004027 cell Anatomy 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 230000002093 peripheral effect Effects 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 8
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 229920002530 polyetherether ketone Polymers 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical compound FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 15
- 239000000110 cooling liquid Substances 0.000 abstract description 3
- 239000002826 coolant Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 55
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0276—Sealing means characterised by their form
-
- 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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic material
-
- 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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0286—Processes for forming seals
-
- 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]
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
本发明提供了一种燃料电池膜电极保护膜密封结构，使得该种燃料电池膜电极质子交换膜处于密封状态，既保障了质子交换膜中的电解质沿保护膜交界处流出，又阻止了冷却液等介质通过保护膜交接出渗入质子交换膜中，解决了该种燃料电池膜电极在应用过程中跑电解液渗冷却液等问题，极大的提高了膜电极使用过程中的可操作性。
The invention provides a fuel cell membrane electrode protective film sealing structure, so that the fuel cell membrane electrode proton exchange membrane is in a sealed state, which not only ensures that the electrolyte in the proton exchange membrane flows out along the junction of the protective film, but also prevents the cooling liquid The other medium is transferred out and infiltrated into the proton exchange membrane through the protective membrane, which solves the problem of the fuel cell membrane electrode running off the electrolyte and infiltrating the coolant during the application process, and greatly improves the operability of the membrane electrode during use.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a membrane electrode protective film sealing structure of a fuel cell.
Background
The fuel cell is a fuel cell capable of storing hydrogen2、O2The chemical energy in (1) is directly converted into electric energy. The conversion process is not limited by the Carnot cycle process, so the energy conversion efficiency is high. In addition, the fuel cell has the characteristics of no noise and vibration in operation, clean emission, environmental friendliness and modularized arrangement, so that the fuel cell technology is inThe method has wide application prospect in the fields of new energy automobiles, distributed power stations and the like. The fuel cell membrane electrode is the core reaction component of the fuel cell, and the reliability and the service life of the fuel cell membrane electrode directly influence the reliability and the service life of a fuel cell system.
The traditional fuel cell membrane electrode consists of an electrolyte membrane, an anode gas diffusion electrode and a cathode gas diffusion electrode, and the edge of the membrane can be in contact with an external medium in the running process of a galvanic pile due to the outward extension of the electrolyte membrane, so that the phenomenon of electrolyte loss or the phenomenon that a cooling medium permeates into a proton exchange membrane is caused, and the reliability and the service life of the membrane electrode are further influenced.
Based on the method, the sealing method of the membrane electrode of the novel fuel cell realizes the sealing of the electrolyte membrane in the membrane electrode and isolates the electrolyte membrane from external media on the premise of not influencing the discharge performance of the membrane electrode, thereby improving the reliability and the service life of the membrane electrode.
Disclosure of Invention
The invention aims to provide a sealing method of a fuel cell membrane electrode, which is characterized in that a proper protective film is selected to seal an electrolyte membrane in the membrane electrode so as to isolate the electrolyte membrane from an external medium, thereby improving the reliability and prolonging the service life of the membrane electrode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a membrane electrode protective film sealing structure of fuel cell, the membrane electrode includes anode gas diffusion electrode, cathode gas diffusion electrode, and electrolyte membrane between the anode gas diffusion electrode and the cathode gas diffusion electrode, the anode gas diffusion electrode and the cathode gas diffusion electrode are oppositely arranged in the middle of two sides of the electrolyte membrane, and the peripheral edges of the anode gas diffusion electrode and the cathode gas diffusion electrode are spaced from the peripheral edge of the electrolyte membrane, namely a distance is left, so that the peripheral edge of the electrolyte membrane forms a covering area without anode gas diffusion electrode and cathode gas diffusion electrode,
two sides of the electrolyte membrane are respectively provided with an annular protective film with a through hole in the middle, the annular protective film is attached to the coverage area of the peripheral edge of the electrolyte membrane without an anode gas diffusion electrode and a cathode gas diffusion electrode, the anode gas diffusion electrode and the cathode gas diffusion electrode are respectively positioned in the middle through holes of the two annular protective films, the shape and the size of the through holes are the same as those of the anode gas diffusion electrode and the cathode gas diffusion electrode, the inner side edges of the two annular protective films are respectively attached to the peripheral edges of the anode gas diffusion electrode and the cathode gas diffusion electrode, and the peripheral edges of the outer ends of the two annular protective films, which are far away from the electrolyte membrane, are hermetically connected.
The opposite surfaces of the closed connecting ends of the two annular protective films are respectively provided with a coating, and the two coating areas are relatively overlapped and then fused into a whole, so that the closed connection of the outer ends of the two annular protective films far away from the electrolyte membrane is realized.
The other kind of fuel cell membrane electrode protecting film sealing structure has two integrated protecting films, which have central through hole in the shape and size the same as that of the anode gas diffusion electrode and the cathode gas diffusion electrode, and one ring notch in the inner wall of the side edge of the ring film, and the electrolyte film with covering area without anode gas diffusion electrode and cathode gas diffusion electrode inside the ring notch and inner side edge adhered to the peripheral edges of the anode gas diffusion electrode and the cathode gas diffusion electrode.
The protective film is made of a material resistant to phosphoric acid corrosion and high temperature.
The phosphoric acid corrosion resistant material is any one of Polysulfone (PSU), polyether ether ketone (PEEK), Polyimide (PI), polyphenylene sulfide (PPS) Polytetrafluoroethylene (PTFE), soluble Polytetrafluoroethylene (PFA) and perfluoroethylene propylene copolymer (FEP).
The thickness of the protective film is 5% -40% of the thickness of the gas diffusion electrode.
The protective film comprises a laminated support layer and a coating layer.
The heat-resistant film materials such as the supporting layer Polysulfone (PSU), the polyether ether ketone (PEEK), the Polyimide (PI), the polyphenylene sulfide (PPS) and the like have the heat-resistant temperature higher than 400 ℃ and have the characteristics of good acid resistance, alkali resistance, insulation and the like. The coating is a high-temperature melting compound such as Polytetrafluoroethylene (PTFE), perfluoroethylene propylene copolymer (FEP), soluble Polytetrafluoroethylene (PFA) and the like, the compound is melted at 300-350 ℃, and after cooling, the compound has good adhesion and has the characteristics of acid resistance, alkali resistance, insulation and the like.
The membrane electrode structure is applied to a high-temperature phosphoric acid fuel cell.
The structure of the invention ensures that the proton exchange membrane of the membrane electrode of the fuel cell is in a sealed state, thereby not only ensuring that the electrolyte in the proton exchange membrane flows out along the junction of the protective membrane, but also preventing the media such as cooling liquid from passing through the protective membrane and permeating into the proton exchange membrane, solving the problems that the electrolyte runs out and the cooling liquid permeates in the membrane electrode of the fuel cell during the application process, and greatly improving the operability of the membrane electrode.
Drawings
Fig. 1 is a gas diffusion electrode-electrolyte membrane assembly.
Fig. 2 is a protective film.
FIG. 3 is a membrane electrode assembly; FIG. 1 shows a gas diffusion electrode; 2 is an electrolyte membrane; and 3 is a protective film.
Detailed Description
Example 1
A fuel cell sealing method comprising the steps of:
1) in the membrane electrode preparation, firstly, the external dimension length and width a x b of the square gas diffusion electrode (anode gas diffusion electrode, cathode gas diffusion electrode) and the external dimension length and width c x d of the electrolyte membrane are designed according to requirements. In this case, the length and width dimensions of the electrolyte membrane are controlled to be 2 to 3mm larger than those of the gas diffusion electrode. And cutting and forming the blank through a cutting die.
2) The anode gas diffusion electrode, the cathode gas diffusion electrode and the electrolyte membrane are pressed together at a certain temperature and pressure through a specific tool, and are integrated into a whole through the liquid tension on the membrane surface, which is called a gas diffusion electrode-electrolyte membrane assembly, and is shown in fig. 1.
3) Selecting a fuel cell protective film, wherein the thickness is generally 20-200 μm (the preferred thickness is 20-120 μm), and for the preferred thickness, the protective film is a square support film with a coating on one side, the thickness of the support film is generally 10-190 μm (the preferred thickness is 10-100 μm), and the thickness of the coating is generally 5-50 μm (the preferred thickness is 5-20 μm);
4) confirming the coating material of the protective film to obtain the melting temperature T and the specific heat capacity C of the coating material;
5) confirming a base material to obtain the heat transfer coefficient lambda and the density rho of the base material;
6) the overall dimension of the protective film is designed, the two protective film coating sides are stacked in layers for fusion, the outer end sides are hermetically connected after fusion, so that the protective film is in a shape of a Chinese character 'hui', namely a square ring, the shape and the dimension of the inner frame of the protective film are the outer edge dimension of the gas diffusion electrode, and the shape and the dimension of the outer frame of the protective film are the outer edge dimension of the stack bipolar plate. As shown in fig. 2. And cutting and forming the blank through a cutting die.
7) And through a designated tool clamp, the upper side and the lower side of an electrolyte membrane of the gas diffusion electrode-electrolyte membrane assembly are covered with protective films, so that the inner protective film frame is just connected with the outer gas diffusion electrode frame. See fig. 3.
8) And designing the sealing size. And sealing the position, which is 1-2mm away from the electrolyte membrane along the outer edge of the electrolyte membrane under the condition that the sealing of the stack is not influenced, wherein the sealing condition is divided into three parameters of pressure, temperature and time. The sealing pressure of the film is generally controlled between 1 and 5bar, the sealing temperature is slightly higher than the melting temperature T of the coating material of the protective film, and the time is between 10 and 20S.
After the high-temperature phosphoric acid fuel cell electrode prepared by the method is assembled into a single cell, a service life test is carried out for 500 hours, and the cell is inspected to find no acid leakage phenomenon generated by the traditional electrode structure.
Example 2
A fuel cell sealing method comprising the steps of:
1) in the membrane electrode preparation, firstly, the external dimension length and width a x b of the square gas diffusion electrode (anode gas diffusion electrode, cathode gas diffusion electrode) and the external dimension length and width c x d of the electrolyte membrane are designed according to requirements. In this case, the length and width dimensions of the electrolyte membrane are controlled to be 2 to 3mm larger than those of the gas diffusion electrode. And cutting and forming the blank through a cutting die.
2) The fuel cell protective film is selected, generally, the thickness delta is 40-400 μm (the preferred thickness is 40-240 μm), and for the protective film with the preferred thickness, the protective film is cut into a shape like a Chinese character 'hui', namely a square ring, by a tool clamp, the shape and the size of the inner frame of the protective film are the outer edge size of the gas diffusion electrode, and the shape and the size of the outer frame of the protective film are the outer edge size of the stack bipolar plate. Meanwhile, an annular groove with the thickness of an electrolyte membrane and the depth of 3-8mm is processed on the inner edge surface.
3) And placing the peripheral edge of the electrolyte membrane into the annular groove of the protective membrane through a tool clamp so as to flatten the electrolyte membrane.
4) The anode gas diffusion electrode, the cathode gas diffusion electrode and the electrolyte membrane are pressed together at a certain temperature and pressure through a specific tool, and are integrated into a whole through the liquid tension on the membrane surface to form a membrane electrode assembly with a protective membrane, as shown in fig. 3.
After the high-temperature phosphoric acid fuel cell electrode prepared by the method is assembled into a single cell, a service life test is carried out for 500 hours, and the cell is inspected to find no acid leakage phenomenon generated by the traditional electrode structure.
Comparative example 1
A fuel cell sealing method comprising the steps of:
1) in the membrane electrode preparation, firstly, the external dimension length and width a x b of the square gas diffusion electrode (anode gas diffusion electrode, cathode gas diffusion electrode) and the external dimension length and width c x d of the electrolyte membrane are designed according to requirements. In this case, the length and width dimensions of the electrolyte membrane are controlled to be 2 to 3mm larger than those of the gas diffusion electrode. And cutting and forming the blank through a cutting die.
2) The anode gas diffusion electrode, the cathode gas diffusion electrode and the electrolyte membrane are pressed together at a certain temperature and pressure through a specific tool, and are integrated into a whole through the liquid tension on the membrane surface, which is called a gas diffusion electrode-electrolyte membrane assembly, and is shown in fig. 1.
3) The fuel cell polyester frame has the same external dimension as the electrolyte membrane, and the inside of the fuel cell polyester frame is die-cut by a cutting die to form a through hole with the same external dimension as the gas diffusion electrode;
4) and placing the polyester frame of the fuel cell on the upper side and the lower side of an electrolyte membrane of the gas diffusion electrode-electrolyte membrane assembly through a designated tool fixture, and pressing to obtain the traditional membrane electrode.
After the traditional high-temperature phosphoric acid fuel cell electrode prepared by the method is assembled into a single cell, a service life test is carried out, the acid climbing phenomenon occurs in 100 hours, and the performance of the cell is obviously reduced.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911266798.3A CN112952137A (en) | 2019-12-11 | 2019-12-11 | Sealing structure of membrane electrode protective film of fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911266798.3A CN112952137A (en) | 2019-12-11 | 2019-12-11 | Sealing structure of membrane electrode protective film of fuel cell |
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| Publication Number | Publication Date |
|---|---|
| CN112952137A true CN112952137A (en) | 2021-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911266798.3A Pending CN112952137A (en) | 2019-12-11 | 2019-12-11 | Sealing structure of membrane electrode protective film of fuel cell |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883583A (en) * | 2022-06-09 | 2022-08-09 | 北京航空航天大学 | High-stability high-temperature membrane electrode for fuel cell and preparation method thereof |
| CN116544474A (en) * | 2023-05-30 | 2023-08-04 | 北京绿钒新能源科技有限公司 | Electrode protection structure and protection method of flow battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6716550B1 (en) * | 2002-12-20 | 2004-04-06 | Ballard Power Systems Inc. | Sealing membrane electrode assemblies for electrochemical fuel cells |
| CN1510770A (en) * | 2002-12-23 | 2004-07-07 | ƽ | Sealing structure of a fuel cell |
| DE10358052A1 (en) * | 2003-12-05 | 2005-06-30 | Stefan Dr. Nettesheim | Fuel cell arrangement for electrochemical fuel cells comprises a membrane-electrode structure arranged between two profiled electrically conducting separator plates |
| CN104167557A (en) * | 2014-08-27 | 2014-11-26 | 中国科学院大连化学物理研究所 | High-temperature fuel cell membrane electrode and assembly method thereof |
| CN109638293A (en) * | 2018-10-26 | 2019-04-16 | 浙江博氢新能源有限公司 | High-temperature fuel cell membrane electrode and preparation method thereof and assemble method |
-
2019
- 2019-12-11 CN CN201911266798.3A patent/CN112952137A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6716550B1 (en) * | 2002-12-20 | 2004-04-06 | Ballard Power Systems Inc. | Sealing membrane electrode assemblies for electrochemical fuel cells |
| CN1510770A (en) * | 2002-12-23 | 2004-07-07 | ƽ | Sealing structure of a fuel cell |
| DE10358052A1 (en) * | 2003-12-05 | 2005-06-30 | Stefan Dr. Nettesheim | Fuel cell arrangement for electrochemical fuel cells comprises a membrane-electrode structure arranged between two profiled electrically conducting separator plates |
| CN104167557A (en) * | 2014-08-27 | 2014-11-26 | 中国科学院大连化学物理研究所 | High-temperature fuel cell membrane electrode and assembly method thereof |
| CN109638293A (en) * | 2018-10-26 | 2019-04-16 | 浙江博氢新能源有限公司 | High-temperature fuel cell membrane electrode and preparation method thereof and assemble method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883583A (en) * | 2022-06-09 | 2022-08-09 | 北京航空航天大学 | High-stability high-temperature membrane electrode for fuel cell and preparation method thereof |
| CN114883583B (en) * | 2022-06-09 | 2023-10-24 | 北京航空航天大学 | High-stability high-temperature membrane electrode for fuel cell and preparation method thereof |
| CN116544474A (en) * | 2023-05-30 | 2023-08-04 | 北京绿钒新能源科技有限公司 | Electrode protection structure and protection method of flow battery |
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Application publication date: 20210611 |