WO2024135924A1 - Procédé permettant de préparer une membrane composite renforcée et ensemble membrane-électrode (mea) pour piles à combustible - Google Patents
Procédé permettant de préparer une membrane composite renforcée et ensemble membrane-électrode (mea) pour piles à combustible Download PDFInfo
- Publication number
- WO2024135924A1 WO2024135924A1 PCT/KR2023/000562 KR2023000562W WO2024135924A1 WO 2024135924 A1 WO2024135924 A1 WO 2024135924A1 KR 2023000562 W KR2023000562 W KR 2023000562W WO 2024135924 A1 WO2024135924 A1 WO 2024135924A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reinforced composite
- membrane
- composite membrane
- fuel cell
- electrode assembly
- Prior art date
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 138
- 239000012528 membrane Substances 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 59
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 22
- 229920000554 ionomer Polymers 0.000 claims description 57
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 32
- 239000011737 fluorine Substances 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 31
- -1 polytetrafluoroethylene Polymers 0.000 claims description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000557 Nafion® Polymers 0.000 claims description 10
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 8
- 239000010702 perfluoropolyether Substances 0.000 claims description 8
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 8
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 8
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229920003934 Aciplex® Polymers 0.000 claims description 4
- 229920003937 Aquivion® Polymers 0.000 claims description 4
- 229920003935 Flemion® Polymers 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001780 ECTFE Polymers 0.000 claims 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 54
- 239000001257 hydrogen Substances 0.000 description 52
- 229910052739 hydrogen Inorganic materials 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 12
- 230000005611 electricity Effects 0.000 description 11
- 239000007800 oxidant agent Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000000429 assembly Methods 0.000 description 4
- 230000000712 assembly Effects 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
Images
Definitions
- the present invention relates to a method of manufacturing reinforced composite membranes and membrane-electrode assemblies (MEAs) for fuel cells.
- a fuel cell is a power generation system that directly converts chemical energy generated by electrochemically reacting fuel (hydrogen or methanol) and an oxidizing agent (oxygen) into electrical energy. It is a next-generation energy source with high energy efficiency and eco-friendly characteristics with low pollutant emissions. Research and development are underway. Fuel cells can be used by selecting high-temperature or low-temperature fuel cells depending on the field of application, and are usually classified according to the type of electrolyte. For high-temperature use, solid oxide fuel cells (SOFC) and molten carbonate fuel cells are used. There are fuel cells (Molten Carbonate Fuel Cell, MCFC), and for low temperature applications, alkaline fuel cells (AFC) and polymer electrolyte membrane fuel cells (PEMFC) are being developed. .
- fuel Hydrogen or methanol
- oxygen oxygen
- polymer electrolyte fuel cells can be subdivided into proton exchange membrane fuel cells (PEMFC), which use hydrogen gas as fuel, and direct fuel cells, which use liquid methanol as fuel by directly supplying it to the anode.
- PEMFC proton exchange membrane fuel cells
- direct fuel cells which use liquid methanol as fuel by directly supplying it to the anode.
- methanol fuel cells Direct Methanol Fuel Cell, DMFC
- Polymer electrolyte membrane fuel cells are attracting attention as portable, automotive, and home power devices due to their advantages such as low operating temperature of less than 100°C, exclusion of water leakage problems due to use of solid electrolyte, fast start-up and response characteristics, and excellent durability.
- it is a high-output fuel cell with a higher current density than other types of fuel cells, and because it can be miniaturized, research into portable fuel cells continues to progress.
- the unit cell structure of this fuel cell consists of an electrolyte membrane made of polymer material with an anode (fuel electrode) and a cathode (oxygen electrode) applied on both sides, which is called a membrane-electrode assembly (Membrane). It is called Electrode Assembly (MEA).
- This membrane-electrode assembly (MEA) is the part where the electrochemical reaction of hydrogen and oxygen occurs and is composed of a cathode, an oxidation electrode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane (e.g., a hydrogen ion conductive electrolyte membrane).
- This membrane-electrode assembly is formed in such a way that the electrode catalyst layers of the anode and cathode are applied to both sides of an ion conductive electrolyte membrane.
- the membrane-electrode assembly (MEA), which can be seen as a key component of the electrochemical reaction of a fuel cell, uses ion conductive electrolyte membranes and platinum catalysts, which have a particularly high cost ratio, and is directly related to power production efficiency, so fuel cells It is considered the most important part in improving performance and increasing price competitiveness.
- the existing method of manufacturing a commonly used MEA is to prepare a paste by mixing a catalyst material with a hydrogen ion conductive binder, that is, fluorine-based Nafion Ionomer, and water and/or an alcohol solvent, This is coated on carbon cloth or carbon paper, which acts as an electrode support that supports the catalyst layer and at the same time as a gas diffusion layer, and then dried and heat-sealed to a hydrogen ion conductive electrolyte membrane.
- a hydrogen ion conductive binder that is, fluorine-based Nafion Ionomer
- water and/or an alcohol solvent This is coated on carbon cloth or carbon paper, which acts as an electrode support that supports the catalyst layer and at the same time as a gas diffusion layer, and then dried and heat-sealed to a hydrogen ion conductive electrolyte membrane.
- Republic of Korea Patent Publication No. 10-2016-0069285 discloses a reinforced film manufacturing apparatus, a reinforced film, and a method of manufacturing the reinforced film.
- the present invention provides a method for manufacturing a reinforced composite membrane and membrane-electrode assembly (MEA) for fuel cells using a surfactant containing a hydrophobic chain and a hydrophilic chain.
- MEA reinforced composite membrane and membrane-electrode assembly
- the present invention provides a reinforced composite membrane and membrane-electrode assembly (MEA) for fuel cells containing a surfactant containing a hydrophobic chain and a hydrophilic chain.
- MEA reinforced composite membrane and membrane-electrode assembly
- the present invention provides a fuel cell including the membrane-electrode assembly (MEA).
- MEA membrane-electrode assembly
- One aspect of the present invention is,
- the surfactant containing the hydrophobic chain and the hydrophilic chain may be represented by the following formula (1).
- x may be an integer from 1 to 10
- n may be an integer from 1 to 40.
- x may be an integer from 4 to 8
- n may be an integer from 10 to 20.
- the fluorine-based ionomer may include an ionomer selected from the group consisting of Nafion, Flemion, Aquivion, 3M TM PFSA ionomer, Aciplex, and combinations thereof. .
- the porous support is polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), fluorinated ethylene-propylene (FEP), and polyethylene.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- PVF polyvinyl fluoride
- PCTFE polychlorotrifluoroethylene
- FEP fluorinated ethylene-propylene
- FEP fluorinated ethylene-propylene
- the content of the surfactant may be 0.01 to 2 parts by weight based on 100 parts by weight of the fluorine-based ionomer.
- the drying may be performed at a temperature of 50°C to 100°C, and the annealing may be performed at a temperature of 100°C to 200°C.
- the method of manufacturing the membrane-electrode assembly (MEA) for a fuel cell includes the drying and annealing steps; Thereafter, the step of washing and pre-treating the reinforced composite membrane for a fuel cell may be further included.
- the washing may be performed using hydrogen peroxide (H 2 O 2 ), and the pretreatment may be performed using sulfuric acid (H 2 SO 4 ).
- Compression of the electrode may be performed through thermal compression.
- thermocompression is performed at a temperature of 100°C to 200°C and a pressure of 5 MPa to 20 MPa, and may be performed for 1 minute to 10 minutes.
- a reinforced composite membrane for a fuel cell comprising a porous support coated on at least one side with a fluorine-based ionomer and a surfactant containing a hydrophobic chain and a hydrophilic chain.
- the surfactant containing the hydrophobic chain and the hydrophilic chain may be represented by the following formula (1).
- x may be an integer from 1 to 10
- n may be an integer from 1 to 40.
- the content of the surfactant may be 0.01 to 2 parts by weight based on 100 parts by weight of the fluorine-based ionomer.
- a membrane-electrode assembly (MEA) for a fuel cell including the reinforced composite membrane for a fuel cell and a fuel cell including the same are provided.
- the fuel cell includes an electricity generator that includes the membrane-electrode assembly and a separator and generates electricity through an electrochemical reaction between fuel and an oxidant; a fuel supply unit that supplies fuel to the electricity generation unit; and an oxidizing agent supply unit that supplies an oxidizing agent to the generator.
- the reinforced composite membrane for fuel cells manufactured according to the present invention may effectively impregnate the porous support with the ionomer by using a surfactant.
- the performance of the membrane-electrode assembly and fuel cell containing the surfactant may be adjustable by adjusting the length of the hydrophobic chain or hydrophilic chain of the surfactant.
- Figure 1 is a schematic diagram showing a method of manufacturing a reinforced composite membrane and a membrane-electrode assembly (MEA) according to an embodiment of the present invention.
- FIGS 2 to 9 are views related to Production Example 1.
- Figures 2 and 3 are graphs measuring the contact angle and ionic conductivity according to the surfactant content of the reinforced composite membrane for fuel cells manufactured according to an embodiment of the present invention, respectively.
- Figures 4 and 5 are cross-sectional SEM photographs and component analysis photographs of reinforced composite membranes for fuel cells manufactured according to Comparative Example 1 and Examples of the present invention, respectively.
- Figure 6 is a graph showing the voltage and power density according to the current density of the membrane-electrode assembly manufactured according to Comparative Example 1 and Examples of the present invention.
- Figure 7 is a graph showing the ohmic resistance of the membrane-electrode assembly manufactured according to Comparative Example 1 and Examples of the present invention.
- Figure 8 is a graph showing the voltage according to the driving time of the membrane-electrode assembly manufactured according to Comparative Example 1 and Example of the present invention.
- Figure 9 is a graph showing the current density according to voltage of the membrane-electrode assembly manufactured according to Comparative Example 1 and Examples of the present invention.
- Figures 10 to 17 are views related to Production Example 2.
- 10 and 11 are graphs measuring the contact angle and ionic conductivity according to the surfactant content of the reinforced composite membrane for fuel cells manufactured according to an embodiment of the present invention, respectively.
- Figures 12 and 13 are cross-sectional SEM photographs and component analysis photographs of reinforced composite membranes for fuel cells manufactured according to Comparative Example 2 and Examples of the present invention, respectively.
- Figure 14 is a graph showing the voltage and power density according to the current density of the membrane-electrode assembly manufactured according to Comparative Example 2 and Example of the present invention.
- Figure 15 is a graph showing the ohmic resistance of the membrane-electrode assembly manufactured according to Comparative Example 2 and Example of the present invention.
- Figure 16 is a graph showing the voltage according to the driving time of the membrane-electrode assembly manufactured according to Comparative Example 2 and Example of the present invention.
- Figure 17 is a graph showing the current density according to voltage of the membrane-electrode assembly manufactured according to Comparative Example 2 and Example of the present invention.
- This invention is the result of the ‘Local Government-University Cooperation-Based Regional Innovation Project (2021RIS-004)’ conducted with the support of the National Research Foundation of Korea with resources from the Ministry of Education.
- the 'fuel cell' is not particularly limited, but is preferably a 'hydrogen fuel cell'.
- the first aspect of the present application is,
- the second aspect of the present application is,
- the method of manufacturing the reinforced composite membrane for a fuel cell may include mixing a fluorine-based ionomer and a surfactant containing a hydrophobic chain and a hydrophilic chain.
- the ionomer may be more smoothly impregnated and coated on a porous support, which will be described later, by using a surfactant containing the hydrophobic chain and the hydrophilic chain.
- the core of the invention of the reinforced composite membrane for fuel cells according to the present invention is to more smoothly impregnate and coat the porous support with the ionomer, and for this purpose, a surfactant may be used as described above.
- the surfactant containing the hydrophobic chain and the hydrophilic chain may be represented by the following formula (1).
- x may be an integer of 1 to 10
- n may be an integer of 1 to 40, preferably x is an integer of 4 to 8, and n may be an integer of 10 to 20.
- the performance of the reinforced composite membrane and membrane-electrode assembly (MEA) for fuel cells according to the present invention may improve.
- x is an integer greater than 10
- the effect on the hydrophobic group greatly increases compared to the hydrophilic group, so a problem may occur in which the ionomer does not dissolve in the solution.
- the smaller the number of n the better the performance of the reinforced composite membrane and membrane-electrode assembly (MEA) for fuel cells according to the present invention.
- n is an integer less than 10
- the fluorine-based ionomer is selected from the group consisting of Nafion, Flemion, Aquivion, 3M TM PFSA ionomer, Aciplex, and combinations thereof. It may contain an ionomer, and Nafion may be preferably used. At this time, the fluorine-based ionomer may be used as a main raw material for forming a reinforced composite membrane for fuel cells. Meanwhile, the Nafion may be represented by the following formula (2), and hydrogen ions (H + ) may be moved using a sulfone group (SO 3 - ).
- the fluorine-based ionomer is mixed with a surfactant and impregnated together with the porous support, the degree of impregnation may be improved, and through this, the performance of the fuel cell including the reinforced composite membrane for fuel cells may be improved.
- the content of the surfactant may be 0.01 to 2 parts by weight based on 100 parts by weight of the fluorine-based ionomer. At this time, if the content of the surfactant is less than 0.01 parts by weight compared to 100 parts by weight of the fluorine-based ionomer, the content of the surfactant is too small and the fluorine-based ionomer may not be smoothly impregnated into the porous support, and if it exceeds 2 parts by weight, the fluorine-based ionomer is relatively small. As the content of , the performance of the reinforced composite membrane or membrane-electrode assembly (MEA) for fuel cells may deteriorate.
- MUA reinforced composite membrane or membrane-electrode assembly
- the method of manufacturing the reinforced composite membrane for a fuel cell may include the step of impregnating the mixed solution with a porous support and coating it with a fluorine-based ionomer.
- the porous support is polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), fluorinated Ethylene-propylene (FEP), polyethylenetetrafluoroethylene (ETFE), polyethylenechlorotrifluoroethylene (ECTFE), perfluoropolyether (PFPE), perfluorosulfonic acid (PFSA), perfluoropolyoxetane and a material selected from the group consisting of combinations thereof, preferably polytetrafluoroethylene (PTFE), and according to an embodiment of the present invention, expandable polytetrafluoroethylene (PTFE) may be used.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- PVF polyvinyl fluoride
- PCTFE polychlorotrifluoroethylene
- FEP fluorinated Ethylene-
- Ethylene may be used.
- the porous support may have excellent physical and chemical properties and may include a large number of pores.
- impregnation of surfactant and ionomer may be possible through the pores.
- the polytetrafluoroethylene (PTFE) may be represented by the following formula (3).
- MEA membrane-electrode assembly
- the method of manufacturing the membrane-electrode assembly (MEA) for a fuel cell may include drying and annealing the reinforced composite membrane for a fuel cell manufactured according to the first aspect of the present application. there is.
- the drying may be performed at a temperature of 50°C to 100°C, and according to an embodiment of the present invention, it may be performed at a temperature of about 80°C.
- an annealing process may be performed, and the annealing may be performed at a temperature of 100° C. to 200° C., and according to an embodiment of the present invention, about 140° C. It may be performed at a temperature of °C.
- the method of manufacturing the membrane-electrode assembly (MEA) for a fuel cell may include the step of washing and pre-treating the reinforced composite membrane for a fuel cell.
- the washing may be performed using hydrogen peroxide (H 2 O 2 ), and the pretreatment may be performed using sulfuric acid (H 2 SO 4 ).
- the method of manufacturing the membrane-electrode assembly (MEA) for a fuel cell may include the step of pressing electrodes on both sides of the reinforced composite membrane for a fuel cell, respectively.
- the compression may be performed through thermal compression.
- the thermal compression may be performed at a temperature of 100°C to 200°C and a pressure of 5 MPa to 20 MPa, and according to one embodiment of the present invention, it may be performed at a temperature of about 140°C and a pressure of 15 MPa. You can. Additionally, the thermal compression may be performed for 1 to 10 minutes, and according to one embodiment of the present invention, may be performed for about 5 minutes.
- the compression may be performed using a catalyst, and the catalyst used in this case is not particularly limited, but platinum (Pt) may be preferably used.
- the third aspect of the present application is,
- a reinforced composite membrane for a fuel cell comprising a porous support coated on at least one side with a fluorine-based ionomer and a surfactant containing a hydrophobic chain and a hydrophilic chain.
- the fourth aspect of the present application is,
- MEA membrane-electrode assembly
- the fifth aspect of the present application is,
- an electricity generator comprising a membrane-electrode assembly and a separator according to the fourth aspect of the present application, and generating electricity through an electrochemical reaction between a fuel and an oxidizing agent; a fuel supply unit that supplies fuel to the electricity generation unit; and an oxidizing agent supply unit that supplies an oxidizing agent to the generator.
- the reinforced composite membrane for a fuel cell may include a porous support coated with a fluorine-based ionomer and a surfactant on at least one surface.
- the porous support is polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), fluorinated Ethylene-propylene (FEP), polyethylenetetrafluoroethylene (ETFE), polyethylenechlorotrifluoroethylene (ECTFE), perfluoropolyether (PFPE), perfluorosulfonic acid (PFSA), perfluoropolyoxetane and a material selected from the group consisting of combinations thereof, preferably polytetrafluoroethylene (PTFE), and according to an embodiment of the present invention, expandable polytetrafluoroethylene (PTFE) may be used. Ethylene (ePTFE) may be used.
- Ethylene (ePTFE) may be used.
- the surfactant containing the hydrophobic chain and the hydrophilic chain may be represented by the following formula (1).
- x may be an integer of 1 to 10
- n may be an integer of 1 to 40, preferably x is an integer of 4 to 8, and n may be an integer of 10 to 20.
- the performance of the reinforced composite membrane and membrane-electrode assembly (MEA) for fuel cells according to the present invention may improve.
- x is an integer greater than 10
- the effect on the hydrophobic group greatly increases compared to the hydrophilic group, so a problem may occur in which the ionomer does not dissolve in the solution.
- the smaller the number of n the better the performance of the reinforced composite membrane and membrane-electrode assembly (MEA) for fuel cells according to the present invention.
- n is an integer less than 10
- the fluorine-based ionomer is selected from the group consisting of Nafion, Flemion, Aquivion, 3M TM PFSA ionomer, Aciplex, and combinations thereof. It may contain an ionomer, and Nafion may be preferably used. At this time, the fluorine-based ionomer may be used as a main raw material for forming a reinforced composite membrane for fuel cells.
- the fluorine-based ionomer and surfactant may be coated on at least one side of the porous support, and preferably, may be coated on both sides.
- the content of the surfactant may be 0.01 to 2 parts by weight based on 100 parts by weight of the fluorine-based ionomer. At this time, if the content of the surfactant is less than 0.01 parts by weight compared to 100 parts by weight of the fluorine-based ionomer, the content of the surfactant is too small and the fluorine-based ionomer may not be smoothly impregnated into the porous support, and if it exceeds 2 parts by weight, the fluorine-based ionomer is relatively small. As the content of , the performance of the reinforced composite membrane or membrane-electrode assembly (MEA) for fuel cells may deteriorate.
- MUA reinforced composite membrane or membrane-electrode assembly
- the membrane-electrode assembly may include electrodes respectively bonded to both sides of the reinforced composite membrane for a fuel cell.
- a catalyst may be used for the bonding, and the catalyst used in this case is not particularly limited, but platinum (Pt) may be preferably used.
- the fuel cell includes at least one electricity generator that generates electrical energy through an oxidation reaction of fuel and a reduction reaction of an oxidizing agent, a fuel supply portion that supplies the above-described fuel to the electricity generator, and , It may be configured to include an oxidizing agent gap that supplies an oxidizing agent to the electricity generation unit.
- the membrane-electrode assembly may include one or more, and a separator for supplying fuel and an oxidizing agent may be disposed at both ends of the membrane-electrode assembly to form an electricity generator. Additionally, at least one such electricity generating unit may be gathered together to form a stack.
- a mixed solution was prepared by mixing Nafion solution (D2021, Chemours) and a surfactant represented by the following formula 1-1.
- x was 4.
- a reinforced composite membrane for a hydrogen fuel cell was manufactured by impregnating the mixed solution with expanded polytetrafluoroethylene (ePTFE, KOMEMTEC) as a porous support.
- ePTFE expanded polytetrafluoroethylene
- the reinforced composite membrane for hydrogen fuel cells prepared in step 1 above was dried and annealed at temperatures of 80°C and 140°C, respectively.
- MEA membrane-electrode assembly
- thermocompression was performed for 5 minutes at a temperature of 140°C and a pressure of 15 MPa.
- a membrane-electrode assembly (MEA) for a hydrogen fuel cell was manufactured in the same manner as in Formula 1-1 of Example 1, except that x was 6.
- a membrane-electrode assembly (MEA) for a hydrogen fuel cell was manufactured in the same manner as in Formula 1-1 of Example 1, except that x was 8.
- a membrane-electrode assembly (MEA) for a hydrogen fuel cell was manufactured using the same method as in step 1 of Example 1, except that no surfactant was used.
- a mixed solution was prepared by mixing Nafion solution (D2021, Chemours) and a surfactant represented by the following formula 1-2. At this time, n was 10 in the following Chemical Formula 1-2.
- a reinforced composite membrane for a hydrogen fuel cell was manufactured by impregnating the mixed solution with expanded polytetrafluoroethylene (ePTFE, KOMEMTEC) as a porous support.
- ePTFE expanded polytetrafluoroethylene
- the reinforced composite membrane for hydrogen fuel cells prepared in step 1 above was dried and annealed at temperatures of 80°C and 140°C, respectively.
- MEA membrane-electrode assembly
- thermocompression was performed for 5 minutes at a temperature of 140°C and a pressure of 15 MPa.
- MEA membrane-electrode assembly
- a membrane-electrode assembly (MEA) for a hydrogen fuel cell was manufactured in the same manner as in Chemical Formula 1-2 of Example 4, except that n was 20.
- a membrane-electrode assembly (MEA) for a hydrogen fuel cell was manufactured using the same method as in step 1 of Example 4, except that no surfactant was used.
Landscapes
- Fuel Cell (AREA)
Abstract
La présente invention se rapporte à un procédé permettant de préparer une membrane composite renforcée et un ensemble membrane-électrode (MEA) pour piles à combustible en utilisant un tensioactif et, plus particulièrement, à un procédé permettant de préparer une membrane composite renforcée et un ensemble MEA pour piles à combustible, caractérisé en ce qu'en ajustant la longueur de chaîne hydrophobe ou la longueur de chaîne hydrophile du tensioactif, la membrane composite renforcée préparée et l'ensemble MEA présentent d'excellentes performances.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20220183635 | 2022-12-23 | ||
KR20220183582 | 2022-12-23 | ||
KR10-2022-0183635 | 2022-12-23 | ||
KR10-2022-0183582 | 2022-12-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2024135924A1 true WO2024135924A1 (fr) | 2024-06-27 |
Family
ID=91588940
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2023/000562 WO2024135924A1 (fr) | 2022-12-23 | 2023-01-12 | Procédé permettant de préparer une membrane composite renforcée et ensemble membrane-électrode (mea) pour piles à combustible |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2024135924A1 (fr) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180053462A (ko) * | 2016-11-11 | 2018-05-23 | 한국화학연구원 | 짧은 불화알킬기를 포함하는 하이브리드형 불소계 비이온 계면활성제 및 이의 제조방법 |
KR20190080580A (ko) * | 2017-12-28 | 2019-07-08 | 현대자동차주식회사 | 고분자 전해질 연료전지용 전해질막의 제조 방법 및 수송용 고분자 전해질 연료전지 |
KR20210062444A (ko) * | 2019-11-21 | 2021-05-31 | 한국에너지기술연구원 | 막전극 접합체의 제조방법, 막전극 접합체 및 연료전지 |
KR102351563B1 (ko) * | 2021-09-03 | 2022-01-17 | (주)미유테크 | 불화알킬글리세린 유도체 및 계면활성제 용도 |
KR20220048254A (ko) * | 2020-10-12 | 2022-04-19 | 한국기술교육대학교 산학협력단 | 연료전지용 강화 복합막 및 그 제조방법 |
-
2023
- 2023-01-12 WO PCT/KR2023/000562 patent/WO2024135924A1/fr unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20180053462A (ko) * | 2016-11-11 | 2018-05-23 | 한국화학연구원 | 짧은 불화알킬기를 포함하는 하이브리드형 불소계 비이온 계면활성제 및 이의 제조방법 |
KR20190080580A (ko) * | 2017-12-28 | 2019-07-08 | 현대자동차주식회사 | 고분자 전해질 연료전지용 전해질막의 제조 방법 및 수송용 고분자 전해질 연료전지 |
KR20210062444A (ko) * | 2019-11-21 | 2021-05-31 | 한국에너지기술연구원 | 막전극 접합체의 제조방법, 막전극 접합체 및 연료전지 |
KR20220048254A (ko) * | 2020-10-12 | 2022-04-19 | 한국기술교육대학교 산학협력단 | 연료전지용 강화 복합막 및 그 제조방법 |
KR102351563B1 (ko) * | 2021-09-03 | 2022-01-17 | (주)미유테크 | 불화알킬글리세린 유도체 및 계면활성제 용도 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2014200286A2 (fr) | Composé à base de sulfonate et membrane électrolytique de type polymère l'utilisant | |
WO2018124645A1 (fr) | Procédé de fabrication d'électrode, électrode fabriquée par ce procédé, ensemble membrane-électrode comprenant ladite électrode et pile à combustible comprenant ledit ensemble membrane-électrode | |
WO2014073934A1 (fr) | Polymère conducteur d'ion comprenant un copolymère à blocs partiellement ramifié et son utilisation | |
WO2014178619A1 (fr) | Membrane électrolytique polymère, ensemble électrodes à membrane comprenant une membrane électrolytique polymère, et pile à combustible comprenant un ensemble électrodes à membrane | |
WO2014081235A1 (fr) | Polymère conducteur d'ions comprenant un groupe phényle latéral substitué par deux groupes aromatiques sulfonés ou plus et son utilisation | |
WO2016089155A1 (fr) | Membrane électrolytique polymère | |
WO2017171285A2 (fr) | Membrane d'échange d'ions, son procédé de fabrication, et dispositif de stockage d'énergie la comprenant | |
WO2015047008A1 (fr) | Membrane d'électrolyte polymère, procédé de fabrication associé, et ensemble membrane-électrode comprenant ladite membrane | |
WO2018199458A1 (fr) | Membrane échangeuse d'ions, son procédé de fabrication, et dispositif de stockage d'énergie comprenant ladite membrane échangeuse d'ions | |
WO2016175502A1 (fr) | Solution de dispersion de nanoparticules d'ionomère perfluoré, et son procédé de préparation | |
WO2021112420A1 (fr) | Nouvel ionomère à base de polyfluorène, membrane échangeuse d'anions et son procédé de production | |
WO2024135924A1 (fr) | Procédé permettant de préparer une membrane composite renforcée et ensemble membrane-électrode (mea) pour piles à combustible | |
WO2019132281A1 (fr) | Catalyseur, son procédé de préparation, électrode le comprenant, ensemble membrane-électrode et pile à combustible | |
WO2016068606A1 (fr) | Composition de polymérisation, polymère utilisant la composition de polymérisation et membrane électrolytique polymère utilisant le polymère | |
WO2021066544A1 (fr) | Dispersion d'ionomères ayant une stabilité de dispersion élevée, son procédé de production, et membrane échangeuse de protons produite au moyen de celui-ci | |
WO2016068605A1 (fr) | Composé à base de fluor pour agent de ramification, polymère l'utilisant et membrane d'électrolyte polymère l'utilisant | |
WO2017175892A1 (fr) | Membrane électrolytique composite pour pile à combustible, ensemble membrane-électrodes comportant une telle membrane, pile à combustible comportant un tel ensemble, et procédé pour la fabrication de membrane électrolytique composite pour pile à combustible, d'ensemble membrane-électrodes comportant une telle membrane, de pile à combustible comportant un tel ensemble | |
WO2013165079A1 (fr) | Matériau de cathode pour pile à combustible à oxyde solide, composition pour cathode contenant celui-ci, cathode pour pile à combustible à oxyde solide, et pile à combustible à oxyde solide | |
WO2016122195A1 (fr) | Composé comprenant un anneau aromatique, polymère comprenant ce composé et membrane polyélectrolytique l'utilisant | |
WO2016089156A2 (fr) | Polymère et membrane électrolytique polymère le comprenant | |
WO2019009594A1 (fr) | Électrolyte polymère pour batterie secondaire et batterie secondaire au lithium le comprenant | |
WO2016089152A1 (fr) | Composé halogéné, polymère comprenant ce composé, et membrane électrolytique polymère comprenant celui-ci | |
WO2021125417A1 (fr) | Acier inoxydable destiné à un séparateur de pile à combustible à membrane d'échange de protons et son procédé de production | |
WO2018194393A1 (fr) | Procédé de fabrication d'une membrane échangeuse d'ions utilisant la modification chimique et membrane échangeuse d'ions ainsi fabriquée | |
WO2022196913A1 (fr) | Structure de catalyseur monoatomique et son procédé de préparation |