WO2015190887A1 - 복합체 전해질막 및 이의 제조방법 - Google Patents
복합체 전해질막 및 이의 제조방법 Download PDFInfo
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- WO2015190887A1 WO2015190887A1 PCT/KR2015/005967 KR2015005967W WO2015190887A1 WO 2015190887 A1 WO2015190887 A1 WO 2015190887A1 KR 2015005967 W KR2015005967 W KR 2015005967W WO 2015190887 A1 WO2015190887 A1 WO 2015190887A1
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
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- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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- C08G75/23—Polyethersulfones
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- a fuel cell is a power generation system that converts chemical reaction energy of a fuel and an oxidant into electrical energy.
- Hydrogen, a hydrocarbon such as methanol, butane, and the like are typically used as an oxidant.
- Fuel cells include polymer electrolyte fuel cells (PEMFC), direct methanol fuel cells (DMFC), phosphoric acid fuel cells (PAFC), alkaline fuel cells (AFC), molten carbonate fuel cells (MCFC), and solid oxide fuels. Batteries (SOFC) and the like.
- PEMFC polymer electrolyte fuel cells
- DMFC direct methanol fuel cells
- PAFC phosphoric acid fuel cells
- AFC alkaline fuel cells
- MCFC molten carbonate fuel cells
- SOFC solid oxide fuels.
- polymer electrolyte fuel cells have been researched most actively because of their high energy density and high output.
- the polymer electrolyte fuel cell differs from other fuel cells in that it uses a solid polymer electrolyte membrane instead of a liquid as an electrolyte.
- the present application is to provide a composite membrane for a fuel cell excellent in hydrogen ion conductivity, mechanical properties, dimensional stability and the like and a method of manufacturing the same.
- a poly (arylene ether sulfone) copolymer comprising a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2;
- Core-shell particles comprising an inorganic particle core and a basic organic polymer shell
- R4 to R7 and R13 to R16 are each independently hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms
- At least one of R11, R12 and R18 is -SO 3 R17 and the other is hydrogen or a linear or branched alkyl group having 1 to 10 carbon atoms,
- R17 is H, Li, Na or K,
- a and A ' are each independently a direct bond, a divalent fluorene group, or a linear or branched alkylene group having 1 to 10 carbon atoms,
- n, o, p and r are each independently 0-4, q, s and t are each independently 0-3,
- y is 0 or 1
- a and b are molar ratios of Formulas 1 and 2, each independently 0.1 to 0.99.
- the poly (arylene ether sulfone) copolymer Preparing a composition comprising core-shell particles comprising an inorganic particle core and a basic organic polymer shell, and
- It provides a method for producing a composite electrolyte membrane comprising a.
- another exemplary embodiment of the present application provides a fuel cell including the composite electrolyte membrane.
- the composite electrolyte membrane according to the present application includes core-shell particles having a basic organic polymer shell and a poly (arylene ether sulfone) copolymer, thereby comparing hydrogen ions with a polymer electrolyte membrane containing only a poly (arylene ether sulfone) copolymer. Conductivity, dimensional stability, mechanical strength and the like can be improved.
- the composite electrolyte membrane according to the present application may improve hydrogen ion conductivity, dimensional stability, and the like, compared to a composite electrolyte membrane including particles having no shell structure and a poly (arylene ether sulfone) copolymer.
- the composite electrolyte membrane according to the present application may improve hydrogen ion conductivity, dimensional stability, and the like, compared to a composite electrolyte membrane including a core-shell particle having an acidic polymer shell and a poly (arylene ether sulfone) copolymer.
- the composite electrolyte membrane according to the present application is characterized in that the hydrogen ion conductivity, mechanical properties, dimensional stability, etc. according to the size of the inorganic core, the size of the organic polymer shell, the content ratio between the poly (arylene ether sulfone) copolymer and the core-shell particles, etc. Flexibility to adjust
- FIG. 1 is a diagram schematically illustrating a process of forming core-shell particles of a composite electrolyte membrane according to an exemplary embodiment of the present application.
- FIG. 2 is a view schematically showing a process of manufacturing a composite electrolyte membrane according to an exemplary embodiment of the present application.
- Hydrocarbon-based polymer electrolyte membranes have excellent thermal and oxidative stability, mechanical properties, processability, etc., but generally have a disadvantage in that hydrogen ion conductivity is lower than that of Nafion.
- hydrogen ion conductivity is lower than that of Nafion.
- the content of sulfonic acid groups is increased to excessively increase the sulfonation degree, the water content increases and a large expansion ratio is obtained, thereby reducing dimensional stability.
- the preparation of a composite electrolyte membrane in which an inorganic substance is added to a polymer matrix has been studied. Among them, the use of silica particles having excellent hygroscopicity was able to improve not only dimensional stability but also hydrogen ion conductivity.
- the composite electrolyte membrane including core-shell silica particles using a polymer shell including a sulfonic acid group may have high hydrogen ion conductivity based on high ion exchange capacity (IEC), but stability is decreased due to high expansion rate. There is a problem. Accordingly, in the present application, by using a basic organic polymer shell, it was intended to simultaneously improve the dimensional stability and hydrogen ion conductivity through the acid-base interaction.
- IEC ion exchange capacity
- Composite electrolyte membrane according to an embodiment of the present application, the poly (arylene ether sulfone) copolymer comprising a repeating unit represented by the formula 1 and the repeating unit represented by the formula (2); And core-shell particles comprising an inorganic particle core and a basic organic polymer shell.
- the repeating unit represented by Chemical Formula 1 is a monomer that does not include a sulfonic acid group
- the repeating unit represented by Chemical Formula 2 is a monomer including a sulfonic acid group
- the sulfonation degree in the copolymer is controlled by adjusting the molar ratio thereof. I can regulate it.
- the hydrogen ion conductivity may not be sufficiently secured, and it is preferable to increase the molar ratio of the repeating unit represented by Formula 2 to the maximum.
- the molar ratio of the repeating unit containing no sulfonic acid group and the repeating unit containing a sulfonic acid group may be similar to or slightly lower than that of Nafion.
- the molar ratio of the repeating unit represented by Formula 1: the repeating unit represented by Formula 2 may be 1: 0.1 to 2: 3, but is not limited thereto.
- Chemical Formula 2 may be represented by the following Chemical Formula 2-1.
- R8 to R16, R18, A ', q, r, s, t, y and b are the same as defined in Formula 2 above.
- the copolymer including the repeating units represented by Formula 1 and Formula 2 as a main chain may be prepared using a dihydroxy monomer, a difluoro monomer, a monomer of the following structural formula, and the like.
- the viscosity of the crosslinked poly (arylene ether sulfone) copolymer may be 1.23 dL g ⁇ 1 , but is not limited thereto.
- the sulfonation degree of the crosslinked poly may be greater than 0 and 0.6 or less, but is not limited thereto.
- the weight average molecular weight of the copolymer is 10,000 to 3,000,000, specifically 50,000 to 1,000,000, and more preferably 50,000 to 800,000. When in the above range, it may have a high solubility and excellent mechanical properties.
- the crosslinked poly (arylene ether sulfone) copolymer according to the exemplary embodiment of the present application includes a crosslinked structure containing a sulfonic acid group, it is possible to increase the sulfonation degree of the entire electrolyte membrane, and thus a favorable effect on the hydrogen ion conductivity.
- the crosslinked electrolyte membrane according to the exemplary embodiment of the present application may show improved performance in not only hydrogen ion conductivity but also dimensional stability and mechanical properties.
- the core-shell particles are characterized by comprising an inorganic particle core and a basic organic polymer shell.
- the inorganic particle core may include silica particles, TiO 2 , ZrO 2 , and the like, but is not limited thereto.
- the inorganic particle core may use inorganic particles or surface treated inorganic particles.
- the surface treatment may be performed by using a silane compound such as vinyltrimethoxysilane and the like, by condensation reaction between the inorganic particles and the silane compound, and the surface treatment preferably includes a vinyl group on the surface of the inorganic particles.
- a silane compound such as vinyltrimethoxysilane and the like
- the surface treatment preferably includes a vinyl group on the surface of the inorganic particles.
- the present invention is not limited thereto.
- the diameter of the core of the inorganic particles may be 20nm to 900nm, specifically 700 to 800nm, but is not limited thereto.
- the diameter of the inorganic particle core can be adjusted by changing the pH of the solution during the synthesis of the inorganic particles.
- the dispersion degree may be increased to prevent aggregation of the inorganic particles and may have excellent surface properties of the electrolyte membrane.
- the "base" in the basic organic polymer shell has an unshared electron pair according to Lewis definition, and may be interpreted as an electron donor capable of giving the electron.
- the basic organic polymer shell may have an acid-base interaction with a copolymer having an acid group including a sulfonic acid group.
- the basic organic polymer shell is poly (4-vinylpyridine); It may include a polymer prepared using at least one selected from monomers of the following structural formula, but is not limited thereto.
- the basic organic polymer shell may have a thickness of 5 to 20 nm, but is not limited thereto.
- the core-shell particles may be formed by radical polymerization between a vinyl group and an organic polymer on an inorganic particle surface.
- the content of the core-shell particles may be greater than 0 to 10 wt% based on the total weight of the poly (arylene ether sulfone) copolymer, but is not limited thereto.
- the composite electrolyte membrane according to the present application has characteristics that can improve not only hydrogen ion conductivity but also mechanical properties and dimensional stability.
- inorganic particles such as silica particles
- stability and mechanical properties may be improved by the interaction between the polymer and the inorganic particles.
- the present application introduces a basic polymer shell to the inorganic particles.
- the acidic poly (arylene ether sulfone) copolymers having a sulfonic acid group can have acid-base interactions with the basic polymeric shell so introduced to help better mix the core-shell silica particles.
- stability and mechanical properties may be further improved by acid-base interactions.
- the amount of sulfonic acid groups should be large.
- the amount of the effective sulfonic acid group may be less than that of the acidic shell.
- the composite electrolyte membrane is prepared by introducing inorganic particles having a basic shell, the expansion of the electrolyte membrane is less likely to occur due to the influence of the acid-base interaction between the shell and the copolymer.
- the number of sulfonic acid groups per unit volume of the electrolyte membrane containing water is higher in the case of the electrolyte membrane in which the inorganic particles having the basic shell are introduced than when the acidic shell is introduced.
- stability and physical properties can be improved and hydrogen ion conductivity can be improved.
- the method for producing a composite electrolyte membrane preparing a poly (arylene ether sulfone) copolymer comprising a repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 And the poly (arylene ether sulfone) copolymer; Preparing a composition comprising core-shell particles comprising an inorganic particle core and a basic organic polymer shell, and forming a composite electrolyte membrane using the composition.
- the composition may further include an organic solvent, and the organic solvent may be used without limitation known in the art. That is, the composition may be prepared by dissolving a poly (arylene ether sulfone) copolymer and core-shell particles in an organic solvent.
- the method of forming the composite electrolyte membrane may use a solution process, but is not limited thereto.
- the solution process may be performed by dispersing the particles by putting the core-shell particles in DMF (N, N-dimethylformamide) and sonicating.
- the solution is added to a solution in which a poly (arylene ether sulfone) copolymer is dissolved in DMF, mixed, and then the solution is cast on a glass plate and heat-treated at 60 ° C. for 12 hours to blow off a solvent to prepare a composite electrolyte membrane. .
- the present application provides a membrane electrode assembly including the composite electrolyte membrane. More specifically, the membrane electrode assembly may further include a cathode provided on one surface of the composite electrolyte membrane and an anode provided on the other surface of the composite electrolyte membrane.
- the cathode and the anode may include a catalyst layer and a gas diffusion layer, respectively, and the polymer electrolyte membrane may be provided between the cathode catalyst layer and the anode catalyst layer.
- the polymer electrolyte membrane may be provided in contact with the cathode catalyst layer and the anode catalyst layer.
- the composite electrolyte membrane may be provided between the cathode catalyst layer and the anode catalyst layer, and may serve as a medium through which hydrogen ions pass and a separator of air and hydrogen gas.
- the cathode and the anode may be an electrode for a fuel cell of the present specification.
- Oxidation reaction of fuel occurs in the catalyst layer of the anode, and reduction reaction of oxidant occurs in the catalyst layer of the cathode.
- the catalyst layer may comprise a catalyst.
- the catalyst is not limited as long as it can serve as a catalyst in a fuel cell, but may include one of platinum, transition metal and platinum-transition metal alloy.
- the transition metal is a group 3 to 11 elements in the periodic table, and may be, for example, any one of ruthenium, osmium, palladium, molybdenum, and rhodium.
- the catalyst may be selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, platinum-molybdenum alloy and platinum-rhodium alloy, but is not limited thereto. Does not.
- the catalysts of the catalyst layer can be used as a catalyst layer as well as being supported on a carbon-based carrier.
- Examples of the carbon-based carrier include graphite (graphite), carbon black, acetylene black, denka black, canyon black, activated carbon, mesoporous carbon, carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon nanorings, carbon nanowires, One or a mixture of two or more selected from the group consisting of fullerene (C60) and Super P black may be a preferred example.
- the catalyst layer may further include an ionomer.
- the ionomer serves to provide a passage for the ions generated by the reaction between the fuel and the catalyst such as hydrogen or methanol to move to the composite electrolyte membrane.
- the ionomer may be a sulfonated polymer such as Nafion ionomer or sulfonated polytrifluoro styrene.
- the fuel cell electrode may further include a gas diffusion layer provided on one surface of the catalyst layer.
- the gas diffusion layer serves as a passage for the reaction gas and water together with a role as a current conductor, and has a porous structure. Therefore, the gas diffusion layer may include a conductive substrate.
- a conventional material known in the art may be used, but for example, carbon paper, carbon cloth, or carbon felt may be preferably used. It doesn't work.
- the present application provides a fuel cell including the composite electrolyte membrane.
- An exemplary embodiment of the present application is a stack including a separator provided between the two or more membrane electrode assembly and the membrane electrode assembly; A fuel supply unit supplying fuel to the stack; And an oxidant supply unit for supplying an oxidant to the stack.
- the stack includes one or more membrane electrode assemblies as described above, and when two or more membrane electrode assemblies are included, the stack includes a separator interposed therebetween.
- the separator serves to prevent the membrane electrode assemblies from being electrically connected and to transfer fuel and oxidant supplied from the outside to the membrane electrode assembly.
- the oxidant supply unit serves to supply an oxidant to the stack.
- Oxygen is typically used as the oxidizing agent, and may be used by injecting oxygen or air into a pump.
- the fuel supply unit serves to supply fuel to the stack, and may include a fuel tank for storing fuel and a pump for supplying fuel stored in the fuel tank to the stack.
- fuel hydrogen or hydrocarbon fuel in gas or liquid state may be used.
- hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.
- Poly (arylene ether sulfone) copolymers include 4,4'-dihydroxy biphenyl monomers and 3,3'-disulfonate-4,4'-difluorodiphenyl sulfones, 4,4-difluoro It was synthesized by nucleophilic substitution reaction between diphenyl sulfone monomers. In this application, 3,3'-disulfonate-4,4'-difluorodiphenyl sulfone and 4,4-difluoro diphenyl sulfone were used in a 1: 1 molar ratio. The synthesized copolymer had a sulfonation degree of 50% and was named "PAES-50".
- VTMS vinyltrimethoxysilane
- Azobisisobutyronitrile (AIBN) was added as a initiator in a solution of silica particles and 4-vinylpyridine in N, N-dimethylacetamide (DMAc), followed by radical polymerization at 60 ° C. for 2 days.
- the silica particles were washed with distilled water and ethanol, and the silica particles thus produced were named "P-Si" as core-she silica particles having a poly (4-vinylpyridine) shell which is a basic polymer.
- Example 1 the same reaction was conducted using styrene-4-sulfonic acid sodium salt instead of 4-vinylpyridine in preparing the core-shell particles.
- the sodium ions of the poly (styrene-4-sulfonic acid group) were treated with 1M sulfuric acid at room temperature for 24 hours to be converted to hydrogen ions, and then washed with distilled water.
- the silica particles thus produced are core-shell silica particles having a poly (styrene-4-sulfonic acid group) shell which is an acidic polymer, and are named "S-Si".
- silica particles were added to N, N-dimethylformamide (DMF) and sonicated.
- the solution in which silica was dispersed in DMF was added to a solution in which PAES-50 was dissolved in 15 wt% of DMF, followed by stirring for 24 hours.
- This mixed solution was cast to a glass plate at 250 ⁇ m through a doctor blade, and then heat-treated at 60 ° C. for 12 hours in an oven.
- the electrolyte membrane made as described above was impregnated with distilled water, separated from the glass plate, treated with 1M aqueous sulfuric acid solution at room temperature for 24 hours, and washed with boiling distilled water.
- Composite electrolyte membrane made by mixing Si and PAES-50 is "Si50”
- composite membrane made by mixing S-Si and PAES-50 is “S-Si50”
- composite membrane made by mixing P-Si and PAES-50 is "P-Si50” 5% by weight of the particles, respectively, of PAES-50 was used.
- silica particles (Si) without introducing a shell structure were added, the silica particles were agglomerated in the composite electrolyte membrane, and compared at 5% by weight.
- the hydrogen ion conductivity of the composite electrolyte membrane can be improved.
- Silica particles can form a composite membrane with a polymer matrix to enhance ionic conductivity based on excellent hygroscopicity while enhancing dimensional stability and mechanical properties, and core-shell silica particles having a polymer shell having sulfonic acid groups deliver hydrogen ions. More sulfonic acid groups can further improve the conductivity of the electrolyte membrane. This behavior is revealed in the hydrogen ion conductivity data measured at 80 ° C, 90% humidity, 80 ° C, and 50% humidity.
- basic polymers are known to reduce hydrogen ion conductivity because they trap hydrogen ions from the sulfonic acid groups of the polymer matrix, but in this application, P-Si50 is 80 ° C, 90% humidity and 50% compared to S-Si50.
- the water content and the expansion rate were measured after immersing the electrolyte membrane in distilled water at 30 ° C. for 24 hours.
- silica particles reduced water content, expansion rate, and IECv (wet).
- P-Si50 Compared with S-Si50, P-Si50 has almost the same moisture content and low expansion rate. The higher the water content, the more the medium through which hydrogen ions can move, which is advantageous in terms of hydrogen ion conductivity, but tends to lose dimensional stability as the expansion rate increases. However, in the present application, P-Si50 has the same water content as S-Si50, but has a low expansion rate, thereby showing an improvement in dimensional stability.
- IECv (wet) is a value indicating how many mmol of sulfonic acid groups per unit volume of the polymer when the electrolyte membrane is wet with water. In this application, since Si has no sulfonic acid group, the IECv (wet) value decreases when added to PAES-50. do. Since S-Si has a polymer shell having sulfonic acid groups, the IECv (wet) value of S-Si50 is increased compared to Si50. Because P-Si has a basic polymer shell that can trap hydrogen ions in sulfonic acid groups, PSi50 has fewer free hydrogen ions than S-Si50.
- the composite electrolyte membrane according to the present application includes core-shell particles having a basic organic polymer shell and a poly (arylene ether sulfone) copolymer, thereby comparing hydrogen ions with a polymer electrolyte membrane containing only a poly (arylene ether sulfone) copolymer. Conductivity, dimensional stability, mechanical strength and the like can be improved.
- the composite electrolyte membrane according to the present application may improve hydrogen ion conductivity, dimensional stability, and the like, compared to a composite electrolyte membrane including particles having no shell structure and a poly (arylene ether sulfone) copolymer.
- the composite electrolyte membrane according to the present application may improve hydrogen ion conductivity, dimensional stability, and the like, compared to a composite electrolyte membrane including a core-shell particle having an acidic polymer shell and a poly (arylene ether sulfone) copolymer.
- the composite electrolyte membrane according to the present application is characterized in that the hydrogen ion conductivity, mechanical properties, dimensional stability, etc. according to the size of the inorganic core, the size of the organic polymer shell, the content ratio between the poly (arylene ether sulfone) copolymer and the core-shell particles, etc. Flexibility to adjust
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Abstract
Description
Claims (10)
- 하기 화학식 1로 표시되는 반복단위 및 하기 화학식 2로 표시되는 반복단위를 포함하는 폴리(아릴렌 에테르 술폰) 공중합체; 및무기 입자 코어 및 염기성 유기 고분자 쉘을 포함하는 코어-쉘 입자를 포함하는 복합체 전해질막:[화학식 1][화학식 2]상기 화학식 1 및 2에서,R1 내지 R3, 및 R8 내지 R10은 각각 독립적으로 -O-, -S-, -SO2-, -C=O- 또는 -C(CH3)2- 이고,R4 내지 R7 및 R13 내지 R16은 각각 독립적으로, 수소, 또는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬기이고,R11, R12 및 R18 중 적어도 하나는 -SO3R17이며 나머지는 수소, 또는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬기이고,R17은 H, Li, Na 또는 K이며,A 및 A'는 각각 독립적으로 직접결합, 2가의 플루오렌기, 또는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬렌기이고,m, n, o, p 및 r은 각각 독립적으로 0 내지 4이며, q, s 및 t는 각각 독립적으로 0 내지 3이고,y는 0 또는 1이며,a 및 b는 화학식 1 및 2의 몰비로서, 각각 독립적으로 0.1 내지 0.99 이다.
- 청구항 1에 있어서, 상기 무기 입자 코어는 실리카 입자, TiO2 및 ZrO2로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 복합체 전해질막.
- 청구항 1에 있어서, 상기 무기 입자 코어의 직경은 20 내지 900nm인 것을 특징으로 하는 복합체 전해질막.
- 청구항 1에 있어서, 상기 무기 입자 코어는 표면처리된 무기 입자를 포함하고,상기 표면처리는 실란계 화합물을 이용하고, 무기 입자와 실란계 화합물 간의 축합반응에 의하여 수행되는 것을 특징으로 하는 복합체 전해질막.
- 청구항 4에 있어서, 상기 무기 입자 코어 표면에 비닐기를 포함하는 것을 특징으로 하는 복합체 전해질막.
- 청구항 1에 있어서, 상기 염기성 유기 고분자 쉘의 두께는 5 내지 20nm인 것을 특징으로 하는 복합체 전해질막.
- 청구항 1에 있어서, 상기 복합체 전해질막은 연료전지용인 것을 특징으로 하는 복합체 전해질막.
- 하기 화학식 1로 표시되는 반복단위 및 하기 화학식 2로 표시되는 반복단위를 포함하는 폴리(아릴렌 에테르 술폰) 공중합체를 준비하는 단계,상기 폴리(아릴렌 에테르 술폰) 공중합체와; 무기 입자 코어 및 염기성 유기 고분자 쉘을 포함하는 코어-쉘 입자를 포함하는 조성물을 준비하는 단계, 및상기 조성물을 이용하여 복합체 전해질막을 형성하는 단계를 포함하는 복합체 전해질막의 제조방법:[화학식 1][화학식 2]상기 화학식 1 및 2에서,R1 내지 R3, 및 R8 내지 R10은 각각 독립적으로 -O-, -S-, -SO2-, -C=O- 또는 -C(CH3)2- 이고,R4 내지 R7 및 R13 내지 R16은 각각 독립적으로, 수소, 또는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬기이고,R11, R12 및 R18 중 적어도 하나는 -SO3R17이며 나머지는 수소, 또는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬기이고,R17은 H, Li, Na 또는 K이며,A 및 A'는 각각 독립적으로 직접결합, 2가의 플루오렌기, 또는 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬렌기이고,m, n, o, p 및 r은 각각 독립적으로 0 내지 4이며, q, s 및 t는 각각 독립적으로 0 내지 3이고,y는 0 또는 1이며,a 및 b는 화학식 1 및 2의 몰비로서, 각각 독립적으로 0.1 내지 0.99 이다.
- 청구항 1 내지 8 중 어느 한 항의 복합체 전해질막을 포함하는 연료전지.
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US10364331B2 (en) | 2019-07-30 |
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