WO2015099208A1 - Membrane composite préparée par imprégnation d'électrolyte à base d'hydrocarbure sur dispositif de support de tissu non-tissé de pan et utilisation de celle-ci - Google Patents

Membrane composite préparée par imprégnation d'électrolyte à base d'hydrocarbure sur dispositif de support de tissu non-tissé de pan et utilisation de celle-ci Download PDF

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WO2015099208A1
WO2015099208A1 PCT/KR2013/012028 KR2013012028W WO2015099208A1 WO 2015099208 A1 WO2015099208 A1 WO 2015099208A1 KR 2013012028 W KR2013012028 W KR 2013012028W WO 2015099208 A1 WO2015099208 A1 WO 2015099208A1
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membrane
pan
electrolyte membrane
composite electrolyte
composite
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PCT/KR2013/012028
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English (en)
Korean (ko)
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유덕만
윤상준
김태호
이장용
홍영택
이재락
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한국화학연구원
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Publication of WO2015099208A1 publication Critical patent/WO2015099208A1/fr

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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]
    • 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
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • 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
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention provides a composite electrolyte membrane comprising a support prepared by oxidizing a nonwoven fabric formed by electrospinning a polyacrylonitrile (PAN) copolymer solution and a hydrocarbon-based polymer electrolyte impregnated thereto; Novel fabric formed by electrospinning polyacrylonitrile copolymer solution was oxidized to form hexagonal rings while forming bonds between nitrogen atoms of side chain nitrile groups and carbon atoms of neighboring nitrile groups, thereby improving solvent resistance or strength.
  • Support A membrane-electrode assembly (MEA) including the composite electrolyte membrane as an electrolyte membrane; And a fuel cell having the membrane-electrode assembly.
  • MEA membrane-electrode assembly
  • fuel cells do not require battery replacement or charging, and are devices that convert chemical energy from fuel into electrical energy through chemical reactions with oxygen or other oxidants.
  • the fuel cell is a high efficiency power generation device with energy conversion efficiency of about 60%. It is more efficient than existing internal combustion engines, so it uses less fuel and is a pollution-free energy source that does not generate environmental pollutants such as SO x , NO x , and VOC. There is an advantage.
  • the fuel cell comprises a cathode (anode) which produces hydrogen ions and electrons by oxidation of a fuel material, an anode (cathode) and an anode from which the reduction of oxygen or another oxidizing agent occurs by reaction with hydrogen ions and electrons. It includes an electrolyte layer that can efficiently transfer hydrogen ions. In the fuel cell, hydrogen ions and electrons respectively move from the anode to the cathode through an external circuit electrically connected to the electrolyte layer.
  • the fuel cell may use hydrogen, hydrocarbons, alcohols (methanol, ethanol, etc.) as a fuel, and oxygen, air, chlorine, chlorine dioxide, and the like may be used as oxidants.
  • Fuel cells include Polymer Electrolyte Membrane Fuel Cells (PEMFC), Direct Methanol Fuel Cells (DMFC) and Direct Ethanol Fuel Cells (DEFC), Alkaline Alkaline Fuel Cell (AFC), Phosphoric Acid Fuel Cell (PAFC), Molten Carbonate Fuel Cell (MCFC) and Solid Oxide Fuel Cell (SOFC) Can be.
  • Dual polymer electrolyte fuel cells, direct methanol fuel cells, and direct ethanol fuel cells are capable of operating at relatively lower temperatures than other fuel cells, and are capable of generating power at levels of 1 to 10 kW.
  • the output can be improved by stacking and easy to carry, so that it can be usefully used for a notebook or as an auxiliary power supply.
  • the electrolyte membrane prepared by using the ion conductive polymer between the fuel electrode and the air electrode is placed in the form of a sandwich and pressed to prepare a membrane-electrode assembly in which the fuel electrode-electrolyte membrane-air electrode forms a conjugate.
  • the battery can be constructed.
  • the electrolyte membrane that can be used for the membrane-electrode assembly has a high hydrogen ion transfer capacity while low permeability of the fuel material, as well as high thermal stability, thus stably exhibiting ion conductivity even in a battery driving condition of about 100 ° C. And it is excellent in chemical durability and must be stable without decomposing even under conditions such as prolonged use and acidity.
  • PEMFCs proton exchange membrane fuel cells
  • PEMFCs proton exchange membrane fuel cells
  • a proton exchange membrane PEM
  • Nafion a perfluorosulfonated ionomer
  • Nafion membranes are expensive and, in addition, their manufacturing process is complex and emits toxic waste.
  • due to the rapid decrease in hydrogen ion conductivity, softening of the membrane, high methanol permeability, etc. due to the decrease in the moisture content above 100 °C, there is a big limitation in commercialization of fuel cells.
  • Sulfonated poly (arylene ether sulfone) (SPAES) has been considered as a PEM material to replace Nafion membranes over the last decades.
  • SPAES arylene ether sulfone
  • PI polyimide
  • PPTA poly (paraphenylene terephthalamide)
  • PV alcohol poly (vinyl alcohol)
  • PVA poly-fibrous manufactured materials
  • PPS polyphenylsulfone
  • the present inventors have tried to find a composite electrolyte membrane that exhibits high conductivity of the polymer electrolyte and at the same time improves its strength by using a support.
  • the PAN and PMMA copolymers are electrospun to form a nonwoven fabric, and then oxidized and crosslinked in a molecule to increase the strength.
  • the composite electrolyte membrane prepared by impregnating the polymer electrolyte with the support can be increased, and the dimensional change, in particular, the dimensional change in the area direction, which can cause breakage of the electrolyte membrane, significantly reduces the performance even after repeated use several hundred times. It was confirmed that it can be used as a battery separator capable of maintaining the present invention was completed.
  • An object of the present invention is an electrolyte membrane for a fuel cell, when using a composite membrane impregnated with an electrolyte polymer on a porous support, a porous support and electrolyte that can provide excellent mechanical properties, dimensional stability, durability while maintaining high porosity It is to provide a composite membrane impregnated with a polymer.
  • the composite membrane impregnated with the electrolyte polymer on the porous support according to the present invention exhibits excellent mechanical properties, dimensional stability, and durability while maintaining high porosity.
  • FIG. 1 is a view schematically showing a synthesis process of a PAN copolymer. (a) shows before oxidation and (b) shows PAN copolymer after oxidation.
  • FIG. 2 is a view schematically showing the synthesis process of SPAES copolymer.
  • FIG. 3 is a view showing SEM images of (a) surface and (b) cross section of the synthesized PAN nonwoven fabric.
  • FIG. 4 is a diagram showing the pore size distribution and solubility in NMP of the PAN nonwoven fabric.
  • FIG. 5 is a view showing an image of a composite film composed of SPAES50 and PAN nonwoven fabric. (a) is real, (b) is surface, and (c) is cross-sectional image.
  • Figure 7 is a diagram showing the proton conductivity of Nafion 212, SPAES50 and PAN / SP50 with temperature under 100% relative humidity conditions.
  • FIG. 8 is a diagram showing proton conductivity of Nafion 212, SPAES50 and PAN / SP50 according to humidity conditions (80 ° C., 50 kPa back pressure).
  • FIG. 9 is a diagram showing the MEA resistance of SPAES50 and PAN / SP50 measured by electrochemical impedance spectroscopy at a DC potential of 0.85 V (70 ° C., 100% relative humidity).
  • FIG. 11 shows the results of durability test of SPAES50 and PAN / SP50 using wet-dry cycling including OCV sustain method.
  • FIG. 12 is a diagram showing the amount of hydrogen crossover of SPAE50 and PAN / SP50 according to the number of cycles.
  • a first aspect of the present invention provides a composite electrolyte membrane comprising a support prepared by oxidizing a non-woven fabric formed by electrospinning a polyacrylonitrile (PAN) copolymer solution and a hydrocarbon-based polymer electrolyte impregnated thereto.
  • PAN polyacrylonitrile
  • the second aspect of the present invention is to oxidize a nonwoven fabric formed by electrospinning a polyacrylonitrile copolymer solution, wherein the polyacrylonitrile copolymer has an alkoxycarbonyl or alk in an ethylene skeleton and a side chain. It comprises 1 to 10% by weight of a unit containing akanonoxy (alkanonoxy), and forming a hexagonal ring by forming a bond between the nitrogen atom of the side chain nitrile group and the carbon atoms of the adjacent nitrile group through oxidation
  • a porous support that is characteristic.
  • a third aspect of the present invention provides a membrane-electrode assembly (MEA) comprising the composite electrolyte membrane according to the first aspect as an electrolyte membrane.
  • MEA membrane-electrode assembly
  • a fourth aspect of the present invention provides a fuel cell having the membrane-electrode assembly according to the third aspect.
  • the present invention is characterized by providing a porous support by electrospinning and oxidizing a polyacrylonitrile (PAN) polymer solution.
  • PAN polyacrylonitrile
  • the present invention also provides a novel composite electrolyte membrane by impregnating the porous support with a hydrocarbon-based polymer electrolyte, such as a sulfonated poly (arylene ether sulfone) copolymer, as an electrolyte. It is characteristic.
  • the present inventors have disclosed a reinforced composite electrolyte membrane in which a conductive polymer is impregnated into a support having improved strength by crosslinking a nonwoven fabric of a polymer material using a heat treatment or a crosslinking agent through a prior study (Korean Patent No. 10-1279352).
  • the heat treatment should be carried out for a long time of several to several ten hours at a high temperature near 300 °C, when using a crosslinking agent it is inevitable to introduce an additional crosslinking agent and involves a repeated washing process to remove it. That is, such methods require long reactions or additional reagents.
  • the support according to the invention can be prepared simply by treating with an oxidizing agent.
  • the oxidant may be an oxygen molecule. That is, it can be performed by heating in an oven containing oxygen, for example, atmospheric conditions. Therefore, oxygen can be oxidized using oxygen in the air as an oxidizing agent only by heating, unless conditions are saturated with vacuum or inert gas.
  • the PAN copolymer which is a material of the porous support, may form a hexagonal ring as a bond is formed between a nitrogen atom of a side chain nitrile group and a carbon atom of a neighboring nitrile group through an oxidation process.
  • the intramolecular cyclization by oxidation can improve the strength by strengthening the skeleton of the PAN polymer portion, thereby not only reducing the dimensional change of the support but also reducing the cleavage of the polymer strand due to swelling due to moisture.
  • breakage of the electrolyte membrane can be prevented.
  • the treatment with the oxidant may be performed at 200 to 300 °C.
  • the process may be performed for 0.5 to 4 hours. More preferably, it may be performed at 230 to 270 ° C for 1 to 3 hours.
  • the intramolecular cyclization in the PAN polymer portion is insufficient to provide the desired strength as a support or used when impregnating the polymer electrolyte solution. It may be dissolved in a solvent.
  • the polymer skeleton becomes excessively rigid due to excessive cyclization, so that the polymer skeleton can be easily crushed even by a small force applied without being able to bend flexibly or catch it.
  • porous structures having high porosity may be crushed due to intermolecular crosslinking. Therefore, it is important to find the optimum conditions by appropriately combining the treatment temperature and time.
  • the PAN copolymer has alkoxycarbonyl or alkanonoxy in the ethylene skeleton and the side chain in order to provide flexibility and hydrophilicity to facilitate molding and improve compatibility with the polymer electrolyte. It is preferable to include 1 to 10% by weight of a unit containing).
  • Non-limiting examples of units containing alkoxycarbonyl or alkanonoxy in the ethylene skeleton and side chains include methyl methacrylate (MMA) and methyl acrylate (methyl acrylate). , Vinyl acetate, and the like. It is preferable that the said unit is methyl methacrylate.
  • acrylonitrile and methyl methacrylate were mixed and polymerized in a mass ratio of 94: 6 to synthesize a PAN copolymer including 6% by weight of methyl methacrylate.
  • the concentration of the PAN copolymer solution used for electrospinning for forming into a nonwoven fabric may be 8 to 15% by weight. Preferably it can be used at a concentration of 10% by weight. If the concentration of the copolymer solution is too low, it is difficult to form into a nonwoven fabric having uniform pores that provide high porosity by electrospinning because the viscosity is short and broken. On the other hand, when the concentration is too high, it may be difficult to mold into a nonwoven fabric having uniform pores since the viscosity may be increased and entangled or aggregated may occur.
  • the porous support according to the present invention has 60 to 80% porosity. Due to the presence of pores in the nonwoven fabric and the high porosity, when the electrolyte solution is subsequently impregnated in the preparation of the electrolyte membrane, a large amount of electrolyte may be contained in the pores, thereby canceling the decrease in ion conductivity by the PAN-based copolymer having low proton conductivity. Can be. At this time, if the porosity is less than 60%, it may not contain a sufficient amount of electrolyte, and thus, sufficient conductivity may not be provided as an electrolyte membrane.
  • the porous support prepared through electrospinning and oxidation of the PAN polymer solution according to the present invention exhibits high porosity and has pores of uniform size, the size of the pores is different from that of other nonwoven fabrics in which the pores are not uniform.
  • it shows remarkably excellent conductivity and durability.
  • the porous support according to the present invention preferably has pores having an average diameter of 0.5 to 1.5 ⁇ m. If the pores are too small, the impregnation of the electrolyte polymer is not easy. If the pores are too large, the electrolyte polymer does not stay in the pores and flows out so that impregnation is difficult.
  • the porous support according to the present invention has a thickness of 10 to 30 ⁇ m.
  • the porous support can provide the mechanical strength or dimensional stability required in the electrolyte membrane of the fuel cell, while the conductivity of the support itself is low, resulting in membrane resistance. Therefore, it is desirable to maintain the mechanical strength but to lower the resistance by minimizing the thickness.
  • the PAN copolymer was electrospun to form a nonwoven fabric, and then, the oxidized support was immersed in NMP, which is a solvent for dissolving the polymer electrolyte.
  • NMP is a solvent for dissolving the polymer electrolyte.
  • non-limiting examples of the polymer electrolyte that can be impregnated in the support according to the present invention is a hydrocarbon-based polymer electrolyte.
  • hydrocarbon-based polymer electrolytes include sulfonated polyimide, sulfonated poly (arylene ether sulfone) (SPAES), sulfonated polyetheretherketone ether ketone; SPEEK), sulfonated polybenzimidazole (SPBI), sulfonated polysulfone (SPSU), sulfonated polystyrene (SPS), sulfonated polyphosphazene sulfonated polyphosphazene (SPP), sulfonated poly (ether sulfone) (SPES), sulfonated poly (ether ketone) (SPEK), sulfonated polyarylene ether benziimi Sulfonated poly (arylene ether benzimi
  • l, m and n are each independently an integer of 1 or more.
  • hydrocarbon-based electrolyte including a sulfonated group can interact with the cyano group of the PAN support through the sulfonic acid group, it can provide excellent miscibility when impregnated into the support.
  • the sulfonated hydrocarbon-based polymer electrolyte preferably has a degree of 40 to 60 mol% sulfonation.
  • the hydrophilicity of the membrane becomes high, so that it may be dissolved in water and eluted without being impregnated in the support, while when the sulfonation degree is less than 40%, the ion conductivity of the membrane may be significantly decreased.
  • a SPAES copolymer was synthesized that exhibited high conductivity but was not dissolved in a solvent with 50 mol% sulfonation. It was confirmed that the composite membrane prepared by impregnating the SPAES copolymer in the porous support according to the present invention (Example 3) improved not only proton conductivity but also mechanical properties, dimensional stability, and durability. In particular, as a result of measuring the dimensional change in the wet and dry state, it was confirmed that the dimensional change in the area direction that can cause breakage of the electrolyte membrane is significantly reduced to show a lower level than Nafion 212 (Fig. 6).
  • a third aspect of the present invention provides a membrane-electrode assembly (MEA) having a composite electrolyte membrane according to the present invention as an electrolyte membrane.
  • MEA membrane-electrode assembly
  • a membrane-electrode assembly may be manufactured by interposing a composite membrane according to the present invention between a cathode and an anode at high temperature.
  • the pressure during thermal compression is 0.5 to 2 tons (ton)
  • the temperature is preferably 40 to 250 °C.
  • the catalyst that can be used in the membrane-electrode assembly may be an alloy catalyst such as Pt, Pt-Ru, Pt-Sn, Pt-Pd, or Pt / C coated with fine carbon particles, Pt-Ru / C, or the like.
  • a metal material such as Ru, Bi, Sn Mo may be deposited on Pt, but any material suitable for oxidation of hydrogen and reduction of oxygen may be used without limitation. You can also use commercially available products from Johnson Matthey, E-Tek, and others. Since the electrode catalysts adhered to both surfaces of the electrolyte membrane act as a cathode and an anode, respectively, they may be used in different amounts depending on the reaction rate at both electrodes, and other types of catalysts may be used.
  • the membrane-electrode assembly may be manufactured using a method known to those skilled in the art, and various non-limiting examples of the manufacturing method may be used, such as a decal method, a spray method, or a CCG method.
  • the membrane-electrode assembly is manufactured using the CCG method, but the method of manufacturing the membrane-electrode assembly is not limited thereto.
  • the non-limiting method of manufacturing the membrane-electrode assembly includes applying a catalyst slurry mixed with a catalyst, a hydrogen ion conductive polymer and a dispersion medium on a GDL and then drying to form a catalyst layer; Stacking the catalyst layer formed on the GDL such that the catalyst layer faces the electrolyte membrane on both surfaces of the composite membrane according to the present invention; And laminating and hot pressing to form a membrane-electrode assembly.
  • a fourth aspect of the present invention provides a fuel cell having the membrane-electrode assembly according to the present invention.
  • non-limiting examples of a fuel cell having a membrane-electrode assembly according to the present invention include a polymer electrolyte fuel cell (PEMFC) and a direct methanol fuel cell (DMFC). have.
  • PEMFC polymer electrolyte fuel cell
  • DMFC direct methanol fuel cell
  • Difluorodiphenyl sulfone (DFDPS) was purchased from Solvay Advanced Polymers (USA) and recrystallized from ethanol. 3,3'-disulfonated-4,4'-difluorodiphenyl sulfone (3,3'-disulfonated-4,4'-difluorodiphenyl sulfone; SDFDPS) was synthesized according to a known method. 4,4'-Bisphenol (4,4'-Bisphenol; BP, TCI) was also recrystallized from ethanol to increase the purity.
  • N-methyl-2-pyrrolidone NMP, Junsei
  • anhydrous toluene Aldrich
  • 95-97% sulfuric acid Merck
  • dimethylsulfoxide DMSO, Aldrich
  • dimethyl Formamide dimethylformamide; DMF, Aldrich
  • azobisisobutyronitrile AIBN, Aldrich
  • Anhydrous potassium carbonate K 2 CO 3 , Aldrich
  • Acrylonitrile (AN) and methyl methacrylate (MMA) were purchased from South Korea.
  • stainless steel needles internal diameter 0.51 mm, external diameter 0.81 mm and length 13 mm
  • MN-21G-13 Iwashita Engineering, Japan
  • Polyacrylonitrile (PAN) copolymers were synthesized using AN and MMA monomers at a mass ratio of 94: 6 and are schematically illustrated in FIG. 1A.
  • AN 70.5 g
  • MMA 4.5 g
  • Deionized water (279.0 g) was added to the reactor.
  • the reactor was heated to 70 ° C. and a 20 wt% AIBN (0.8 g) solution dissolved in DMF was added to the mixture and stirred for 30 minutes.
  • the polymerized sample was filtered and washed thoroughly three or four times with methanol to remove the remaining reactants. It was then dried for 48 hours at 50 ° C. under convection.
  • a PAN nonwoven fabric was manufactured using the electrospinning method.
  • a 10 wt% PAN solution dissolved in DMSO was released from the syringe.
  • the electrospun fibers were collected on a cylindrical drum collector.
  • the electrical voltage was 10 kV and a syringe pump (KD Scientific-100, USA) was used to supply the solution at a constant throughput.
  • the distance from the nozzle tip to the collector was fixed at 10 cm.
  • the PAN nonwoven formed was dried at 160 ° C. for 2 hours under vacuum to remove excess solvent.
  • the dried PAN nonwoven fabric was oxidized by treatment with an oxidizer at 240 ° C. for 1.5 hours (FIG. 1B). Specifically, the mixture was treated at 240 ° C. for 1.5 hours in an oven containing oxygen.
  • SPAES50 copolymer synthesis method used as an ionomer for producing a composite membrane.
  • a composite film was prepared by impregnating a solution of 15 wt% of a polymer (SPAES50) dissolved in NMP into a PAN nonwoven fabric prepared according to Example 2 using a bar coating method. .
  • the polymer solution together with the PAN nonwoven was dried in an oven at 80 ° C.
  • the membrane thus prepared was subsequently dried at 120 ° C. under vacuum for 12 hours to completely remove excess solvent. Finally, the membrane was acidified in 1.5 M sulfuric acid for 24 hours and then washed with deionized water for 24 hours at room temperature.
  • the molecular weight (Mw) of the PAN copolymer synthesized according to Example 2 was confirmed by gel permeation chromatography (GPC, Waters, Tosoh).
  • the pore size distribution of the PAN nonwovens was measured using a high order capillary flow porometer (ACFP-1500AE, wet up / dry up method using Galwick solution).
  • the dimensional change (area, thickness and volume) and the amount of water uptake were determined from the difference in volume and mass between the wet membrane in the fully hydrated state and the dry membrane measured after vacuum drying at 120 ° C.
  • a mechanical testing instrument (LLOYD instrument LR5K) was used to confirm the mechanical properties of the membrane at a crosshead speed of 50 mm / min at 25 ° C. in a fully hydrated state.
  • Scanning electron microscopy (SEM, XL-30S FEG, Philips) was used to observe the surface and cross-sectional images of the PAN nonwoven fabric and composite membrane. Prior to SEM image processing, the samples were coated with platinum for 2 minutes in vacuo using a sputter coating machine (Sputter Coater, Q150T ES, Quorumtech, USA).
  • the equivalent titer of sulfonic acid groups per unit mass of membrane (1 g) was measured with an automatic titrator (Metroohm 794 Basic Titrino) and expressed as ion exchange capacity (IEC).
  • IEC ion exchange capacity
  • SP AC impedance analyzer
  • SP 4-probe conductivity cell with varying temperature (from 25 ° C. to 80 ° C.) at 100% relative humidity in the in-plane direction over a frequency range of 0.1 Hz to 4 MHz.
  • the proton conductivity of the membrane was measured using an Impedance / Gain Phase Analyzer. Equilibration was performed for 1 hour in a temperature chamber (ESPEC, SH-241) before each measurement. Proton conductivity was calculated using the following formula (1):
  • EIS electrochemical impedance spectroscopy
  • x axis real part (Z ')
  • y axis imaginary part (Z' ') using the intercept x value
  • S is the cross-sectional surface area of the membrane, and the in-plane conductivity system (BekkTech, BT) that can control humidity conditions using the same 4-probe. Proton conductivity was measured under various conditions (relative humidity 20% to 80%) at 80 ° C.
  • Example 3 with gas-diffusion layers coated with Pt / C and Nafion binder (50 wt% Pt / C, 0.4 mg Pt / cm 2 , FuelCellPower Inc.) to evaluate single cell performance
  • the membrane electrode assembly (MEA) was prepared using the composite membrane prepared in the above as an electrolyte membrane.
  • the active surface area of the electrode was 25 cm 2 .
  • test station FCT-TS300, Fuel Cell Technologies, Inc.
  • FCT-TS300 Fuel Cell Technologies, Inc.
  • FCT-TS300 Fuel Cell Technologies, Inc.
  • FCT-TS300 Fuel Cell Technologies, Inc.
  • a working electrode and a reference electrode were connected to the anode and the cathode, respectively, and a potential of 0.15 to 0.3 V was applied to the single cell.
  • the morphological properties of the electrospun PAN nonwovens with appropriate feasible oxidative stability of 450 kg / mol of molecular weight (Mw) prepared according to Example 2 were analyzed using SEM images.
  • the diameters of the fibers in the PAN nonwovens were determined to range from 600 nm to 1200 nm, and the PAN fibers appeared to be somewhat dissolved and bound to each other.
  • the pore size and pore size distribution of the PAN nonwoven fabric were quantitatively analyzed and the results are shown in FIG. 4A.
  • the average pore diameter of the PAN nonwovens was about 1 ⁇ m and uniformly distributed in the range of 0.5 ⁇ m to 1.5 ⁇ m. In addition, it was confirmed to have a porosity of 80% by using the weight and volume of the PAN nonwoven fabric.
  • FIG. 5 is a view showing a real image and a SEM image of the surface and side of the composite film (hereinafter referred to as PAN / SP50) prepared by using a PAN nonwoven fabric and SPAES50 according to Example 3.
  • the composite film is black due to the oxidative PAN substrate (FIG. 5A).
  • SPAES50 copolymer was successfully impregnated into PAN nonwovens (FIG. 5B). The pores of the PAN nonwoven fabric did not appear on the surface of the composite membrane. It was confirmed that the PAN nonwoven fabric was well mixed with the SPAES50 copolymer from the cross-sectional shape located at the center of the membrane.
  • the thickness of the composite membrane was about 35 ⁇ m (FIG. 5C).
  • multifibrous substrates contribute to strengthening the mechanical properties of the polymer composite membrane.
  • the tensile test of the composite membrane was performed in a fully hydrated state at room temperature. The results are shown in Table 1 below. Young's modulus and yield strength of membranes for use in PEMFCs are important factors for durability in operation. When a change is caused by an external force, these properties indicate the degree of durability and the limits of restorability.
  • the Young's modulus of PAN / SP50 due to the use of a multi-fibrous material having a rigid filler effect, that is, a PAN nonwoven fabric (Young's modulus 704.6 MPa) as a support (692.1 MPa) was significantly higher than the value for SPAES50 (244.6 MPa) and Nafion 212 (112.6 MPa).
  • the yield strength of the membrane showed a tendency similar to Young's modulus.
  • the yield strength of PAN / SP50 (13.8 MPa) was improved by 50% over the values for SPAES50 (9.2 MPa) and Nafion 212 (9.0 MPa). This mechanical property is an important factor in the operation of the PEMFC under extreme conditions.
  • the proton conductivity of the composite membrane was confirmed by varying the temperature under completely hydrated conditions, and the results are shown in FIG. 7 in comparison with the pure polymer membrane and Nafion 212. As the temperature increased from 25 ° C. to 80 ° C., the proton conductivity of all the membranes used for the measurement increased. Proton conductivity of PAN / SP50 was 0.062 S / cm and 0.164 S / cm at 25 ° C and 80 ° C at 100% relative humidity, respectively, lower than the values for SPAES50 (0.092 S / cm and 0.181 S / cm). .
  • the IEC value of PAN / SP50 was also 1.71 meq / g, lower than the value for SPAES50 (2.01 meq / g), as expected. Therefore, the decrease in the proton conductivity of the composite membrane can be determined by the porosity of the PAN nonwoven fabric. Although the proton conductivity of PAN / SP50 decreased compared to SPAES50, the value was close to that for Nafion 212 at 80 ° C / 100% relative humidity. In order to confirm the temperature dependence of the proton conductivity, the slope of the proton conductivity shown with respect to the inverse of the absolute temperature was calculated to confirm the activation energy (E a ).
  • SPAES50 At low relative humidity, SPAES50 exhibited particularly lower proton conductivity than Nafion 212, which may be due to ineffective connectivity of the proton pathway by sulfonic acid groups of SPAES50 compared to Nafion 212.
  • PAN / SP50 had the lowest connectivity among the membranes used for the measurement because the PAN nonwovens act as proton barriers and thus exhibited the lowest proton conductivity at low relative humidity (FIG. 8).
  • OCR ohmic and interfacial contact resistance
  • the relative performance improvement of PAN / SP50 is due to the thinner molding compared to SPAES50 (45 ⁇ m) and Nafion 212 (50 ⁇ m), and consequently the cell resistance can be reduced by shortening the proton path.
  • the measurement conditions are 70 ° C / 50% relative humidity
  • the performance of SPAES50 (788 mA / cm 2 ) and PAN / SP50 (691 mA / cm 2 ) at 0.6 V is lower than Nafion 212 (884 mA / cm 2 ). Therefore, in the case of low relative humidity conditions, the result was the same as for the proton conductivity.
  • the endurance protocol used was a method using hydration / dehydration cycling and the OCV hold method to simultaneously identify physical and chemical damage characteristics.
  • the hydration / dehydration cycle time was 10 minutes in total (5 minutes each).
  • the SPAES50 dropped below 0.9 V after about 500 cycles, while the PAN / SP50 continued up to 1000 cycles due to the PAN nonwoven fabric reinforcement effect. This indicates that the polymer nanofibers can improve the durability of the membrane while driving PEMFC under various conditions.
  • Hydrogen crossmixing results from the diffusion of hydrogen gas through the membrane from the cathode to the anode. Membrane damage in PEMFC can be confirmed by determining whether diffusion of the hydrogen gas occurs.
  • New composite membranes have been successfully developed by impregnating SPAES50 in PAN resin nonwovens.
  • the PAN nonwoven fabric for producing composite membranes suitable for long time operation under various conditions was produced by electrospinning. PAN nonwovens were analyzed by measuring fiber thickness, pore size and porosity. The introduction of PAN nonwovens was found to be an effective means to improve dimensional stability as well as mechanical properties.
  • blocking proton conduction path by PAN nonwoven fabric decreased proton conductivity in composite membrane compared to pure polymer membrane.
  • composite membranes not only showed improved durability compared to pure polymer membranes but also showed similar levels of performance. The excellent durability of the composite membrane was again confirmed by hydrogen cross mixing. This advantage of composite membranes using PAN nonwovens can improve membrane technology for PEMFC applications.

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Abstract

La présente invention concerne une membrane à électrolyte composite comprenant un dispositif de support, qui est préparée par acidification d'un tissu non-tissé formé par électrofilage d'une solution de copolymère de polyacrylonitrile (PAN), et un électrolyte de polymère à base d'hydrocarbure imprégné sur le dispositif de support; un nouveau dispositif de support; un ensemble d'électrode à membrane (MEA) équipé de la membrane à électrolyte composite en tant que membrane à électrolyte; et une pile à combustible équipée du MEA, le dispositif de support ayant une résistance aux solvants ou une solidité améliorées en formant un anneau hexagonal par acidification du tissu non-tissé formé par électrofilage de la solution de copolymère de PAN de manière à former une liaison entre un atome d'azote d'un groupe nitrile d'une chaîne latérale et un atome de carbone dans un groupe nitrile adjacent. Selon la présente invention, la membrane composite dans laquelle un polymère d'électrolyte est imprégné sur un dispositif de support poreux présente d'excellentes propriétés mécaniques, stabilité dimensionnelle et durabilité tout en conservant une porosité élevée.
PCT/KR2013/012028 2013-12-23 2013-12-23 Membrane composite préparée par imprégnation d'électrolyte à base d'hydrocarbure sur dispositif de support de tissu non-tissé de pan et utilisation de celle-ci WO2015099208A1 (fr)

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