WO2015022021A1 - Piles à combustible à membrane électrolytique polymère à performance améliorée - Google Patents

Piles à combustible à membrane électrolytique polymère à performance améliorée Download PDF

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Publication number
WO2015022021A1
WO2015022021A1 PCT/EP2013/066945 EP2013066945W WO2015022021A1 WO 2015022021 A1 WO2015022021 A1 WO 2015022021A1 EP 2013066945 W EP2013066945 W EP 2013066945W WO 2015022021 A1 WO2015022021 A1 WO 2015022021A1
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WO
WIPO (PCT)
Prior art keywords
membrane
etfe
polymer
grafting
fuel cell
Prior art date
Application number
PCT/EP2013/066945
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English (en)
Inventor
Selmiye ALKAN GURSEL
Lale ISIKEL SANLI
Original Assignee
Sabanci Universitesi
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Publication date
Application filed by Sabanci Universitesi filed Critical Sabanci Universitesi
Priority to PCT/EP2013/066945 priority Critical patent/WO2015022021A1/fr
Publication of WO2015022021A1 publication Critical patent/WO2015022021A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • 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
    • 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
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • 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
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1088—Chemical modification, e.g. sulfonation
    • 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
    • C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2339/08—Homopolymers or copolymers of vinyl-pyridine
    • 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
    • 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
    • C08J5/2287—After-treatment
    • C08J5/2293—After-treatment of fluorine-containing membranes
    • 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 relates to a polymer electrolyte membrane having high durability and improved proton conductivity.
  • the invention further relates to a novel preparation method of these membranes as well as their novel use in high temperature fuel cells operating at a temperature ranging from 80°C to 120°C.
  • the invention pertains to particular fuel cell arrangements comprising the aforesaid membranes, and methods of operating the said fuel cells in the particular temperatures where the electrolyte of the invention has superior performance.
  • MEA Membrane Electrode Assemblies
  • PEM polymer electrode membrane
  • Fuel cells with polymeric electrolytes are sought to have high ionic conductivity.
  • Nafion® membranes made by DuPont, are a typical example of the above mentioned membranes.
  • PEMFC polymer electrolyte membrane fuel cell
  • Nafion® polymer membranes account for 20% of the total cost of Nafion® based membrane electrode assemblies.
  • a Nafion® membrane based MEA for DMFC is expected to cost much more due to the thicker membranes needed for reduced methanol crossover.
  • Nafion® membranes for DMFC applications typically have a price in the range of $600-1200 m "2 depending on the thickness. Besides the high costs, a very well-known drawback of Nafion® is that it limits the PEMFC operating temperature to be below 90°C due to its water dependent proton conduction mechanism and also the disadvantageous glass transition temperature
  • Celtec® P is a well-known commercial membrane electrode assembly available from BASF which contains a Polybenzimidazole (PBI) based polymer containing carrier acids, i.e. phosphoric acid and sulfuric acid. These membranes operate with their optimum performance at temperatures between 150-200°C, which bring the difficulties in their use such as long durations to reach the optimum temperatures.
  • PBI Polybenzimidazole
  • EP 1 1 10 992-A1 discloses solid polymer electrolytes comprising a hydrocarbon part, a chelate group and an electrolyte part.
  • sulfonic acid type graft membranes of ethylene-tetrafluroethylene copolymer (ETFE) are prepared with relatively high dose of electron ray, i.e. 20 kGy, with a thickness of 50 ⁇ .
  • the inventors of the current invention surprisingly achieved the foregoing objects by providing a novel process for producing 4VP grafted ETFE polymeric membranes as described in the following description.
  • the inventors also unexpectedly found that the polymeric membrane structures have excellent conductivity performance independently of relative humidity when the fuel cell arrangement is operated within a temperature 80-130°C, thus filling the gap that is needed in the current state of the art.
  • Figure 1 is a schematic demonstration of the basic steps for preparation of the grafted polymers according to the present invention.
  • Figure 2 is a diagram representing Proton Conductivity vs. RH values of NafionONR and ETFE-g-P4VP membrane according to the present invention, at different temperatures.
  • Figure 3 is a diagram representing Current Density vs. Voltage and Power Density values of the ETFE-g-P4VP membrane of the current invention at different temperatures.
  • Figure 4 is a diagram representing Current Density vs. Voltage values of PBI/H 3 P0 4 membranes at different temperatures according to the literature.
  • Radiation-induced grafting method has the advantages such as simplicity, low cost, control over process and adjustment of the materials composition and structure. In addition, this method assures the grafting of monomers that are difficult to polymerize by conventional methods without residues of initiators and catalyst. Radiation-induced grafting method is simply based on the irradiation of a base polymer either in the presence of a monomer (simultaneous radiation grafting) or without a monomer (pre- irradiation grafting) to create active sites as schematically shown in Figure 1.
  • the present invention aims at providing advantageous ETFE based electrolyte materials that are produced with low dose of irradiation and lower costs while providing excellent proton conductivity and mechanical endurance within the targeted temperatures of ca. 80-120°C. It is also aimed to provide novel method of operating a fuel cell system including the membrane electrode assembly (MEA) as mentioned above at the temperatures mentioned above.
  • MEA membrane electrode assembly
  • the current invention provides a novel method for producing ethylene- tetraflu methylene copolymer (ETFE) based electrolyte materials, namely ETFE base films grafted with 4-vinylpyridine (4VP) monomers, which in other terms is named as ETFE-g-P4VP.
  • ETFE ethylene- tetraflu methylene copolymer
  • the radiation grafting reaction is governed by the diffusion of monomers into the base film, step growth reaction of the grafted chains, and termination reactions. Since the base polymer films are insoluble in all common solvents and barely swell, grafting takes place at the film surface and behaves as the grafting front. This grafted layer swells in the reaction medium and further grafting proceeds by the progressive diffusion of the monomer through this swollen layer and grafting front movement to the middle of the film. This mechanism is known as grafting front mechanism. Grafting occurs uniformly and smoothly in a solvent which provides the swelling of grafting front. The diffusion of the monomer to the base polymer and swelling of grafting front are mainly determined by the solubility parameters of the grafting components (solvent, monomer/polymer).
  • graft level of the copolymers is strongly dependent on the type of solvent used during grafting.
  • various solvents are tested in reaction media of the grafting procedure, and n-propanol is found to be quite advantageous for obtaining higher levels of grafting.
  • Graft levels of ETFE-g-P4VP copolymers are found to be decreasing in the order of n-propanol > isoproponol > ethanol > THF > benzyl alcohol > nitromethane > methanol > 1 ,4- dioxane > n-heptane.
  • a fuel cell assembly comprising 4VP grafted and phosphoric acid doped ETFE polymer membrane (ETFE-g-P4VP) treated with ⁇ -ray irradiation, which membrane has a thickness of 10-30 ⁇ , and
  • a fuel cell operated at a temperature inbetween the range of 80-130°C refers to a PEM fuel cell arrangement having a proton conductivity of at least 40 mS/cm, and more particularly of 40-60 mS/cm.
  • the present invention advantageously enables production of ETFE-g-P4VP copolymers with reduced dose of ⁇ -ray irradiation in between 0.1 and 10 kGy.
  • a novel method of operating a Polymer Electrolyte Membrane (PEM) fuel cell assembly comprising the steps of:
  • ETFE-g-P4VP phosphoric acid doped ETFE polymer membrane
  • a membrane thickness of about 25 ⁇ is particularly preferred.
  • Preferred is also an irradiation dose of about 10 kGy although lower doses still provide satisfactory grafting levels.
  • the ETFE-g-P4VP membrane structures according to the first and second aspect of the current invention are advantageously treated with low dose irradiation at 0.1 to 10 kGy, for instance at 10 kGy as mentioned above. It is also unexpectedly found that the irradiation procedures are not required to be in special conditions such as an N 2 atmosphere, and that the such irradiation environment in ambient conditions still provide desired levels of grafting without substantial formation of impurities and homopolymers. This is attributed to the low dose of irradiation which eventually helps homogenous formation of the active sites on the film surface without substantial deterioration.
  • ETFE-g-P4VP membrane structures comprising the steps of:
  • the present invention provides ETFE based polymer membranes which provides excellent proton conductivity and mechanical properties when grafted with 4VP in the presence of n-propanol with low dose of irradiation along with a special thickness of 10-30 ⁇ .
  • the base polymer poly(ethylene-alt-tetrafluoroethylene), ETFE was purchased in the form of a 25 ⁇ thick film (Nowoflon ET-6235) from Nowofol GmbH (Siegsdorf, Germany).
  • the monomer (4-vinylpyridine) to be grafted onto the ETFE base film and solvents (Sigma Aldrich) were used without any further purification.
  • the base polymer, ETFE was cut into a 7 cm x 7 cm piece, washed with ethanol and then dried in a vacuum oven at 80°C for 1 hour.
  • the dried film was placed in a polyethylene zip-lock bag to prevent contamination. Irradiation of the film was performed at Gamma-Pak Sterilization (Cerkezkoy, Turkey) using gamma rays from a Co source. The irradiation was carried out in air at room temperature with a dose of 10 kGy. After exposure, the film was stored at -80°C until used.
  • Irradiated film was placed into a glass tube reactor and then grafting solution composed of monomer (4VP) and solvent (n-propanol) was added to the reactor which was then purged with dry nitrogen for 30 minutes. The reactor was subsequently sealed and placed in thermostated water bath, and grafting reactions were carried out. The grafted film was washed with the solvent used during grafting in order to remove residual monomer and/or polymer, which were not bonded to the base film, then dried at 70°C and reweighed. The polymer film so obtained was then treated with phosphoric acid to obtain acid doped ETFE-g-P4VP copolymer.
  • the grafted film was then placed into a Bekktech Conductivity Cell Assembly that includes an air control and a Bekktech control unit that connects the PC and probes.
  • Greenlight FC G50 test station integrated the aforesaid assembly maintained the control on the cell temperature and RH.
  • the grafted film in this way was assayed with four point probe proton conductivity tests in different temperatures (80°C, 120°C, 130°C) and relative humidity values.
  • a conventional membrane, Nafion® NR was also tested to provide comparative data.
  • proton conductivity of the ETFE-g-P4VP copolymers according to the current invention provided prominent and stable results at temperatures between 80-130°C independent from humidity.
  • the proton conductivity of the membrane was in between about 40-60 mS/cm. Nafion®, on the other hand required higher relative humidity levels for higher efficiency of the fuel cell stuck as expected.
  • Figure 3 shows high temperature fuel cell performance of the copolymers prepared according to the present invention wherein current density is shown depending on voltage (V) and Power Density.
  • V voltage
  • Power Density As the diagram shows, the ETFE-g-P4VP membrane operated at 80°C, 100°C and 120°C exhibits excellent current density values.
  • a steady state current density of about 800 mA/cm 2 was obtained for instance at 80°C, and about 1600 mA cm 2 was obtained for instance at 120°C.
  • a comparative diagram obtained from the literature for a PBI/H 3 P0 4 system as shown in Figure 4 exhibits that similar current densities were obtained at higher temperatures, i.e. 100°C and 190°C, respectively.
  • ETFE-g- P4VP copolymers of the current invention demonstrate very surprising results at operating temperatures inbetween the range of 80°C-120°C or 80°C-130°C. This comparatively lower operation temperature range is also advantageous for reducing the startup time and material protection of the fuel cells which are cited as the important factors in commercialization of fuel cell energy generators.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Fuel Cell (AREA)

Abstract

La présente invention concerne une membrane électrolytique polymère ayant une durabilité élevée et une conductivité protonique améliorée qui est formée en utilisant un film à base polymère ETFE ayant une épaisseur de 10-30 μm que l'on traite avec une faible dose d'exposition à des rayons γ, en greffant le film ETFE avec 4VP en présence de n-propanol suivi d'un dopage avec acide du polymère obtenu avec de l'acide phosphorique. L'invention concerne également un nouveau procédé de fonctionnement d'une pile à combustible PEM comprenant la membrane susmentionnée à des températures comprises entre 80 et 130 °C.
PCT/EP2013/066945 2013-08-13 2013-08-13 Piles à combustible à membrane électrolytique polymère à performance améliorée WO2015022021A1 (fr)

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PCT/EP2013/066945 WO2015022021A1 (fr) 2013-08-13 2013-08-13 Piles à combustible à membrane électrolytique polymère à performance améliorée

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200295394A1 (en) * 2019-03-15 2020-09-17 University Of Maryland, College Park Ionic liquid conductive membrane and methods of fabricating same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1110992A1 (fr) 1999-11-29 2001-06-27 Kabushiki Kaisha Toyota Chuo Kenkyusho Electrolyte polymère solide ayant une haute durabilité
JP2001213987A (ja) * 2000-02-02 2001-08-07 Toyota Central Res & Dev Lab Inc 高温プロトン伝導性電解質膜
JP2004220837A (ja) * 2003-01-10 2004-08-05 Toyota Motor Corp 高分子電解質及び高分子電解質の製造方法並びに燃料電池
DE102005023897A1 (de) * 2005-05-24 2006-11-30 Volkswagen Ag Verfahren zur Herstellung einer Polymerelektrolytmembran für eine Brennstoffzelle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1110992A1 (fr) 1999-11-29 2001-06-27 Kabushiki Kaisha Toyota Chuo Kenkyusho Electrolyte polymère solide ayant une haute durabilité
JP2001213987A (ja) * 2000-02-02 2001-08-07 Toyota Central Res & Dev Lab Inc 高温プロトン伝導性電解質膜
JP2004220837A (ja) * 2003-01-10 2004-08-05 Toyota Motor Corp 高分子電解質及び高分子電解質の製造方法並びに燃料電池
DE102005023897A1 (de) * 2005-05-24 2006-11-30 Volkswagen Ag Verfahren zur Herstellung einer Polymerelektrolytmembran für eine Brennstoffzelle

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LALE ISIKEL SANLI ET AL: "Synthesis and characterization of novel graft copolymers by radiation-induced grafting", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 120, no. 4, 15 May 2011 (2011-05-15), pages 2313 - 2323, XP055111531, ISSN: 0021-8995, DOI: 10.1002/app.33419 *
NASEF ET AL., J. APPL. POLYM. SCI., 2012
SCHMIDT, C.; SCHMIDT-NAAKE, G.: "Proton Conducting Membranes Obtained by Doping Radiation-Grafted Basic Membrane Matrices with Phosphoric Acid", MACROMOL. MATER. ENG., vol. 292, 2007, pages 1164 - 1175

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200295394A1 (en) * 2019-03-15 2020-09-17 University Of Maryland, College Park Ionic liquid conductive membrane and methods of fabricating same

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