WO2003030289A2 - Membrane polymere pour piles a combustible et procede de production de ladite membrane - Google Patents

Membrane polymere pour piles a combustible et procede de production de ladite membrane Download PDF

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Publication number
WO2003030289A2
WO2003030289A2 PCT/DE2002/003736 DE0203736W WO03030289A2 WO 2003030289 A2 WO2003030289 A2 WO 2003030289A2 DE 0203736 W DE0203736 W DE 0203736W WO 03030289 A2 WO03030289 A2 WO 03030289A2
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Prior art keywords
membrane
segment
acid
ether
block
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PCT/DE2002/003736
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German (de)
English (en)
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WO2003030289A3 (fr
Inventor
Dieter Lehmann
Jochen Meier-Haack
Claus Vogel
Antje Taeger
Suzana Pereira Nunes
Dieter Paul
Klaus-Viktor Peinemann
Kai Jakoby
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Institut Für Polymerforschung Dresden E.V.
Gkss-Forschungszentrum Gessthacht Gmbh
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Priority to EP02776768A priority Critical patent/EP1430560A2/fr
Priority to AU2002339343A priority patent/AU2002339343A1/en
Publication of WO2003030289A2 publication Critical patent/WO2003030289A2/fr
Publication of WO2003030289A3 publication Critical patent/WO2003030289A3/fr

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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
    • 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
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • 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
    • H01M8/102—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]
    • 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
    • H01M8/1041—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
    • 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
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C08J2365/02—Polyphenylenes
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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 invention relates to the fields of power generation, vehicle construction and chemistry and relates to polymer fuel cell membranes, such as those that can be used, for example, in direct methanol fuel cells, and a method for their production.
  • B. the hydrogen-powered fuel cells or the direct methanol fuel cells comes to the polymer electrolyte membranes (PEM).
  • PEM polymer electrolyte membranes
  • the task is, on the one hand, to separate the two electrode compartments from each other and to minimize the methanol permeability, and on the other hand, the proton transport between the anode compartment (in which the hydrogen is oxidized to protons or methanol to protons and carbon dioxide) and the cathode compartment (in which oxygen is reduced) to ensure.
  • the minimization of the methanol permeability is necessary because the reaction of methanol with oxygen in the cathode compartment leads to a reduction in performance.
  • the requirements for the PEM for use in fuel cells are as follows: 1. high chemical and electrochemical stability, especially under operating conditions 2. high mechanical stability during operation
  • cation exchange membranes based on perfluorinated hydrocarbons, which were initially developed for chlor-alkali electrolysis, have been used in fuel cells. Proton conductivity is achieved through sulfonic acid groups in the side chains of these polymers.
  • Such membranes are known under the trade names Nafion® (DuPont), Dow ⁇ Membran (Dow Chemical), Flemion® (Asahi Glass Co., Ltd) and Aciplex® (Asahi Chemical Industry Co., Ltd).
  • a big disadvantage of these membranes is their high price (approx. US $ 800 / m 2 ).
  • Another disadvantage is their methanol permeability, especially at higher methanol concentrations, so that the fuel cells cannot be operated under optimal conditions.
  • these membranes dry out at operating temperatures> 100 ° C, which leads to a reduction in proton conductivity. Nevertheless, these temperatures are e.g.
  • Reinforced membranes based on PTFE microfiltration membranes coated with a perfluorinated ionomer are also known (GoreSelect TM, Gore and Associates; US 5,547,551). This technique allows the production of thinner membranes, leading to a reduction of the ohmic resistance.
  • the proton conductivity is lower than that of the Nafion ® or Dow ® membranes mentioned above.
  • Membrane materials in fuel cells have been developed e.g. B. described by Ballard (US 5,422,411). Compared to the analog, non-fluorinated polymers, these materials have a significantly higher oxidation stability. In hydrogen fuel cells, these membranes have better electrical properties than Nafion ® or Dow ® membranes.
  • Polybenzimidazole membranes have been described (B. Cahan, JS Wainright, J. Electrochem. Soc. 140, L185 (1994); P. Staiti, M. Minutoli, S. Hocevar, J. Power Sources 90, 231 - 235 (2000) ). These membranes have to be impregnated with phosphoric acid, poly-tungstic acid or phosphorotungstic acid in order to achieve proton conductivity. The acid is bound to the matrix with salt formation with the imidazole groups of the polymer. The ratio of imidazole to acid is of the order of 1: 3 to 1: 5. With these materials, however, there is a risk that the acid will be carried out of the membrane by the water formed during operation and thus the proton conductivity will be lost.
  • PES polyaryl ether sulfone
  • PEM polyaryl ether sulfone
  • Degrees of sulfonation above 29.5% lead to water-soluble products.
  • Degrees of sulfonation of up to 29% give products that are soluble in hot water.
  • these materials swell very much, which leads to poor mechanical properties.
  • Crosslinked sulfonated polyether sulfones have a lower swellability, but the specific conductivity decreases by a factor of 2 compared to the uncrosslinked products.
  • EP 0 574 791 A2 describes sulfonated polyether ether ketone (PEEK) as membrane material for use in fuel cells.
  • PEEK polyether ether ketone
  • high degrees of sulfonation which are necessary for sufficient proton conductivity, lead to materials with high degrees of swelling and thus poor mechanical properties (shortening the life of the membrane).
  • inhomogeneously sulfonated PEEK there is a risk of embrittlement due to recrystallization, since PEEK itself is partially crystalline.
  • a major disadvantage of all previously known polymeric membranes for fuel cells is the insufficient mechanical stability and / or the insufficient methanol retention capacity.
  • the object of the present invention is to provide a polymer fuel cell membrane which has improved mechanical stability and / or a substantially improved methanol retention capacity.
  • the present invention provides polymer fuel cell membranes that can overcome existing deficiencies in the prior art.
  • the polymeric fuel cell membranes according to the invention can consist of one or more separation-active layers. It is also possible for one or more carriers to be present. Materials are used as supports which at least do not completely prevent or prevent the function of the release-active layer (s), advantageously they support the function of the release-active layer (s). One or more release-active layer (s) can be applied to a support, the release-active layer (s) can be arranged between two supports, the material of the release-active layer (s) can also be applied, for example, in cavities, pores of a support material , Combinations of these options can also be implemented.
  • the carrier should primarily ensure and / or increase the mechanical stability of the membrane. It is advantageously constructed from a textile or porous material.
  • the release-active layer according to the invention consists of at least one di- and / or multiblock copolymer with one of the general segment structures A- (B- A) k and / or B- (AB) ⁇ and / or (AB) m with k> 1 and I> 1 and m> 1.
  • these segment structures can also be present side by side and in different numbers.
  • the di- and / or multiblock copolymers can be linear or branched.
  • the block segments (A) and (B) each consist of oligomer segments, the block segment (A) consisting of at least one Electron-non-conductive and proton-non-conductive oligomer segment, and the block segment (B) is composed of at least one proton-conductive and electron-non-conductive oligomer segment.
  • oligomers are compounds which consist of a small number of monomeric molecules. They are called dimers, trimers, tetramers, etc. (Stoeckhert, Kunststofflexikon 9th edition, Carl Hanser Verlag Ober Wien 1998).
  • the oligomers advantageously have degrees of polymerization of 2 to 50.
  • the oligomers present, both from block segment (A) and from block segment (B), can each consist of the same or different oligomer units, with (A) and (B) not having the same oligomer units.
  • the length of the block segment (B) in particular should advantageously be selected according to an optimal proton conductivity.
  • the membrane according to the invention must have a morphologically structure with an essentially continuous proton conductivity. This means that the structure of the membrane with regard to the arrangement of supports and separation-active layers must be selected according to this criterion. Of course, the highest possible proton conductivity is sought. It is advantageous if the separation-active layer is structured in essentially unmixed proton-conducting and non-conducting polymer regions.
  • compositions in which the block segments (A) and (B) have imide structures and the block segment (B) have sulfonic acid groups bonded directly to an aromatic diamine component of the aromatic imide structure are excluded from the composition of the membrane according to the invention. Also excluded from the composition according to the invention are compositions in which the block segment (B) contains sulfonic acid groups which are bonded directly to the aromatics and which, under the respective operating or. Desulfonate operating conditions. This desulfonation occurs particularly in the case of deactivated aromatics, ie aromatics with strongly electron-withdrawing substituents / groups.
  • polyether sulfones bearing sulfonic acid groups in which the sulfonic acid group is present directly bound to the aryl sulfone component (aromatics coupled via sulfone group), relatively easily in the aqueous system or under operating or operating conditions in a fuel cell.
  • no desulfonation of the sulfonic acid groups which are directly coupled to the ether building block has been found.
  • the oligomeric block segments (A) comprise at least one oligomer of the compound classes Oligoarylimid and / or Oligoarylensulfid and / or Oligoarylsulfon and / or Oligoarylethersulfon and / or Oligoarylenether and / or Oligoaryletherketon and / or Oligoarylenetheretherketon and / or synthesized oligoaramide and / or Oligoarylharnstoff and / or Oligoarylenoxadiazole and / or oligoarylenesulfonamide and / or oligobenzimidazole and / or oligobenzoxazole and / or oligobenzothiazole and / or oligoquinoxaline.
  • the degree of polymerization of the block segments (A) is in the range from 1 to 50, advantageously in the range from 4 to 30 and still advantageously between 5 and 10.
  • the block segment (B) advantageously consists of at least one oligomer segment of the compound classes oligoarylene sulfide and / or oligoaryl sulfone and / or oligoaryl ether sulfone and / or oligoarylene ether and / or oligoaryl ether ketone and / or oligoarylene ether ether ketone and / or oligoaramide and / or oligoaryol urea and / or oladialol or urea and / or oxadiall urea and / or Oligoarylenesulfonamide and / or oligobenzimidazole and / or oligobenzoxazole and / or oligobenzthiazole and / or oligoquinoxaline and / or oligoarylimide, with the exception of this oligoarylimide a sulfonic acid group B directly attached to an aromatic amine component of an aromatic
  • the block segment (B) consists of at least one oligomer segment of the compound classes oligoarylene sulfide and / or oligoaryl sulfone and / or oligoaryl ether sulfone and / or oligoarylene ether and / or oligoaryl ether ketone and / or oligoarylene ether ether ketone and / or oligoaryl amide and / or oligoaryl urea and / or oligoarylenoxadiazole and / or oligoarylene sulfonamide and / or oligobobolizole / and / or oligobobolizole / and / or oligobenzolid / and / or oligobenzolid / and / or oligobenzolid / and / or oligobenzolid / and / or oligobenzolid / and / or oligobenzolid / and /
  • the block segment (B) can advantageously also be composed of at least one oligomer segment of the compound classes oligoarylene sulfide and / or oligoaryl sulfone and / or oligoaryl ether sulfone and / or oligoarylene ether and / or oligoaryl ether ketone and / or oligoarylene ether ether ketone and / or oligoaramide and / or oligoaryol urea and / or oladialol or urea and / or oladialol or urea and / or oladialol or urea and / or oladialol or urethane and / or Oligoarylenesulfonamide and / or oligobenzimidazole and / or oligobenzoxazole and / or oligobenzthiazole and / or oligoarylimide and / or oligoquinoxaline
  • the membrane in the separating layer can advantageously contain further polymers and / or further additives.
  • the block segment (A) acts primarily Improve mechanical stability and methanol retention.
  • the block segment (B) is itself proton-conductive and retains the methanol with high selectivity.
  • Such a membrane is advantageously composed of a block segment (A) made from oligoimide (s) and / or oligophenylene sulfide (s) and / or oligosulfonamide (s) and / or oligoarylsulfone (s) and / or oligobenzimidazole (s) and from a block segment (B ) built up from oligophenylene sulfide (s) and / or oligosulfonamide (s) and / or oligoarylsulfone (s) and / or oligobenzimidazole (s) and / or oligoimide (s) with the proton-conducting sulfonic acid and / or phosphonic acid groups, with the exception of the block segments (A) and (B) have an imide structure and the block segment (B) has a sulfonic acid group bonded directly to an aromatic diamine building block of the aromatic imide structure, and has
  • starting materials are used which lead to block segments (A) with at least one electron-non-conductive and proton-non-conductive oligomer segment and which lead to block segments (B ) lead with at least one proton-conducting and electron-non-conducting oligomer segment.
  • At least one of the starting materials for the production of the block segment (A) and / or (B) is present as a solution or as a melt.
  • the oligomeric block segments (A) and (B), each with different reactive end groups, which are necessary for coupling the block segments (A) with the block segments (B), are first prepared in separate reactions. Both the block length and the type of reactive end groups are determined by the composition of the starting materials.
  • the chain lengths of the block segments and the reactive functional end groups are adjusted by a defined excess of one of the monomers of the type CC or DD, as shown schematically in Formula 1.
  • a check is made to control the chain length and the reactive functional end groups difunctional monomer of type CC and / or DD added in a defined ratio to component CD to the reaction mixture (see formula 2).
  • block segments according to the invention Another property of the block segments according to the invention is that the functionalities of their end groups only allow the block segments (A) and (B) to be coupled.
  • the block segments (B) are obtained by reacting monomers, the sulfonic acid (s) and / or phosphonic acid (s) and / or (perfluoro) alkylsulfonic acid (s) and / or (perfluoro) alkylphosphonic acid (s) and / or (perfluoro ) Alkyl carboxylic acid (s) and / or of monomers which contain at least one further proton non-conductive functional group such as.
  • B. contain hydroxyl groups, which is not involved in the chain structure and which can be converted into a proton-conducting group by polymer-analogous reactions of the block segments.
  • a criterion for the selection of the monomers to be used to produce a block segment (B) is the density of the proton-conducting groups DPIG, defined by:
  • the density Dp ⁇ G should advantageously be adjusted by adding monomers without proton-conducting groups in the range from 20% to 200%.
  • the group density is advantageously between 50 and 100%.
  • the degree of polymerization of the proton-conducting block segments (B) is in the range from 1 to 50, advantageously in the range from 1 to 30 and even more advantageously between 2 and 10.
  • ⁇ -propane sultone, ⁇ -butane sultone, or 1, 2,2-trifluoro-2-hydroxy-1-trifluoromethylethane sultone (perfluoro) alkyl lactones can be obtained from the corresponding oligomeric block segments of type (A). This method is particularly advantageous if the oligomer synthesis must be carried out in melt but also in solution at temperatures above 200 ° C.
  • the multiblock copolymers of the general form A- (BA) ⁇ are advantageously obtained, k advantageously Can take values between 2 and 10.
  • This structure enables the finished membrane to have a largely phase-separated morphology with block segment (A) -rich phases (A-phase) and block segment (B) -rich phases (B-phase) and with essentially continuous proton conductivity.
  • Proton-non-conductive A phases of this type do not swell or only swell to a small extent in water or water / methanol mixtures and essentially give the membranes mechanical stability. Furthermore, they form a barrier for water and when using the membranes in DMFC for methanol between the anode and cathode compartments of a fuel cell unit.
  • Proton conduction between the anode and the cathode takes place via swellable B phases of the membrane materials.
  • the lower mechanical stability due to swelling is compensated for by the A phases.
  • the B phases in operation in a DMFC form a barrier essentially for methanol between the anode and cathode spaces of a fuel cell unit.
  • auxiliaries and additives and / or crosslinking agents can then be added.
  • the swellability of the B phase can be controlled during or after membrane production by adding crosslinking agents.
  • they are formed as a separation-active layer (s) alone or on and / or between and / or in a support as a membrane, the membrane having a structure with an essentially continuous structure Has proton conductivity.
  • Advantageous monomers for the production of oligomeric block segments (A) can be:
  • Terephthalic acid isophthalic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5- dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-4,4 '-dicarboxylic acid,
  • Diaminopyridine 3.5 diaminopyridine, piperazine, 2,4-diamino-pyrimidine, 4,6-
  • Terephthalic acid isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4, 4 '-dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid, pyridine-dicarboxylic acid 2,6-, 5-hydroxyisophthalic acid and
  • Terephthalic acid isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid,
  • Terephthalic acid isophthalic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5- dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, biphenyl-4,4 '-dicarboxylic acid, diphenyl ether-4, 4'-dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid, pyridine 2,6-dicarboxylic acid, 5-hydroxyisophthalic acid and
  • Advantageous monomers which only lead to the production of the oligomeric block segments (B), in addition to those mentioned for the production of the block segments (A), can be:
  • 5-lsophthalphosphonklare 5-lsophthalsulfonkladish, Terephthalsulfonklad, p-phenylenediaminesulfonic acid, m-phenylenediaminesulfonic acid, 4,4 '-Diaminobiphenyl- 2,2' disulfonic acid, 4,4 'diaminostilbene-2,2' disulfonic acid, 2,4-diaminomesitylene -6- sulfonic acid, 3,5-diaminobenzoic acid 4.
  • Combinations of the monomers within a block segment (A) and / or (B) are possible.
  • the criterion for the selection of the monomers and their combinations are the properties of the block segments (A) and (B) according to claim 1.
  • the carboxylic acid and sulfonic acid-containing monomers are advantageously used as acid chlorides for the synthesis of the oligomeric block segments (A) and (B).
  • the carboxylic acid-containing monomers can also be used as methyl or phenyl esters. It is also advantageous to silylate the amino, thiol and hydroxy groups which are involved in the formation of the oligomer. Monomers containing hydroxyl groups can be used in the form of their acetates.
  • the conversion of the monomers to the oligomeric block segments (A) and (B) and the preparation of the di- and / or multi-block copolymers takes place in solution or in the melt, at least one of the monomers used being in solution or in the melt.
  • Polar aprotic solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), 1,4-dioxane or N-methylpyrrolidone (NMP) are used in particular for the reactions which are carried out in solution , If necessary, up to 5% by mass of low molecular weight salts, such as lithium chloride or calcium chloride, are added to these solvents in order to increase the solubility of the oligomers in the corresponding solvents.
  • low molecular weight salts such as lithium chloride or calcium chloride
  • the ratio solvent / monomers is chosen so that the oligomer and later the di- and / or multi-block copolymer concentration is in the range between 5 and 30 mass%, preferably between 10 and 20 mass%.
  • these solutions are used to produce the membranes.
  • the di- and / or multi-block copolymer concentration of these solutions is adjusted so that the solutions have a viscosity which is advantageous for the manufacture of the membranes.
  • the viscosity can also be adjusted by partially evaporating the solvent in vacuo or by adding solvent.
  • solutions which contain at least one of the di- or multiblock copolymers according to the invention or solutions which contain at least one oligomeric block segment (A) and at least one oligomeric block segment (B) or solutions, which contain at least one oligomeric block segment (A) and / or at least one oligomeric block segment (B) and at least one di- or multiblock copolymer using a doctor blade to form a film with a thickness of 100-500 ⁇ m on an inert, smooth base e.g. B. made of glass, PTFE or stainless steel.
  • the oligomeric block segments (A) and (B) are coupled. and / or the or the di- or multiblock copolymers to di- and / or multiblock copolymers instead.
  • the solvent is either partially evaporated by supplying energy in air and then completely in a vacuum or immediately completely in a vacuum. The temperatures for this are in the range of 50 - 150 ° C.
  • the dry membranes obtained in this way have thicknesses of 50 to 150 ⁇ m, preferably between 60 and 100 ⁇ m, the thickness of the membranes being dependent on the thickness of the polymer film pulled out and the polymer concentration.
  • the membranes have a phase-separated morphology with essentially continuous proton conductivity.
  • the support material which consists of a porous or textile material, for example polyphenylene oxide or polyphenylene sulfide
  • an inert, smooth base e.g. B. made of glass, PTFE or stainless steel or fixed.
  • the application of the release-active layer is carried out as described under 1.
  • the separation-active layer on the carrier has a phase-separated morphology with essentially continuous proton conductivity.
  • the support material which consists of a porous or textile material, for example polyphenylene oxide or polyphenylene sulfide, is impregnated with a solution containing the di- and / or multiblock copolymer.
  • the membrane is obtained by evaporating the solvent as described under 1.
  • the separation-active layer which is located in the cavities of the carrier, has a phase-separated morphology with essentially continuous proton conductivity.
  • a polymer film is first applied to a carrier material as described under 2. Before the solvent is evaporated, a second carrier material is applied to this polymer film. This membrane is finished by evaporating off the solvent, as described under 1.
  • the separation-active layer between the supports has a phase-separated morphology with essentially continuous proton conductivity.
  • a membrane which has been produced according to one of the options 1 to 4 is coated with a further polymer solution which may contain the same or a different di- and / or multiblock copolymer.
  • the membrane is finished by evaporating the solvent as described in 1.
  • the additional separation-active layer (s) on the support has a phase-separated morphology with essentially continuous proton conductivity.
  • a Nafion membrane (DuPont) is used as the standard membrane for DMFC. This membrane swells in methanol-water solutions (5% by mass of methanol) and the membrane properties are established. Sufficient conductivity is achieved with a proton conductivity of 0.2 S / cm at 80 ° C. The barrier properties of Nafion membranes with a methanol permeability of 30% and more are not suitable for use in DMFC.
  • % LiCI contains, at -18 ° C to 0.1 mol of tris-trimethylsilyl-p-phenylenediaminesulfonic acid 0.08 mol of isophthalic acid dichloride are added and the mixture is reacted for one hour at -18 ° C. and 8 hours at 100 ° C. with stirring.
  • - Reaction solution B1 (amine-terminated).
  • reaction solution B1 is slowly added dropwise to the reaction solution A1 with stirring. After stirring for 1 hour at 120 ° C., 0.05 mol of acetic anhydride are added dropwise and stirring is continued for 1 hour.
  • the solution is concentrated under vacuum and stirring and drawn into a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 1/20 of the Nafion comparison membrane
  • Block copolymer membrane 2 is a block copolymer membrane
  • reaction solution B1 is slowly added dropwise to the reaction solution A2 with stirring. After stirring for 1 hour at 120 ° C under vacuum and stirring
  • reaction solution B1 is slowly added dropwise to the reaction solution A3 with stirring. After stirring for 1 hour at 130 ° C under vacuum and stirring
  • Block copolymer membrane 4
  • reaction solution B2 is slowly added dropwise to the reaction solution A1 with stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring in such a way that the solution is introduced into a fine glass fiber fabric and is slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 3/100 of the Nafion comparison membrane
  • Block copolymer membrane 5
  • reaction solution B3 is slowly added dropwise to the reaction solution A4 with stirring. After stirring for 8 hours at 130 ° C under vacuum and stirring
  • Block copolymer membrane 6
  • reaction solution A5 is added to reaction solution B3 with stirring. After stirring at 130 ° C. for 8 hours, the solution is cooled and 0.01 mol of dianediglycidyl ether is added as a crosslinking agent. The solution is immediately drawn out to the membrane, dried under vacuum and annealed at 100 ° C. for 5 hours. An easily manageable, mechanically stable membrane is obtained.
  • reaction solution A5 is added to reaction solution B3 with stirring. After stirring at 130 ° C. for 8 hours, the solution is cooled and 0.01 mol of 4,4'-difluorodiphenyl sulfone is added as crosslinking agent. The solution is drawn out to the membrane, dried under vacuum and annealed at 120 ° C. for 8 hours. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 5/100 of the Nafion comparison membrane
  • Block copolymer membrane 8
  • reaction solution B3 100 ml of reaction solution B3 are slowly added dropwise to 50 ml of reaction solution A2 and 50 ml of reaction solution A4 while stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring and drawn out to a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained.
  • Block copolymer membrane 9 is a block copolymer membrane
  • reaction solution B1 and 50 ml of reaction solution B3 are slowly added dropwise to 100 ml of reaction solution A1 with stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring and drawn out to a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 4/100 of the Nafion comparison membrane
  • Block copolymer membrane 10 is a block copolymer membrane
  • reaction solution B1 and 45 ml of reaction solution B3 are slowly added dropwise to 100 ml of reaction solution A1 with stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring and drawn out to a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained.
  • reaction solution B2 and 50 ml of reaction solution B3 are slowly added dropwise to 90 ml of reaction solution A1 with stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring and drawn out to a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 7/100 of the Nafion comparison membrane

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Abstract

Cette invention se rapporte au secteur de la chimie et concerne des membranes, telles que celles appliquées par exemple dans des piles à combustible directes au méthanol. L'objectif de cette invention est de produire des membranes, présentant une capacité de rétention du méthanol sensiblement améliorée. A cet effet, une membrane polymère pour piles à combustible présente une(des) couche(s) de séparation, au moins constituée(s) de copolymères deux- et/ou multi-blocs présentant les structures générales de segments A-(B-A)k et/ou B-(A-B)l et/ou (A-B)m avec k ≥ 1 et l ≥ 1 et m ≥ 1, le segment de bloc (A) étant constitué d'un segment oligomère non conducteur d'électrons et non conducteur de protons et le segment de bloc (B) étant constitué d'un segment oligomère conducteur de protons et non conducteur d'électrons. Cette invention concerne également un procédé consistant à mettre en réaction les substances de départ, afin de produire les segments de blocs (A) à partir d'au moins un segment oligomère non conducteur d'électrons et non conducteur de protons et les segments de blocs (B) à partir d'au moins un segment oligomère conducteur de protons et non conducteur d'électrons.
PCT/DE2002/003736 2001-09-28 2002-09-27 Membrane polymere pour piles a combustible et procede de production de ladite membrane WO2003030289A2 (fr)

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EP02776768A EP1430560A2 (fr) 2001-09-28 2002-09-27 Membrane polymere pour piles a combustible et procede de production de ladite membrane
AU2002339343A AU2002339343A1 (en) 2001-09-28 2002-09-27 Polymer membrane for fuel cells and method for the production thereof

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DE10149716.4 2001-09-28
DE10149716A DE10149716A1 (de) 2001-09-28 2001-09-28 Polymere Brennstoffzellen-Membran und Verfahren zu ihrer Herstellung

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DE10316323A1 (de) * 2003-04-10 2004-10-28 Daimlerchrysler Ag Verfahren zur Herstellung eines basisch funktionalisierten Polyarylethersulfons
WO2005090439A2 (fr) * 2004-03-12 2005-09-29 Polyfuel, Inc. Copolymeres conducteurs d'ions contenant un ou plusieurs oligomeres conducteurs d'ions
DE102004055129A1 (de) * 2004-11-16 2006-05-18 Volkswagen Ag Polymer-Elektrolyt-Membran für eine Brennstoffzelle sowie Verfahren zu deren Herstellung
WO2008012222A2 (fr) * 2006-07-28 2008-01-31 Leibniz-Institut Für Polymerforschung Dresden E.V. Composés de polyarylène sulfonés, matériau pour membrane obtenu à partir de ces derniers, procédé de production et d'utilisation desdits composés
US7459505B2 (en) 2005-05-03 2008-12-02 General Motors Corporation Block copolymers with acidic groups
US7507771B2 (en) 2003-11-13 2009-03-24 Polyfuel, Inc. Ion conductive copolymers containing one or more hydrophobic oligomers
WO2009075974A1 (fr) * 2007-12-11 2009-06-18 Bose Corporation Membrane électrolyte polymère de pile à combustible
US7572535B2 (en) 2002-05-13 2009-08-11 Polyfuel, Inc. Ion conductive copolymers containing one or more hydrophobic oligomers
US7977394B2 (en) 2005-05-03 2011-07-12 GM Global Technology Operations LLC Triblock copolymers with acidic groups
US7993792B2 (en) 2006-07-26 2011-08-09 GM Global Technology Operations LLC Polymer blocks for PEM applications
US8216740B2 (en) 2006-12-12 2012-07-10 Bose Corporation Fuel cell
CN102643546A (zh) * 2012-05-03 2012-08-22 长春工业大学 含1,3,4-噁二唑环的聚芳醚砜中高温质子交换膜及其制备方法
US8492460B2 (en) 2006-07-28 2013-07-23 GM Global Technology Operations LLC Fluorinated polymer blocks for PEM applications

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7572535B2 (en) 2002-05-13 2009-08-11 Polyfuel, Inc. Ion conductive copolymers containing one or more hydrophobic oligomers
DE10316323A1 (de) * 2003-04-10 2004-10-28 Daimlerchrysler Ag Verfahren zur Herstellung eines basisch funktionalisierten Polyarylethersulfons
US7507771B2 (en) 2003-11-13 2009-03-24 Polyfuel, Inc. Ion conductive copolymers containing one or more hydrophobic oligomers
US7504461B2 (en) 2004-03-12 2009-03-17 Polyfuel, Inc. Ion-conductive copolymers containing one or more ion-conducting oligomers
JP2007528930A (ja) * 2004-03-12 2007-10-18 ポリフューエル・インコーポレイテッド １種若しくは複数種のイオン伝導性オリゴマーを含有するイオン伝導性コポリマー
WO2005090439A3 (fr) * 2004-03-12 2005-11-24 Polyfuel Inc Copolymeres conducteurs d'ions contenant un ou plusieurs oligomeres conducteurs d'ions
WO2005090439A2 (fr) * 2004-03-12 2005-09-29 Polyfuel, Inc. Copolymeres conducteurs d'ions contenant un ou plusieurs oligomeres conducteurs d'ions
DE102004055129A1 (de) * 2004-11-16 2006-05-18 Volkswagen Ag Polymer-Elektrolyt-Membran für eine Brennstoffzelle sowie Verfahren zu deren Herstellung
US7459505B2 (en) 2005-05-03 2008-12-02 General Motors Corporation Block copolymers with acidic groups
US8263672B2 (en) 2005-05-03 2012-09-11 GM Global Technology Operations LLC Triblock copolymers with acidic groups
US7977394B2 (en) 2005-05-03 2011-07-12 GM Global Technology Operations LLC Triblock copolymers with acidic groups
US7993792B2 (en) 2006-07-26 2011-08-09 GM Global Technology Operations LLC Polymer blocks for PEM applications
WO2008012222A2 (fr) * 2006-07-28 2008-01-31 Leibniz-Institut Für Polymerforschung Dresden E.V. Composés de polyarylène sulfonés, matériau pour membrane obtenu à partir de ces derniers, procédé de production et d'utilisation desdits composés
WO2008012222A3 (fr) * 2006-07-28 2008-04-24 Leibniz Inst Polymerforschung Composés de polyarylène sulfonés, matériau pour membrane obtenu à partir de ces derniers, procédé de production et d'utilisation desdits composés
US8492460B2 (en) 2006-07-28 2013-07-23 GM Global Technology Operations LLC Fluorinated polymer blocks for PEM applications
US8163864B2 (en) 2006-07-28 2012-04-24 Leibniz-Institut Fuer Polymerforschung Dresden E.V. Sulfonated polyarylene compounds, membrane material made therefrom, method for the production thereof and use
US8216740B2 (en) 2006-12-12 2012-07-10 Bose Corporation Fuel cell
WO2009075974A1 (fr) * 2007-12-11 2009-06-18 Bose Corporation Membrane électrolyte polymère de pile à combustible
US8557473B2 (en) 2007-12-11 2013-10-15 Bose Corporation Fuel cell polymer electrolyte membrane
CN102643546A (zh) * 2012-05-03 2012-08-22 长春工业大学 含1,3,4-噁二唑环的聚芳醚砜中高温质子交换膜及其制备方法

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