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WO2011043758A1 - Piles à combustible à échange anions/hydroxydes, comportant ionomères et membranes - Google Patents

Piles à combustible à échange anions/hydroxydes, comportant ionomères et membranes Download PDF

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Publication number
WO2011043758A1
WO2011043758A1 PCT/US2009/005553 US2009005553W WO2011043758A1 WO 2011043758 A1 WO2011043758 A1 WO 2011043758A1 US 2009005553 W US2009005553 W US 2009005553W WO 2011043758 A1 WO2011043758 A1 WO 2011043758A1
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WIPO (PCT)
Prior art keywords
ionomer
tpqpoh
ttmopp
hydroxide
polysulfone
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Ceased
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PCT/US2009/005553
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English (en)
Inventor
Yushan Yan
Rui CAI
Shuang Gu
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University of California Berkeley
University of California San Diego UCSD
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University of California Berkeley
University of California San Diego UCSD
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Application filed by University of California Berkeley, University of California San Diego UCSD filed Critical University of California Berkeley
Priority to EP09850302.2A priority Critical patent/EP2401785B1/fr
Priority to HK12110815.8A priority patent/HK1170078B/xx
Priority to PCT/US2009/005553 priority patent/WO2011043758A1/fr
Priority to US13/123,477 priority patent/US8641949B2/en
Priority to CN200980140052.6A priority patent/CN102449840B/zh
Publication of WO2011043758A1 publication Critical patent/WO2011043758A1/fr
Anticipated expiration legal-status Critical
Priority to US14/171,546 priority patent/US9263757B2/en
Ceased legal-status Critical Current

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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
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. 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
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • 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
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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
    • H01M8/1032—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]
    • 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

Definitions

  • anion/hydroxide exchange membrane fuel cells (AEMFCs/HEMFCs). It provides a family of polymers/ionomers capable of forming membranes having exceptional OH " ionic conductivity as well as advantageous mechanical properties.
  • the invention also provides membranes including the provided polymers/ionomers and AEMFC/HEMFC fuel cells incorporating such membranes.
  • Anion/hydroxide exchange membrane fuel cells have received increasing attention due to their dominant advantages such as (a) more facile fuel oxidation and oxygen reduction in high pH media, (b) electro osmotic drag by OH- from cathode to anode, which not only reduces fuel crossover but also realizes anode drainage, and (c) complete elimination of the crippling bi/carbonate contamination problem of traditional liquid alkaline fuel cells (AFCs) whose electrolyte contains free metal cations.
  • AFCs liquid alkaline fuel cells
  • a suitable anion/hydroxide exchange ionomer i.e., a charged polymer
  • PEMFCs proton exchange membrane fuel cells
  • AEMFCs/HEMFCs This greatly limits AEMFCs/HEMFCs performance and development.
  • Non ionic conductive PTFE has also been used as ionomer, which doesn't provide OFT transfer in the electrode at all. See, e.g., E. H. Yu and K. Scott, Journal of Applied Electrochemistry 35 (1), 91 (2005). Sometimes acid National ionomer was used as ionomer, which restrains the OFT transfer in the electrode dramatically. See, e.g., H. Y. Hou, G. Q. Sun, R. H. He et al., Journal of Power Sources 182 (1), 95 (2008); A. Verma and S. Basu, Journal of Power Sources 174 (1), 180 (2007).
  • This invention provides a family of polymers capable of forming membranes having exceptional OH " ionic conductivity as well as advantageous mechanical properties.
  • the invention also provides membranes including the provided polymers and AEMFC/HEMFC fuel cells including such membranes.
  • the provided polymers typically carry a positive charge, and therefore are also referred to herein as "ionomers”.
  • TPQPOH tris(2,4,6-trimethoxyphenyl)phosphine based quaternary phosphonium polysulfone hydroxide
  • the ionomer of the invention has hydroxide conductivity one to two orders of magnitude greater than the closely related alkyl and phenyl phosphonium functionalized ionomers
  • TPQPOH was synthesized by chloromethylation and quaternary
  • the TPQPOH contains quaternary phosphonium hydroxide functional group, and it not only provides the OH- transfer but also has excellent solubility. Owing to the extremely high basicity (pK t ,: 2.8) and large molecular size,
  • TTMOPP tris(2,4,6-trimethoxyphenyl)phosphine
  • the invention provides a highly basic ionomer comprising (OH " ) m , wherein Ml is a polymer-forming monomer comprising an aromatic moiety or a plurality of such monomers at least one of which comprises an aromatic moiety and B + OH " is a highly basic functional group having a p3 ⁇ 4 of 0.2 or smaller.
  • the present invention provides a highly basic ionomer having a polymer backbone including aromatic moieties and a plurality of a highly basic functional
  • the ionomer of claim 1 has an M3 configured linking Ml and B + , wherein M3 is selected from -(CR'R") n -, -Ar- (aromatic), and -substituted -Ar-, and wherein n is 1, 2, or 3 and wherein R 1 and R" are independently selected from H, a halogen, a short chain alkyl, and halogenated a short chain alkyl, or includes at least one quaternary X*, where X is selected from P, As, and Sb, or S, Se and Te.
  • the highly basic functional group, B + can be represented by the scheme (R'R"R"')P + , wherein one or more of R', R", and R'" is independently selected from an electron donating group, or wherein one or more of R', R", and R'" can be independently an unshared electron pair adjacent to X or an unshared electron pair adjacent to an unsaturated system adjacent to X, or wherein one or more of R', R", and R !
  • R', R", and R'" can independently be a group selected from Ar (aromatic) and an Ar further having electron donating substituents.
  • R' or R" or R'" can be (2,4,6-RO) 3 Ph wherein R is selected from a short chain alkyl or allyl.
  • the ionomer of the invention is selected from one or more of polysulfone, polystyrene, poly(ether sulfone), poly(ether sulfone)-cardo, poly(ether ketone), poly(ether ketone)-cardo, poly(ether ether ketone), poly(ether ether ketone ketone), poly(phthazinone ether sulfone ketone), polyetherimide, and poly(phenylene oxide), and the polymer backbone of the ionomer can include a first monomer and a second monomer in approximately equal mol ratios.
  • the present invention also provides ionomers having one or more pairs of cross linked polymer backbones.
  • at least one pair of polymer backbones are linked by at least one -(B + ) " group, or at least one short chain alkyl.
  • the present invention also provides methods of making (tris(2,4,6-trimethoxyphenyl) phosphine) x based polysulfone hydroxide (TPQPOH-x) that, first, chloromethylate polysulfone (PSf) dissolved in an inert solvent for a selected reaction time, and second, combine tris(2,4,6-trimethoxyphenyl)3 phosphine (TTMOPP) + Y " and chloromethylated polysulfone (CMPSf) in a polar, aprotic solvent under conditions leading to synthesis of (tris(2,4,6-trimethoxyphenyl) phosphine) x based polysulfone hydroxide, wherein Y " comprises
  • the mol ratio of choloromethylene groups to polysulfone monomers is measured by 'HNMR.
  • PSf can be chloromethylated in the presence of
  • TTMOPP and CMPSf can be combined at a mol ratio of TTMOPP to CMPSf chloromethylene groups so that substantially all TTMOPP molecules are each linked to at most one polysulfone polymer chain, for example a mol ratio equal to or greater than about 1 but less than about 2.
  • TTMOPP and CMPSf are combined at a mol ratio of TTMOPP to the chloromethylene groups in CMPSf so that at least one pair of polysulfone polymer chains are linked to the same TTMOPP group, for example a mol ratio between about 0.5 and about 0.95.
  • (tris(2,4,6-trimethoxyphenyl) phosphine ) x based polysulfone hydroxide with can be combined with a multi-halogenated short chain alkyl under conditions leading to linking short chain alkyls to two or more TTMOPP groups.
  • the present invention also provides an anion/hydroxide exchange membrane configured and sized to be suitable for use in a fuel cell and including an ionomer of this invention, preferably (tris(2,4,6-trimethoxyphenyl) phosphine ) x based polysulfone hydroxide (TPQPOH), wherein x is between about 0 and 2.
  • an ionomer of this invention preferably (tris(2,4,6-trimethoxyphenyl) phosphine ) x based polysulfone hydroxide (TPQPOH), wherein x is between about 0 and 2.
  • the membrane includes an ionomer wherein the ratio of TTMOPP groups bound to each (PSf) monomer in TPQPOH is DC, and wherein DC is selected so that the ionic hydroxide conductivity of the membrane is greater than about 20 mS/cm greater than about 40 mS/cm, and wherein the number of TTMOPP groups bound to two (PSf) ionomer chains in TPQPOH is DSCL, and wherein DSCL is selected so that the degree of swelling is less than about 15%
  • the present invention also provides an anion/hydroxide exchange membrane fuel cell including an ionomer of this invention, and preferably where the ionomer is
  • quaternary-phosphonium functionalized anion/hydroxide exchange ionomers and membranes of this invention can be used for many other purposes such as: dialysis/electrodialysis, desalination of sea/brackish water; demineralization of water; ultra-pure water production; waste water treatment; concentration of electrolytes solution in food, drug, chemical, and biotechnology fields; electrolysis (e.g., chlor-alkali production and H2/O2 production); energy storage (e.g., super capacitors and redox batteries); sensors (e.g., pH/RH sensor), and in other applications what an anion-conductive ionomer is advantageous.
  • electrolysis e.g., chlor-alkali production and H2/O2 production
  • energy storage e.g., super capacitors and redox batteries
  • sensors e.g., pH/RH sensor
  • Fig. 1 illustrates an exemplary HEMFC fuel cell of this invention
  • Fig. 2 A illustrates polarization curves of HEMFC with (2-1) and without (2-2) TPQPOH ionomer.
  • Inset Resistances of MEA (membrane electrode assembly) of HEMFC with (2-3) and without (2-4) TPQPOH ionomer;
  • Fig. 2B illustrates power densities of HEMFC with (2-5) and without (2-6) TPQPOH ionomer
  • Fig. 3 A illustrates polarization curves of HEMFC with TPQPOH ionomer at cell temperatures of 50 °C (3-1), 60 °C (3-2), 70 °C (3-3), 80 °C (3-4).
  • Inset Resistances of MEA of HEMFC with TPQPOH ionomer at cell temperatures of 50 °C (3-5), 60 °C (3-6), 70 °C (3-7), 80 °C (3-8);
  • Fig. 3B illustrates power densities of HEMFC with TPQPOH ionomer at cell temperatures of 50 °C (3-9), 60 °C (3-10), 70 °C (3-11), 80 °C (3-12);
  • Fig. 4 illustrates hydroxide-conductivity vs. IEC at -20 °C for the following QAOH functionalized polymers immersed in deionized water;
  • Fig. 5 illustrates polarization curves (open symbols) at cell temperatures of 50 °C (5-1), 60 °C (5-2), 70 °C (5-3) and power density (solid symbols) and at cell temperatures of 50 °C (5-4), 60 °C (5-5), 70 °C (5-6), both sets of curves being for a 50 ⁇ TPQPOH 152 HEM (hydroxide exchange membrane) incorporated HEMFC;
  • Fig. 6 illustrates polarization curves (open symbols) at cell temperatures of 50 °C (6-1) and 60 °C (6-2) and power density curves (solid symbols) and at cell temperatures of 50 °C (6-3) and 60 °C (6-4), both sets of curves being for a 100 ⁇ TPQPOH 152 HEM incorporated HEMFC;
  • Fig. 7 illustrates polarization curves (open symbols) at cell temperatures of 50 °C (7-1) and 80 °C (7-2) and power density curves (solid symbols) and at cell temperatures of 50 °C (7-3) and 80 °C (7-4), both sets of curves being for a 50 ⁇ Nafion212 PEM (proton exchange membrane) incorporated PEMFC;
  • Fig. 8 illustrates comparison of IR-free (internal resistance) and MT-free (mass transport) cell voltage between TPQPOH 152 HEM incorporated HEMFC and Nafion212 PEM incorporated PEMFC;
  • Fig. 9 illustrates comparison of IR-free cell voltage between TPQPOH152 HEM incorporated HEMFC and Nafion212 PEM incorporated PEMFC;
  • Figs. 2A-B anode and cathode electrodes, respectively, 0.2 mg Pt (Pt black) cm -2 and 0.05 mg TPQPOH cm -2 ; cell temperature of 50 °C; H 2 and 0 2 flows are humidified at temperatures 70 °C and 80 °C, respectively, at flow rates of 0.2 L min -1 , and at back pressures of 250 kPa; the electrolyte membranes are 70 um thick FT-FAA (FuMA-Tech, GmbH);
  • Figs. 3A-B anode and cathode electrodes, respectively, 0.5 mg Pt (Pt black) cm and 0.125 mg TPQPOH cm -2 ; cell temperatures of 50 °C, 60 °C, 70 °C, and 80 °C; H 2 and 0 2 flows are humidified at temperatures 70 °C and 80 °C, respectively, at flow rates of 0.2 L min -1 , and at back pressures of 250 kPa; the electrolyte membranes are 70 um thick FT-FAA;
  • Fig. 5 anode and cathode electrodes, respectively, 0.2 mg Pt (Pt black) cm and 0.05 mg TPQPOH cm -2 ; cell temperatures of 50 °C, 60 °C, 70 °C; H 2 and 0 2 flows are humidified at temperatures 70 °C and 80 °C, respectively, at flow rates of 0.2 L min -1 , and at back pressures of 250 kPa; TPQPOH 152 membrane thickness of 50 ⁇ ;
  • Fig. 6 anode and cathode electrodes, respectively, 0.2 mg Pt (Pt black) cm and 0.05 mg TPQPOH cm -2 ; cell temperatures of 50 °C and 60 °C; H 2 and 0 2 flows are humidified at temperatures 70 °C and 80 °C, respectively, at flow rates of 0.2 L min -1 , and at back pressures of 250 kPa; TPQPOH 152 membrane thickness of 100 ⁇ ;
  • Fig. 7 anode and cathode electrodes, respectively, 0.2 mg Pt (Pt/C 20 wt%) cm and 0.54 mg Nafion212 cm -2 ; cell temperatures of 50 °C and 80 °C; H 2 and 0 2 flows are humidified at temperatures 70 °C and 80 °C, respectively, at flow rates of 0.2 L min -1 , and at back pressures of 250 kPa; the electrolyte is 50 ⁇ thick Nafion212;
  • Fig. 8 anode and cathode electrodes, respectively, 0.2 mg Pt cm -2 of Pt black for HEMFC (Pt black) and Pt/C 20 wt.% for PEMFC; cell temperature of 50 °C; H 2 and 0 2 flows are at flow rates of 0.2 L min -1 , and at back pressures of 250 kPa; the electrolyte membranes are 50 ⁇ TPQPOH 152 for HEMFC and 50 ⁇ Nafion212 for PEMFC;
  • Fig. 9 anode and cathode electrodes, respectively, 0.2 mg cm -2 of Pt black for HEMFC and Pt/C 20 wt.% for PEMFC; cell temperature of 50 °C; H 2 and 0 2 flows are at flow rates of 0.2 L min -1 , and at back pressures of 250 kPa.
  • This invention is a family of membrane-forming polymers having exceptional OH " ionic conductivity by virtue of their being functionalized with, preferably highly, basic groups.
  • Membranes formed from the polymers of this invention has applicability in many areas such as but not limited to high-performance HEMFCs.
  • the other applicability includes dialysis/electrodialysis, desalination of sea/brackish water; demineralization of water;
  • ultra-pure water production e.g., waste water treatment; concentration of electrolytes solution in food, drug, chemical, and biotechnology fields; electrolysis (e.g., chlor-alkali production and H 2 /0 2 production); energy storage (e.g., super capacitors and redox batteries); sensors (e.g., pH/RH sensor), and in other applications what an anion-conductive ionomer is advantageous.
  • electrolysis e.g., chlor-alkali production and H 2 /0 2 production
  • energy storage e.g., super capacitors and redox batteries
  • sensors e.g., pH/RH sensor
  • FIG. 1 illustrates a typical fuel cell with an anode portion (illustrated on the left) and a cathode portion (illustrated here in the right) which are separated by an electrolyte; supporting members are not illustrated.
  • the anode portion carries out an anode half-reaction which oxidizes fuel releasing electrons to an external circuit and producing oxidized products;
  • the cathode portion carries out a cathode half-reaction which reduces an oxidizer consuming electrons from the external circuit.
  • the gas diffusion layers (GDL) serves to deliver the fuel and oxidizer uniformly across the catalyst layer.
  • Charge neutrality is maintained by a flow of ions from the anode to the cathode for positive ions and from cathode to anode for negative ions.
  • the dimension illustrated here is for convenience and are not representative, as the electrolyte membrane are usually selected to be as thin as possible consistent with membrane structural integrity.
  • the anode half-reaction consumes fuel and OH " ions and produces waste H 2 0 (also C0 2 in the case of carbon containing fuels); the cathode half reaction consumes 0 2 and produces OH " ions; and OH " ions flow from the cathode to the anode through the electrolyte membrane.
  • Fuels are limited only by the oxidizing ability of the anode catalyst but typically can include H 2 , MeOH, EtOH, ethylene glycol, glycerol, and similar compounds.
  • Catalysts are usually Pt or based on Ag or one or more transition metals, e.g., Ni.
  • the anode half-reaction consumes fuel and produces FT 1" ions and electrons; the cathode half reaction consumes 0 2 , H + ions, and electrons and produces waste H 2 0; and FT 1" ions (protons) flow from the anode to the
  • electrolyte membrane is a key to fuel cell performance.
  • high fuel cell efficiency requires low internal resistance, and therefore, electrolyte membranes with high ionic conductivity (low ionic resistance) are preferred.
  • electrolyte membranes with high ion-current carrying capacity are preferred.
  • practical electrolyte membranes should resist chemical degradation and be mechanically stable in the fuel cell environment, and also should be readily manufactured.
  • This invention provides polymers/ionomers linked with basic functional groups, preferably highly basic groups that are generically described by Scheme 1.
  • polymers include repeating monomer unit, Ml , with linked basic functional group, B + .
  • the monomer unit polymerizes to form an aromatic polymer (e.g., by containing aromatic functionality) that is selected from one of polysulfone (PSf), polystyrene (PSt), poly(ether sulfone) (PES), poly(ether sulfone)-cardo (PESC), poly(ether ketone) (PEK), poly(ether ketone)-cardo (PEKC), poly(ether ether ketone) (PEEK), poly(ether ether ketone ketone) (PEEKK), poly(phthazinone, ether sulfone ketone) (PPESK), polyetherimide (PEI), Poly(phenylene oxide) (PPO), and so forth.
  • PSf polysulfone
  • PSt polystyrene
  • PES poly(ether sulfone)-cardo
  • PESC poly(ether ketone
  • n is defined as the number of repeat unit containing Ml and (multiple) M2 sections and can be between 10 - 10,000 (more preferably between 50-2000); n' is defined as the number of repeat unit of M2 and can be between 0-100 (more preferably between 0-3); y" illustrates a polymer chain (i.e. top chain) that is crosslinked to the main chain (i.e. middle
  • the polymer can be a copolymer as known in the art, for example a copolymer of Ml and a second monomer, M2, such as -(O)R-, -(O)Ar-, -CO(O)-, -SO(O)-, and so forth, as well as combinations of different monomers.
  • Ml can be poly (vinylbenzyl chloride) (PVBC) in which case the M2 moiety is not necessary.
  • a third single or repeating monomer (can be between 0-100 (more preferably between 0-3)) could be attached alongside M2 (which is linked to Ml) according to scheme 1 above. This version has not been illustrated.
  • other not shown single or repeating monomers (can be between 0-100 (more preferably between 0-3)) could be linked to this third monomer, and so forth.
  • These third or fourth etc. monomers can be, but not limited to, -(O)R-, -(O)Ar-, -CO(O)-, -SO(O)-, and so forth.
  • M2 and the possible third, fourth and subsequent monomers can be all independently selected from the aforementioned groups; and furthermore, these third, fourth and subsequent monomers can be present on both the polymer chain (i.e. [Ml-[M2]n']n) that is crosslinked to the main chain or on the main chain itself.
  • the mole ratio of the basic group to the Ml, x is an adjustable parameter selected to give suitable properties in a particular application. Possible ratios depend on the chemistry of the attachment of B + to Ml as exemplified subsequently. Among possible ratios, a higher ratio is preferable as it leads to a higher ion exchange capacity (IEC), and a higher IEC is expected to lead to a higher ion-carrying capacity. However, a higher ratio can also lead to undesirable physical properties, such as excessive water absorption, swelling, and loss of mechanical stability. Generally, preferred ratios are between one-half and two, 0.5 ⁇ x ⁇ 2. A particular
  • the polymer can be cross-linked in order to improve mechanical stability, e.g., resistance to swelling in an aqueous or an organic solvent environment.
  • the degree of cross-linking is that which ensures minimum required mechanical stability, as excessive cross-linking can restrict the ionic conductivity of the subsequent membrane.
  • This invention can take advantage of many cross-linking techniques known in the art; Scheme 1 illustrates two exemplary techniques.
  • group y the polymer chains themselves are cross-linked by a linker M4", which can be a functional group of Ml (M2) (or of the third monomer, fourth monomer etc) or provided in a separate cross-linking reaction.
  • group y' polymer chains are cross linked through functional group B + by means of linker M4'.
  • M4' is another copy of linker M3 attached to an adjacent polymer chain.
  • M4' is a separate linker such as di- and tri-halogenated lower alkanes and alkenes and halogenated polymers for example, where the preferred halogen is chlorine. Examples include
  • Ml is polysulfone containing -OPhC(CH 3 ) 2 Ph and -OPhSO(0)Ph repeat units and cross-linking, if present, is of the SCL type.
  • This polymer is referred to herein simply as 'polysulfone' (PSf).
  • the basic functional group is one of the important aspects of this invention. It is believed that, when formed into a membrane, the basic groups form a hospitable environment for OH " ions facilitating their transfer through the membrane. Corresponding, positive ions are relatively blocked by this environment.
  • Basic groups useful in this invention have a p3 ⁇ 4 (in the environment of the particular polymer) of between -2.0 - 2.0. Highly preferred basic groups have a p3 ⁇ 4 of -2 or smaller.
  • preferred basic groups are generically described by Scheme 2, with more basic groups being more preferred.
  • M3 is a bridge chain between X* and the polymer backbone, which can be, for example, a short chain alkyl or halogenated alkyl or an aromatic or a substituted aromatic.
  • M3 can be -(CH 2 ) n , -(CR 2 ) n , -(CY 2 ) n , -Ar-, or -substituted Ar-, where n is preferably 1 , 2, or 3 and Y is a halogen (F, CI, Br, I); and the n" is defined as the number of repeat unit of M3.
  • Both X and the substituents SI, S2, and (optionally) S3 are the key to the basicity of B + OH " , and are advantageously chosen to have a p3 ⁇ 4 (in the environment of the particular polymer) of between -2.0 - 2.0 or close to this range, or highly preferably chosen to have a pK b of -2 or smaller.
  • preferred basic groups are generically described by Scheme 2, with more basic groups being more preferred.
  • X is preferably selected from the elements of P, As, Sb, S, Se, Te, and similar, with P, As, and Sb being preferred and P being more preferred (at least because of its lower toxicity).
  • X is preferably not the element of N.
  • Preferred substituents can also have an unshared electron pair connected to an unsaturated system adjacent to X, such as -Ar or substituted -Ar where the substituents on Ar are also electron donating.
  • S 1 , S2, and S3 can have the form illustrated at the left of Scheme 2.
  • Rl , R2, and (optionally) R3 (as shown in scheme 2 above as (R3)) can also be the same or different but all should also be electron donating, preferably strongly electron donating, such as one or more the electron-donating groups already listed.
  • TTMOPP tris(2,4,6-trimethoxyphenyl) phosphine
  • B + is -(2,4,6-Me0 3 Ph) 3 P + and the polymer is PSf (polysulfone), either not cross-linked or SCL.
  • PSf polysulfone
  • TPQPOH-x a polysulfone hydroxide
  • TPQPOH-x a polysulfone hydroxide
  • x is the mole ratio of the quaternary phosphonium groups to the polysulfone monomers.
  • TTMOPP Tris(2,4,6-trimethoxyphenyl) phosphine
  • TPQPOH-x has been synthesized by first chloromethylating polysulfone (PSf) to form the intermediate chloromethylated polysulfone (CMPSf), and second, adding TTMOPP to CMPSf.
  • PSf chloromethylating polysulfone
  • CMPSf intermediate chloromethylated polysulfone
  • TTMOPP TTMOPP
  • CMPSf Chloromethylated Polysulfone
  • CMPSf Separation and purification of CMPSf was carried out by a precipitation method.
  • the reaction mixture was poured into ethanol (95%) to end the reaction.
  • White CMPSf immediately precipitated.
  • the product was recovered by filtration from the ethanol, washed well with ethanol, and dried in vacuum at room temperature for 12 h.
  • CMPSf x% See, e.g., V. Cozan and E. Avram, European Polymer Journal 39 (1), 107 (2003).
  • TPQPOH Tris(2,4,6-trimethoxyphenyl) phosphine based quaternary phosphonium polysulfone chloride
  • TPQPCl Tris(2,4,6-trimethoxyphenyl) phosphine based quaternary phosphonium polysulfone chloride
  • TTMOPP trifluoromethylphosphorization reaction
  • CMPSf chloromethylated groups in CMPSf
  • the quaternary phosphorization reaction was held at 80 °C for 12 h; the reaction mixture was poured into a Petri dish; and the DMF was evaporated at 40 °C for 2 d to obtain TPQPCl.
  • TPQPOH was obtained by treating TPQPCl in 1 M OH at room temperature for 48 h, followed by thoroughly washing and immersion in DI (deionized) water for 48 h to remove residual KOH.
  • the number of phosphonium groups bound to each polysulfone monomer is approximate equal the DC of the CMPSf.
  • SCL-TPQPOH Self-cross linked Tris(2,4,6-trimethoxyphenyl) phosphine based quaternary phosphonium polysulfone chloride
  • SCL-TPQPC1 Self-cross linked Tris(2,4,6-trimethoxyphenyl) phosphine based quaternary phosphonium polysulfone chloride
  • chloromethylated groups in CMPSf was varied in the range from 60% (or 40% or 50%) to 95% (or 96% or 98%). As is understood from the art, lower more ratios leads to a greater degree of cross-linking as then each TTMOPP group is likely to become linked by more than one to the chloromethylated group from different polymer chains. At higher mole ratios, the degree of
  • the number of phosphonium groups bound to each polysulfone monomer is approximately equal to the DC of the CMPSf but a certain number of TTMOPP groups are expected to be bound to at least two separate ionomer chains thereby cross-linking the two ionomer chains.
  • This average number of doubly-linked TTMOPP groups is expected to be on average approximately the mol ratio of the chloromethylated groups in CMPSf to TTMOPP minus one (but not less than 0). Accordingly, the latter number, the mol ratio of the chloromethylated groups in CMPSf to TTMOPP minus one (but not less than 0) is referred to herein as the degree of self-crosslinking (DSCL).
  • Multi-halogenated cross-linked TPQPOH has been prepared by reacting TPQPOH with 1,3-dichloropropane.
  • Multi-halogenated cross-linked PVC-TTMOPP and PVBC-TTMOPP have been similarly prepared.
  • halogenated alkyl/phenyl group (here, chloromethylated methylene) can covalently link to the TTMOPP from different polymer chains by the condensation we mentioned before, forming the multi-halogenated cross-linked pol mers.
  • TPQPOH is insoluble in water, even at 80 °C, which permits its use in electrodes for water-based fuel cells without soluble loss.
  • TPQPOH exhibits excellent solubility in MeOH, EtOH and PrOH in both 50 vol.% in water and pristine solvent at room temperature, which makes TPQPOH a useful soluble ionomer for fuel cell electrode preparation.
  • TPQPOH membranes for the tests described herein were prepared by, first, preparing TPQPC1 membranes by casting TPQPC1 in DMF on a glass plate and then curing and drying at 40 °C for 1-2 days. TPQPC1 membranes (thickness: 100-150 ⁇ ) were obtained by peeling off on the glass plate in deionized (DI) water. Then, TPQPOH membranes were prepared by treating TPQPC1 membranes in 1 M KOH at room temperature for 48 h, followed by thorough washing and immersion in DI water for 48 h to remove residual KOH.
  • DI deionized
  • membrane electrode assembly with commercial anion exchange polymers: Commercial anion exchange membranes were also tested in the study, for example FT-FAA (Fuma-Tech GmbH). FT-FAA membrane had the following characteristics: thickness of 70 ⁇ ; ionic conductivity of 17 mS cm -1 (milli-siemens) in DI water at 20 °C; and ion exchange capacity of 1.6 mmol g _1 .
  • Membrane electrode assemblies (MEA) with 5 cm 2 active area were prepared by pressing the anode, FAA commercial anion exchange membrane (OH- form) and cathode at 60 °C under 120 kgf/cm 2 for 5 min.
  • the MEA was assembled in a single cell fixture for the HEMFC test. After activation, the cell was discharged at constant current density from 0 to maximum current density in steps of 20 mA cm -2 every 5 min.
  • the I-V polarization curves were obtained under the operation conditions: pure 3 ⁇ 4 and 0 2 as fuel and oxidant, 0.2 L min -1 and 250 kPa of flow rate and back pressure for both H 2 and 0 2 , the temperatures of anode and cathode humidifiers are 70 °C and 80 °C, respectively, the cell temperature was kept at 50-80 °C accordingly.
  • Ionic conductivity in the longitudinal direction was measured by a four-electrode method using AC impedance spectroscopy under water immersion. A conductivity cell was made from two platinum foils carrying the current and two platinum wires sensing the potential drop. The impedance measurements were carried out using an impedance/phase gain analyzer (Solartron SI 1260) and a potentiostat (Solartron SI 1287) over the frequency range from lHz to 100 kHz. All the membrane samples were thoroughly washed and immersed in DI water for at least 12 h before testing. The conductivity of the membrane was calculated using the equation:
  • ⁇ is ionic conductivity
  • L is distance between the two reference electrodes
  • W and d are width and thickness of membrane sample, respectively
  • R is resistance of the membrane derived from the right-side intersect of semi-circle on the complex impedance plane with the Re(Z) axis.
  • TPQPOH 124 membrane has 70% and 145% water uptake at 20 °C and 60 °C, respectively, indicating good water absorption. At the same time, its swelling ratios are 21% and 34% at 20 °C and 60 °C, respectively, indicating good dimension stability. Since TPQPOH 124 also has good ionic conductivity as described subsequently TPQPOH 124 is a preferred material for hydroxide exchange membranes. Water uptake (swelling ratio) at 60 oC can be selected to be any value between about 35% (about 14%) and about 2429% (about 157%) by choosing a DC between about 75 and about 178.
  • TPQPOH 178 has an excessive water uptake and swelling ratio, i.e., making the membrane's mechanical strength unacceptable.
  • TPQPOH doesn't lose ionic conductivity, even after being immersed in 10 M KOH solution (half saturated) at room temperature for 48 h, indicating excellent alkaline stability. Only KOH solution at 15 M and higher could turn TPQPOH a deep color and make TPQPOH membranes brittle.
  • Table 5 shows temperature stability of TPQPOH- 124 membrane.
  • TPQPOH doesn't lose ionic conductivity after being immersed in both DI water and even 1 M KOH at 60 °C for 48 h.
  • temperature stability of TPQPOH is excellent as both an ionomer and an anion exchange membrane.
  • TPQPOH exhibits excellent hydroxide conductivity.
  • ionic conductivity of TPQPOH increases remarkably with DC of CMPSf (although mechanical stability decreases concurrently).
  • Hydroxide ionic conductivity of TPQPOH can be selected to be any value between about 8 mS/cm and about 45 mS/cm by choosing a DC between about 75 and about 75%- 178%.
  • TPQPOH 152 exhibits the highest hydroxide-conductivity of among all currently known HEMs.
  • Currently commercially available HEMs or HEMs reported by academic or industry labs are based on ionomers quaternary amines (QAOH) containing functional groups.
  • Scheme 7 shows an exemplary QAOH functional group along with the quaternary phosphonium (QPOH) functional group of this invention.
  • TPQPOHl 52 exhibits the highest hydroxide-conductivity of 45 mS cm 1 (20 °C) among all known HEMs.
  • Fig. 4 illustrates the hydroxide conductivity of several all current QAOH functionalized HEMs available commercially or reported by academic or industry labs plotted against their ion exchange capacity (IEC) (Fig. 4). Commonly higher conductivity is found at higher IEC, and this relationship is represented in Fig. 4 by line 4-10, which slopes upward toward increasing conductivities as the IEC increases.
  • IEC ion exchange capacity
  • QAOH functionalized HEMs are located below line 4-10, while only the QPOH functionalized TPQPOHl 52 of this invention, as a surprising exception, is above the line.
  • TPQPOHl 52 has high conductivity at an IEC at which QAOH functionalized HEMs have only much lower conductivities.
  • QAOH functionalized HEMs require significantly higher IECs which usually compromises mechanical stability membranes (e.g., by causing excessive solvent swelling).
  • TPQPOHl 52 has OH- conductivity 2.6 times that of commercial QAOH functionalized FAA (17 mS cm -1 , Fuma-Tech GmbH). It also has significantly higher conductivity than those QAOH functionalized HEMs (0.031-40 mS cm -1 ) currently in the research sample stage. See, e.g., L. Li and Y. X. Wang, Journal of Membrane Science 262 (1-2), 1 (2005); R. C. T. Slade and J. R. Varcoe, Solid State Ionics 176 (5-6), 585 (2005); D. Stoica, L. Ogier, L. Akrour et al., Electrochim Acta 53 (4), 1596 (2007); J. R. Varcoe, R.
  • TPQPOH has a conductivity ca. 2.4 times of that (19 mS cm "1 ) of PSf functionalized with QAOH, PSf-QAOH at 4-7. This difference is due to the substantially higher basicity of the QPOH functional group in TPQPOH 152 in comparison to the QAOH function group in QAOH functionalized HEMs.
  • TPQPOH 152 is also consistent with its better alkaline stability, because the efficient decentralization of positive charge of phosphorus atom by the electron-donating triple 2, 4, 6-trimethoxyphenyl groups, enhances substantially and simultaneously the stability and basicity.
  • the ratio of hydroxide conductivity of TPQPOH 152 to the proton conductivity of Nafionl 12 is 0.54: 1, which is close to 0.57: 1 that is the ratio of the ion-mobility of the hydroxide to the proton (20.50 vs. 36.25 cm 2 V "1 s "1 , 25 °C)).
  • Electrode preparation Catalyst ink was prepared by mixing platinum black powder and TPQPOH ionomer in the presence of ethanol and DI water. Briefly, platinum black was well dispersed in DI water, followed by addition of 5wt.% TPQPOH in a mixture of ethanol and DI water (50/50 wt./wt.), and then addition of an additional 1.5 g water and an additional 1.5 g anhydrous ethanol. Summarizing, the recipe used was 100 mg Pt; 0.5 g 5wt.% TPQPOH in 50/50 EtOH/H 2 0 solution (25 mg TPQPOH); 1.5 g additional DI H 2 0; and 1.5 g
  • the electrodes (both anode and cathode) were prepared by spraying the catalyst ink onto the commercial gas diffusion layer (GDL), (SGL, 25cc) for certain Pt loadings, typically 0.2 and 0.5 mg Pt/cm 2 .
  • GDL gas diffusion layer
  • SGL SGL, 25cc
  • Figs. 2A and 2B illustrate the comparison of HEMFC performance with and without TPQPOH ionomer in the catalyst layer.
  • Fig, 2A illustrates polarization curves with electrode containing the same Pt catalyst loading of 0.2 mg/cm 2 .
  • TPQPOH adopted HEMFC clearly has a dramatically higher performance, with the maximum current density increasing from 168 to 420 mA/cm 2 (a factor of 2.5 increase).
  • the open circuit voltage (OCV) changes little much, 1.070 vs. 1.100 V, indicating that the TPQPOH ionomer did not affect the catalytic activity of Pt catalyst.
  • Fig. 2A inset illustrates the resistance of fuel cells with and without the TPQPOH ionomer.
  • the resistance of TPQPOH adopted HEMFC reduces from 1.05 to 0.50 ⁇ 2 , which indicates the TPQPOH ionomer can considerably improve the OH- transfer in the electrodes.
  • Fig. 2B illustrates the power density with and without the TPQPOH ionomer.
  • the maximum power density increases from 40 to 138 mW/cm 2 (a factor of 3.5 increase). To the best of the inventors knowledge, this is highest maximum power density among metal cation free HEMFCs.
  • the TPQPOH ionomer enhances HEMFC current density and power density and reduces internal resistance.
  • Figs. 3A-B illustrate HEMFC performance with TPQPOH ionomer in the catalyst layer at elevated temperatures.
  • Fig. 3A illustrates polarization curves demonstrating that TPQPOH adopted HEMFC performance improves with increasing fuel cell temperature.
  • the maximum current density increases from 380 mA/cm 2 at 50 °C to 570 mA/cm 2 at 80 °C (a factor 50% increase).
  • the OCV of TPQPOH adopted HEMFC decreases slightly from 1.080 V at 50 °C to 1.060 V at 80 °C (largely due to the Nernst law).
  • Fig. 3 A inset illustrates the internal resistance of TPQPOH adopted HEMFCs at elevated temperatures.
  • the resistance of TPQPOH adopted HEMFC decreases from 0.48 ⁇ 2
  • Fig. 3B illustrates the power density of TPQPOH adopted HEMFC at elevated temperatures.
  • the maximum power density increases form 141 mW/cm 2 at 50 °C to 196
  • FIG. 5 illustrates polarization curves for an H 2 /0 2 HEMFC with a 50 ⁇ TPQPOH 152 HEM. It is apparent that the peak power density increases with cell temperature (207, 236 and 258 mW cm at 50, 60 and 70 °C, respectively), while the measured internal resistance decreases with increasing cell temperature (0.225, 0.214 and 0.210 ⁇ cm 2 at 50, 60 and 70 °C, respectively).
  • Fig. 6 illustrates results with a thicker (100 ⁇ ) TPQPOH 152 incorporated HEMFC.
  • the peak power densities were 176 and 202 mW cm -2 and the internal resistances were 0.334 and 0.299 ⁇ cm 2 at 50 and 60 °C, respectively.
  • Table 8 show comparable results QAOH functionalized HEMs.
  • HEM incorporated HEMFC, and its internal resistance is 13%-50% that of the QAOH fuel
  • ⁇ cm are the highest and lowest values, respectively, among these HEMFCs.
  • the HEMFC has about a quarter of peak power density and 2.3 times of internal resistance of the PEMFC.
  • Fig. 8 illustrates that the IR-free (IR for internal resistance) and MT-free (MT for mass transport) cell voltage of HEMFC is clearly higher than that of PEMFC, providing further evidence that the catalysts in HEMFC are more active than in the PEMFC.
  • Fig. 9 illustrates that the MT voltage loss of the HEMFC is larger than that of the PEMFC at middle-to-high current density range. This is likely due to the more demanding needs for water transport in a HEMFC, where water is both a product at the anode and a reactant at the cathode reaction, respectively. See, e.g., Jin-Soo Park, Gu-Gon Park, Seok-Hee Park et al., Macromol Symp 249-250 (1), 174 (2007).
  • This solvent resistance of SCL-TPQPOH can be an advantageous for HEMs, considering the diversity of fuels (including low-level alcohols) for HEMFCs and long-term stability of the HEMs.
  • Table 1 1 shows the water uptake and swelling ratio of SCL-TPQPOH HEM.
  • DSCL means 'degree of self-cross-linking'. Because of high hydrophilicity, pristine TPQPOH 186 has a water uptake of around 3000% and a swelling ratio of 200%. This very poor mechanical stability prevents pristine TPQPOHl 86 from practical application as an HEM in HEMFCs. However, it is apparent that self-cross linking can significantly reduce water uptake and swelling ratio by about 1-2 orders of magnitude. Thus, SCL- TPQPOH with high DCs are possibly applicable for use as HEMs. Water uptake (swelling ratio) of TPQPOHl 86 at 60 oC can be selected to be any value between about 98% (about 15%) and about 17% (about 6%) by choosing a DSCL between about 5% and about 40%.
  • SCL-TPQPOH 186-DSCL05 and SCL-TPQPOH 186-DSCL 10 have an advantageous balance of high conductivity and good dimension stability. Hydroxide conductivity of TPQPOH 186 at
  • 1279-507XX-XPC 091009 31 20 oC can be selected to be any value between about 32 mS/cm and about 4 mS/cm by choosing a DSCL between about 5% and about 40%.
  • SCL-PVBC hydroxide exchange membranes Self-cross linked poly (vinylbenzyl chloride) hydroxide exchange membranes:
  • PVBC is another important commercial polymer. Because of excessively high IEC (1.5 mmol/g), pristine quaternary-phosphonium functionalized PVBC is water-soluble polymer, and accordingly, is not suitable for HEMs.
  • self-cross linking is not limited to polysulfone; it can also be applied to, at least, PVBC.
  • Synthetic procedures similar to those used with PSf, SCL are similar to those used with PSf, SCL
  • SCL-QPPVBC HEMs with DSCLs of approximately 10-50% were found to have a flexible and tough membrane morphology, to exhibit good dimension stability (swelling ratio of 5-10%), and to have high hydroxide conductivity (10-40 mS/cm)).

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Abstract

L'invention concerne une famille de polymères fonctionnalisés qui sont capables de former des membranes qui présentent une conductivité ionique OH' exceptionnelle ainsi que des propriétés mécaniques avantageuses. L'invention concerne en outre des membranes qui comprennent les polymères fournis et des piles à combustible AEMFC et HEMFC comprenant ces membranes. Dans un mode de réalisation préférée, les groupements fonctionnels préférés comprennent un phosphonium quaternaire et, mieux encore, le polymère fourni est l'hydroxyde polysulfone phosphonium fonctionnalisé (tris(2,4,6-triméthoxyphényl)phosphine)3.
PCT/US2009/005553 2008-10-10 2009-10-09 Piles à combustible à échange anions/hydroxydes, comportant ionomères et membranes Ceased WO2011043758A1 (fr)

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HK12110815.8A HK1170078B (en) 2009-10-09 Highly basic ionomers and membranes and anion/hydroxide exchange fuel cells comprising the ionomers and membranes
PCT/US2009/005553 WO2011043758A1 (fr) 2009-10-09 2009-10-09 Piles à combustible à échange anions/hydroxydes, comportant ionomères et membranes
US13/123,477 US8641949B2 (en) 2008-10-10 2009-10-09 Highly basic ionomers and membranes and anion/hydroxide exchange fuel cells comprising the ionomers and membranes
CN200980140052.6A CN102449840B (zh) 2009-10-09 2009-10-09 高度碱性的离聚物和膜以及包括该离聚物和膜的阴离子/氢氧化物交换燃料电池
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JP2013045696A (ja) * 2011-08-25 2013-03-04 Sharp Corp アニオン交換膜型燃料電池システム
EP2639577A1 (fr) 2012-03-16 2013-09-18 SolviCore GmbH & Co KG Capteur de gaz électrochimique comprenant une membrane d'échange d'anions

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