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
  • H01M8/08—Fuel cells with aqueous electrolytes
  • H01M8/083—Alkaline fuel cells
• • 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
  • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
  • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
  • C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
• • 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
• • 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

• the present invention relates to anion exchange polymer electrolytes comprising a guanidine base, and to liquid compositions and membranes for fuel cells comprising same.
• Ion exchange polymer electrolytes and their dispersion in liquid medium are an essential part of fuel cells and other electrochemical applications.
• electrochemical reactions occur either in acidic or alkaline media.
• proton exchange membranes offer the required combination of adequate longevity and good conductivity at relatively low temperatures (25-100°C)
• alkaline fuel cells require anion-conducting polymer electrolytes.
• the efficiency of the oxygen reduction reaction is much higher than in acidic conditions, which allows the use of low-cost, abundant electro-catalysts as opposed to precious metal catalysts.
• alkaline fuel cells use an aqueous solution of potassium hydroxide as the electrolyte, with typical concentrations of about 30%.
• a major operating constraint is the requirement for low carbon dioxide concentrations in the oxidant feed stream, as carbon dioxide can result in the formation of carbonate precipitates.
• One approach for addressing this issue is the use of solid anion conducting membranes.
• Alkaline fuel cell systems based on such membranes utilize the desirable properties of the solid electrolytes, such as the lack of requirement of liquid electrolyte circulation, less corrosion, and the capability of applying differential pressure and system design simplification.
• anion exchange polymer electrolytes that have i) good electrolyte stability in alkaline media, ii) high anionic conductivity, and iii) good processibility.
• the low stability of anion exchange polymer electrolytes is due to fast hydrolysis of polymer electrolytes in highly basic conditions. The degradation process can be accelerated by electron- withdrawing molecules in the vicinity of cation functional group.
• Alkyl ammonium cation-based (and other cation-based) anion exchange polymer electrolytes may be synthesized by chloride substitution of a -CH 2 C1 moiety of the polymers. Because the cation form of the polymer electrolytes is directly synthesized via chloride substitution, the resultant cation functionalized polymer electrolytes has limited solubility. The limited solubility has been a significant inhibitor of successful application of alkaline fuel cells.
• the prior art teaches that stability of anion exchange polymer electrolytes can be improved by introducing highly basic and bulky cations such as sulfonium, phosphazenium, phosphazene and guanidinium.
• highly basic and bulky cations such as sulfonium, phosphazenium, phosphazene and guanidinium.
• the cation functionality is directly attached to the hydrocarbon- based polymer backbone, which is technically challenging to synthesize.
• the stability of fluorinated polymer electrolytes comprising the directly-attached highly basic cations is questionable since electron withdrawing characteristics of fluorine tend to weaken the stability of the bulk cations.
• fluorination of polymer electrolytes is desirable, as it is understood to contribute to high gas permeability.
• anion conducting polymer electrolytes that are more stable to chemical degradation at high pH than currently available anion exchange polymer electrolytes, that have improved anionic conductivity, and that have better solubility in a dispersing medium, which in turn improves processibility. Additionally, a need exists for methods of fabrication of high performance solid anion exchange membrane fuel cells which comprise the aforementioned anion conducting polymer electrolytes.
• the present invention meets the aforementioned needs by providing anion exchange polymer electrolytes comprising a guanidine base, and a cation-stabilizing spacer moiety between the base and the polymer. This allows for desirable fluorination of the polymer, while counteracting the destabilizing electron-withdrawing capability of the fluorine atoms.
• a solid anion exchange polymer electrolyte comprising a polymeric core having the structure:
• Ri, R 2 , R 3 and R4 each are independently H, F or a Ci - C 6 alkyl group
• R 5 , R , R 7 and Rg each are independently -H, -NH 2 , F, CI, Br, CN, or a Ci-C 6 alkyl group, or any combination of thereof;
• G is a guanidine base having the structure:
• R9, Ri 0 , Rn , Ri 2 , or R13 is hydrogen and wherein the non-hydrogen groups each independently are a non-cyclic heteroatomic group comprising nitrogen, oxygen, sulfur or a halide selected from the group consisting of fluoride, bromide, chloride and iodide.
• a solid anion exchange polymer electrolyte comprising a polymeric core having the structure:
• Ri 6 is CH 2 or CF 2 ;
• n 1-10, S0 2 -Ph, CO-Ph,
• R 5 , Re, R 7 and Rg each are independently -H, -NH 2 , F, CI, Br, CN, or a Ci-Ce alkyl group, or any combination of thereof;
• G is a guanidine base having the structure:
• a solid anion exchange polymer electrolyte comprising:
• R 5 , R6, R 7 and Rs each are independently -H, -NH 2 , F, CI, Br, CN, or a Ci-C 6 alkyl group, or any combination of thereof;
• G is a guanidine base having the structure:
• a composition comprising a chemical compound
• said chemical compound comprising a polymeric core, a spacer A, and a guanidine base, wherein said chemical compound is uniformly dispersed in a suitable solvent and has the structure:
• R 5 , R6, R 7 and Rs each are independently -H, -NH 2 , F, CI, Br, CN, or a Ci-C 6 alkyl group, or any combination of thereof;
• composition is suitable for use in a membrane electrode assembly.
• the present invention relates to solid anion exchange polymer electrolytes, their dispersion in liquid media, and to membranes and membrane electrode assemblies comprising the solid anion exchange polymer electrolytes, in which the solid anion exchange polymer electrolyte is a chemical compound comprising a polymeric core, a guanidine base, and a cation- stabilizing spacer therebetween, having the structure:
• R 5 , Re, R 7 and Rg each are independently -H, -NH 2 , F, CI, Br, CN, or a Q-C6 alkyl group, or any combination of thereof;
• At least one of R9, R 10 , R11, Ri 2 and R 13 is hydrogen, and the non-hydrogen groups each independently may be a non-cyclic heteroatomic group comprising nitrogen, oxygen, sulfur or a halide (X), wherein X is selected from the group consisting of fluoride, bromide, chloride or iodide.
• R 9 , Rio, R11, R 12 and R 13 all are hydrogen.
• Hydrogenated guanidine has the advantage of superior stability in anion exchange polymer electrolytes.
• R9, R ⁇ o, i 1 , R12, and R] 3 all are -
• the solid anion exchange polymer electrolytes comprise a polymeric core having the following structure:
• R wherein and R], R 2 , R 3 and R4 each are independently H, F or a C ⁇ - C 6 alkyl group; ii) X, Y, Z are independently a direct bond, O, S, S0 2 ,
• R5, R6, R 7 and Rg each are independently -H, -NH 2 , F, CI, Br, CN, or a Ci-C 6 alkyl group, or any combination of thereof;
• G is a guanidine base having the structure:
• R9, Rio, Rn , R12 , or Ri 3 is hydrogen and wherein the non-hydrogen groups each independently are a non-cyclic heteroatomic group comprising nitrogen, oxygen, sulfur or a halide selected from the group consisting of fluoride, bromide, chloride and iodide.
• R9, Rio, Rn , R12 , or R13 all are hydrogen.
• Ri, R 2 , R 3 and R4 are fluorine.
• X, Y and Z are S0 2 .
• A is CO-Ph, where Ph is a phenyl moiety, and R 5 , R6, R 7 and R 3 ⁇ 4 are hydrogen.
• a solid anion exchange polymer electrolyte comprising a polymeric core having the structure:
• R 5 , R6, R 7 and Rg each are independently -H, -NH 2 , F, CI, Br, CN, or a Ci-C6 alkyl group, or any combination of thereof;
• G is a guanidine base having the structure:
• R9, Rio, Rn, Ri 2) and Rj 3 all are -CH 3 .
• R9, Rio, Rn, Ri 2) and Rn all are -H.
• RH, R15, and Rie are all CF 2 .
• R5, R and R 8 are hydrogen.
• the solid anion exchange polymer electrolytes comprise a polymeric core having the following structure:
• R5, R6, R 7 and R 8 each are independently -H, -NH 2 , F, CI, Br, CN, or a Ci-C 6 alkyl group, or any combination of thereof;
• G is a guanidine base having the structure:
• R9, Rio, R11 , Ri 2 , or R13 each independently are -H, -CH3, -NH 2 , -NO, -CH proceduraCH 3
• n 1-6, -(CH 2 ) n -C(NH 2 )-COOH
• 3 all are hydrogen.
• R 9 , Ri 0 , Rn , Ri 2, and Ri 3 all are -CH 3 .
• A is CO-Ph, where Ph is a phenyl moiety.
• R 5 , R ⁇ , R 7 and 3 ⁇ 4 are hydrogen.
• the anion exchange polymer electrolytes comprising a guanidine base of the present invention are extremely stable, highly conductive, highly gas permeable and have good processiblity compared to state of the art anion exchange polymer electrolytes comprising alkyl ammonium bases.
• the degradation of anion exchange polymer electrolytes occurs via elimination reaction (E2) or nucleophilic substitution (SN2) reaction.
• E2 reactions can occur in cationic functional groups having ⁇ -hydrogens with a dihedral angle of 0 or 180°.
• the anion exchange polymer electrolytes comprising a guanidine base of the present invention do not have a ⁇ -hydrogen or a dihedral angle of 0 or 180°, which may greatly reduce the potential of E2 degradation.
• the rate of S N 2 reaction depends strongly on the basicity of the leaving group. In general, the weaker the basicity of the group (the higher the pKa), the greater its leaving ability.
• the pKa value of the guanidine base is approximately five orders of magnitude higher than trialkyl amine, which suggests a much higher stability.
• Another factor that affects the S N 2 reaction rate is the electron density of the cationic functional group.
• the pKa value is lower than that of alkyl ammonium, however, the non-ionized nitrogen can donate its unpaired electrons to the ionized nitrogen, thus stabilizing the cationic group.
• Guanidine bases also have high electron density and resonance structures, which greatly stabilize the functional group. The stability of the guanidine base can further be improved by introducing electron-donating (cation-stabilizing) spacer groups.
• the anionic conductivity of the anion exchange polymer electrolytes of the present invention is excellent.
• the molecular volume of the guanidine base is relatively small compared with other highly basic functionalities such as diaza(l,3)bicyclo[5.4.0]undecane (DBU), Verkade bases and Schwesinger phosphazene bases.
• DBU diaza(l,3)bicyclo[5.4.0]undecane
• Verkade bases Verkade bases
• Schwesinger phosphazene bases The relatively small volume of the guanidine base decreases among cationic functional groups, which improves anionic conductivity.
• the higher conductivity as compared to alkyl ammonium based anion exchange polymer electrolytes is likely due to its resonance structure, wherein the cation in the guanidine base is delocalized, which provides three ion exchange sites.
• the resonance structures provide not only stability but also good conductivity in that three nitrogen atoms participate in anionic conduction, whereas traditional alkyl ammonium bases have only a single nitrogen.
• the anion exchange polymer electrolytes of the present invention also have excellent processibility. Unlike anion exchange polymer electrolytes, guanidine base anion exchange polymer electrolytes can be synthesized via a neutral form and subsequently ionized.
• the neutral form (I) in Scheme 1 of the guanidine base functionalized polymer electrolytes have relatively good solubility (or dispersibility) in aprotic solvents such as dimethylsulfoxide, dimethylformamide, and n-methyl m-pyrrolidone, and protic solvents such as glycerol, at elevated temperatures. Even the ionized form (II) and (III) are soluble (or dispersible) in a few aprotic solvents.
• the ability to disperse the polymer electrolyte in a liquid medium results in versatility and processibility.
• the good dispersion qualities of the anion exchange polymer electrolytes of the present invention allows the use of state of the art processing methods of proton exchange membrane fuel cells, which are far advanced compared to those of alkaline anion exchange membrane fuel cells.
• the present invention is related to polymers, anion conducting membranes, and polymer dispersions in liquid mediums.
• the functionalized anion exchange polymer electrolytes of the present invention can be synthesized from wholly perfluorinated, partially perfluorinated, and polyaromatic polymers. Alternatively, synthesis may be performed by first functionalizing the monomers, followed by direct polymerization. Polymer modification has the advantages of being simpler and more economical whereas direct polymerization of the monomer has the advantage of allowing more precise control over the polymer architecture.
• the anion exchange polymer electrolytes of the present invention may be synthesized by the reaction of methyl brominated polymers with a guanidine base (Scheme 2).
• the anion exchange polymer electrolytes of the present invention may be synthesized using the precursor to the perfluorinated sulfonic acid or sulfonated hydrocarbon based polymers.
• Scheme 3 shows an example of a functionalized perfluorinated polymer comprising a guanidine base by using a known procedure such as a Grignard reaction. Here, the guanidine base is directly connected to a -CH 2 group. In contrast to Scheme 2, the absence of a ⁇ -hydrogen may improve polymer stability.
• the anion exchange polymer electrolytes of the present invention may be synthesized using the precursor to the perfluorinated sulfonyl fluoride or carboxylic acid based polymers and a spacer.
• Scheme 5 shows an example of a functionalized perfluorinated polymer comprising a spacer and guanidine base.
• the guanidine base is connected to a spacer having one of the aforementioned structures.
• Functionalized polymer electrolytes also may be synthesized by the direct polymerization of functionalized monomer with a guanidine base (anion exchange unit) with a commercially available monomer, as shown in Scheme 6.
• D a halide such as F, CI, Br, or I
• G is a guanidine base having one of the aforementioned structures
• Ar] and Ar2 include a monomer having the structure
• D is halide (such as F, CI, Br, I), -OH,-SH, or -NH 2 ;
• Ri- Rg each independently may denote H, an alkyl, cycloalkyl, alkenyl, aryl, or aralkyl groups having 1 to 10 carbon atoms, or a heterocylclic group having 4 to 20 carbon atoms; and
• the polymer structure which forms the anion-exchange polymer electrolytes of the finally obtained in addition to the aforementioned compounds, other suitable compounds which would be known to one of skill in the art may be used.
• Engineering plastic-based, radiation grafted and fluorocarbon polymers may produce superior mechanical properties in anion exchange membranes. Fluorocarbon polymers are preferred for electrode materials due to higher reactant permeability and inertness to catalysts. Fluorocarbon polymers using direct reaction of the sulfonyl fluoride polymer with the guanidine base is more economical.
• the number of anion exchange groups of the polymer electrolytes is not particularly limited, however, in one embodiment an ion exchange capacity (IEC) of from about 0.2 meq/g to about 5.0 meq/g, and alternatively is from about 0.5 meq/g to about 3.0 meq/g, is preferred for superior conductivity and mechanical properties.
• IEC ion exchange capacity
• Guanidine base functionalized anion-exchange membranes can be prepared in a variety of methods that would be known to one of skill in the art, including solution casting, extrusion, blade method, spin coating, melt processing, etc.
• the thickness of the final polymer membrane of the present invention may be from about 5 ⁇ to about 150 ⁇ , and alternatively is from about 10 ⁇ to 100 ⁇ .
• the guanidine base functionalized polymer electrolytes can be used as a filler in organic or inorganic substrates.
• the substrate may be any one of a variety of suitable substrates, such as woven fabric or unwoven fabric. Alternatively, a porous membrane may be used.
• the neutral and ionized forms of guanidine base functionalized polymers may be readily dissolved or dispersed in protic or aprotic solvents or dispersion media.
• suitable liquid media include water, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, iso-butanol, tert-butanol, ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3- butanediol, 1,4-butanediol, 1,5 pentanediol, propane- 1,2,3-triol, 1,2,4 butanetriol, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), and combinations thereof.
• DMF dimethylformamide
• DMAc dimethylacetamide
• NMP N-methylpyrrol
• the solvent is an aprotic solvent, which is advantageous because when a proton is donated in a protic solvent, this converts the neutral from to the ionized form, which is more difficult to dissolve or disperse in a liquid medium.
• hydrolysis may occurs in water-based protic solvents at high temperature processing (ca. >200°C).
• the aprotic solvent is selected from the group consisting of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and combinations thereof.
• the solvent is an alcohol.
• the solvent is ah alcohol selected from the group consisting of ethanol, n- propanol, iso-propanol, n-butanol, sec-butanol, iso-butanol, tert-butanol, ethylene glycol, propylene glycol, 1,2-butanediol, 1 ,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5 pentanediol, propane-1 ,2,3-triol, 1 ,2,4 butanetriol, and combinations thereof.
• the concentration of the polymer electrolytes in the liquid medium is not particularly limited, and depends on a variety of factors that would be known to one of skill in the art, such as the type of solvent, the amounts used in the electrode catalyst, viscosity, permeability, etc. In one embodiment, the concentration of the polymer electrolytes is from about 0.1% to about 20%, and alternatively is from about 0.5% to 10%, wherein the % represents the weight of the polymer electrolytes as a percentage of the weight of the composition.
• a further aspect of the present invention provides a membrane electrode assembly (MEA) comprising the guanidine base, functionalized polymer membrane and dispersion according to the present invention and a method for preparing such a membrane electrode assembly.
• MEA membrane electrode assembly
• a catalyst ink can be made from the polymer electrolyte dispersion and catalyst.
• the term "catalyst” will be well understood by a person skilled in the art by meaning a catalyst that when incorporated into the electrode, facilitates an electrochemical reaction.
• the catalyst may be selected from platinum, palladium, rhodium, ruthenium, iridium, iron, cerium, titanium, vanadium, osmium, gold, silver, nickel, cobalt, manganese, or alternatively may be a base metal or base metal oxide, pyrolyzed (or unpyrolyzed) macrocyles, spinel, pyrochlores, perovskite-type oxides, or an alloy or mixture comprising one or more of these metals preferably supported on a conductive substrate, such as carbon.
• a conductive substrate such as carbon.
• Various from of carbon such as particulate carbon, carbon nanotubes, nanotube/perovskite composites can be used as electrode materials.
• the polymer electrolyte dispersion is typically prepared by dispersing the anion exchange membrane which can be processed to make electrodes, which in turn allow fabrication of durable membrane electrode assemblies (MEAs) by using fabrication methods described, e.g., in U.S. Patent 5,998,057 (Koschany et al.) and U.S. Patent Application 2010/0183804 (Kim et al.).
• Other known method such as direct painting of catalyst ink onto a membrane, decal transfer, spray painting, screen printing, roll coating, hot pressing etc. as would be known to one of skill in the art also may be used.
• Using these fabrication methods a highly stable and durable interface between the membrane and electrode can be obtained without using a cross-linking reaction.
• EW equivalent weight
• a perfluorinated polymer precursor (film thickness: 25 ⁇ , carboxylic acid form, EW1 100) was treated with tetrabutylammonium hydroxide (TBAOH) solution at room temperature for 24hr.
• the perfluorinated polymer precursor (TBA + form) was treated with 4- fluoroaniline in dimethylformamide (DMF) solution at 130 °C for 24 hr.
• the result polymer was treated with 1,1,3,3-tetramethylguanidine in dimethylformamide (DMF) solution at 90 °C for 24 hr. After the polymer was dried under a vacuum oven at 75°C, the polymer was washed with NaOH(0.5M) solution and pure water at boiling temperature.
• Tetramethlguanidine functionalized perfluorinated polymers were further treated with dimethyl sulfate (DMS) in DMF at 90°C for 24 hr. Pentamethylguanidine functionalized perfluorinated polymer was obtained. Guanidine functionalized perfluorinated polymers was further treated with 1 M NaOH followed by washing with water.
• DMS dimethyl sulfate
• a perfluorinated polymer precursor (film thickness: 25 ⁇ , carboxylic acid form, EW1100) was treated with tetrabutylammonium hydroxide (TBAOH) solution at room temperature for 24hr.
• the perfluorinated polymer precursor (TBA + form) was treated with 4- fluoroaniline in dimethylformamide (DMF) solution at 130 °C for 24 hr.
• the result polymer was treated with 1,1,3,3-tetramethylguanidine in dimethylformamide (DMF) solution at 90 °C for 24 hr. After the polymer was dried under a vacuum oven at 75°C, the polymer was washed with NaOH(0.5M) solution and pure water at boiling temperature.
• Tetramethylguanidine functionalized perfluorinated polymer was further treated with allyl bromide in DMF at 90°C for 24 hr. Functionalized perfluorinated polymer was obtained. Guanidine functionalized perfluorinated polymers was further treated with 1 M NaOH followed by washing with water, Example 3.
• a perfluorinated polymer precursor (film thickness: 25 ⁇ , carboxylic acid form, EW1100) was treated with tetrabutylammonium hydroxide (TBAOH) solution at room temperature for 24hr.
• the perfluorinated polymer precursor (TBA + form) was treated with 4- chloro-l,2-phenylenediamine, triphenylphosphite, and LiCl in dimethylformamide (DMF) solution at 100°C for 5hr and 130 °C for 24 hr.
• the result polymer was treated with 1,1,3,3- tetramethylguanidine in dimethylformamide (DMF) solution at 90 °C for 24 hr. After the polymer was dried under a vacuum oven at 75°C, the polymer was washed with NaOH(0.5M) solution and pure water at boiling temperature.
• Tetramethlguanidine functionalized perfluorinated polymers were further treated with dimethyl sulfate (DMS) in DMF at 90°C for 24 hr. Pentamethylguanidine functionalized perfluorinated polymer was obtained. Guanidine functionalized perfluorinated polymers was further treated with 1 M NaOH followed by washing with water.
• DMS dimethyl sulfate
• a perfluorinated polymer precursor (film thickness: 25 ⁇ , carboxylic acid form,
• EW1100 was treated with tetrabutylammonium hydroxide (TBAOH) solution at room temperature for 24hr.
• TSAOH tetrabutylammonium hydroxide
• the perfluorinated polymer precursor (TBA + form) was treated with 4- chloro-l,2-phenylenediamine, triphenylphosphite, and LiCl in dimethylformamide (DMF) solution at 100°C for 5hr and 130 °C for 24 hr.
• the result polymer was treated with 1,1,3,3- tetramethylguanidine in dimethylformamide (DMF) solution at 90 °C for 24 hr. After the polymer was dried under a vacuum oven at 75°C, the polymer was washed with NaOH(0.5M) solution and pure water at boiling temperature.
• Tetramethylguanidine functionalized perfluorinated polymer was further treated with allyl bromide in DMF at 90°C for 24 hr. Functionalized perfluorinated polymer was obtained. Guanidine functionalized perfluorinated polymers from Example 6 was further treated with 1 M NaOH followed by washing with water.
• Comparative Example 1 Synthesis of guanidine base functionalized perfluorinated anion exchange polymer electrolytes without stabilizing spacer.
• DMF dimethylformamide
• Comparative Example 2 Synthesis of other base functionalized anion exchange membranes. Trimethylamine, triethylamine and l,4-diazabicyclo-[2,2,2]-octane (DABCO) functionalized anion exchange polymer electrolytes were prepared. The C peak of -CH 3 and -CH 2 N in triethylamine were observed at 9 and 45 ppm by 13 C NMR, respectively. The C peak of CH 2 N in DABCO was observed at 45 ppm by 13 C NMR. However after soaking these membranes in 1 M NaOH for 10 hr, membrane degradation was observed.
• DABCO l,4-diazabicyclo-[2,2,2]-octane
• Examples 5-11 describe the synthesis of guanidine base functionalized hydrocaron anion exchange polymer electrolytes.
• Fluorinated poly aromatic polymer was synthesized from decafluorobiphenyl and methyl hydroquinone.
• the synthesized polymer was brominated with N-bromosuccinimide and 2,2'- azobisisobutyronitrile.
• Brominated polymer was treated with pentamethylguanidine in dimethylformamide (DMF) solution at 90 °C for 24 hr.
• the membrane was dried under a vacuum plate at 75°C. The absorption by CN 3 and CH 3 was observed at 1620 cm "1 and 1400 by FT-IR respectively.
• Guanidine functionalized hydrocarbon polymers were further treated with 1 M NaOH for 4 hr at boiling temperature followed by washing with water.
• PSU Modified Polysulfone
• PSU was synthesized with 4-fluorobenzoyl chloride.
• PSU was dissolved in anhydrous THF.
• Butyllithium and 4-fluorobenzoly chloride were added into solution at -78°C.
• the modified PSU was reacted with TMG in DMF at 130°C.
• the membrane was dried under a vacuum plate at 75°C.
• Tetramethylguanidine functionalized PSU polymer was further treated with dimethyl sulfate (DMS) in DMF at 90oC for 24hr.
• DMS dimethyl sulfate
• the absorption by CN 3 and CH 3 was observed at 1620 cm "1 and 1400 by FT-IR respectively.
• Guanidine functionalized hydrocarbon polymers were further treated with 1 M NaOH for 4 hr at boiling temperature followed by washing with water.
• Example 7 Modified Polysulfone (PSU) was synthesized with 4-fluorobenzoyl chloride. PSU was dissolved in anhydrous THF. Butyllithium and 4-fluorobenzoly chloride were added into solution at -78°C. The modified PSU was reacted with TMG in DMF at 130°C. The membrane was dried under a vacuum plate at 75°C. Tetramethylguanidine functionalized PSU polymer was further treated with allyl bromide in DMF at 90°C for 24hr. The absorption by CN 3 and CH 3 was observed at 1620 cm "1 and 1400 by FT-IR respectively. Guanidine functionalized hydrocarbon polymers were further treated with 1 M NaOH for 4 hr at boiling temperature followed by washing with water.
• the fluorinated sulfone polymer was synthesized from decafluorobiphenyl and 4,4- sulfonydiphenol in dimethyl sulfoxide (DMSO) at 90°C.
• Modified fluorinated sulfone polymer was synthesized with 4-fluorobenzoyl chloride.
• the fluorinated sulfone polymer was dissolved in anhydrous THF.
• Butyllithium and 4-fluorobenzoly chloride were added into solution at -78°C.
• the modified fluorinated sulfone polymer was reacted with TMG in DMF at 130°C.
• Tetramethylguanidine functionalized fluorinated sulfone polymer was further treated with dimethyl sulfate (DMS) in DMF at 90°C for 24hr. Guanidine functionalized hydrocarbon polymers were further treated with 1 M NaOH for 4 hr at boiling temperature followed by washing with water.
• DMS dimethyl sulfate
• the fluorinated sulfone polymer was synthesized from decafluorobiphenyl and 4,4- sulfonydiphenol in dimethyl sulfoxide (DMSO) at 90°C.
• Modified fluorinated sulfone polymer was synthesized with 4-fluorobenzoyl chloride.
• the fluorinated sulfone polymer was dissolved in anhydrous THF.
• Butyllithium and 4-fluorobenzoly chloride were added into solution at -78°C.
• the modified fluorinated sulfone polymer was reacted with TMG in DMF at 130°C.
• Tetramethylguanidine functionalized fluorinated sulfone polymer was further treated with allyl bromide in DMF at 90°C for 24hr. Guanidine functionalized hydrocarbon polymers were further treated with 1 M NaOH for 4 hr at boiling temperature followed by washing with water.
• Example 10 Tetramethylguanidine functionalized fluorinated sulfone polymer was further treated with allyl bromide in DMF at 90°C for 24hr. Guanidine functionalized hydrocarbon polymers were further treated with 1 M NaOH for 4 hr at boiling temperature followed by washing with water.
• the poly(arylene ether sulfone) polymer containing activated fluorine group was synthesized from difluorodiphenylsulfone and l,l-bis(4-hydroxyphenyl)-l-(4-((4-fluorophenyl) thio) phenyl- 2,2,2-trifluoroethane)(3FBPT monomer synthesized from 4-fluoro-2,2,2-trifluoroacetophenone (F3FAP), 4-fluorothiophenol (FTP), and phenol).
• F3FAP 4-fluoro-2,2,2-trifluoroacetophenone
• FTP 4-fluorothiophenol
• phenol 4-fluorothiophenol
• Tetramethylguanidine functionalized fluorinated sulfone polymer was further treated with dimethyl sulfate (DMS) in DMF at 90°C for 24hr. Guanidine functionalized hydrocarbon polymers were further treated with 1 M NaOH for 4 hr at boiling temperature followed by washing with water.
• DMS dimethyl sulfate
• the poly(arylene ether sulfone) polymer containing activated fluorine group was synthesized from difluorodiphenylsulfone and l,l-bis(4-hydroxyphenyl)-l-(4-((4-fluorophenyl) thio) phenyl- 2,2,2-trifluoroethane)(3FBPT monomer synthesized from 4-fluoro-2,2,2-trifluoroacetophenone (F3FAP), 4-fluorothiophenol (FTP), and phenol).
• F3FAP 4-fluoro-2,2,2-trifluoroacetophenone
• FTP 4-fluorothiophenol
• phenol 4-fluorothiophenol
• Tetramethylguanidine functionalized fluorinated sulfone polymer from was further treated with allyl bromide in DMF at 90°C for 24hr.
• Guanidine functionalized hydrocarbon polymers were further treated with 1 M NaOH for 4 hr at boiling temperature followed by washing with water.
• Table 1 shows the hydrolytic stability in 1 M NaOH of Examples 1-11 and Comparative

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