COMBINED MATERIAL SYSTEM FOR ION EXCHANGE MEMBRANES AND THEIR USE IN ELECTROCHEMICAL PROCESSES

Abstract

Described is a method for producing covalently and/or ionically cross-linked blend membranes from a halomethylated polymer, a polymer comprising tertiary N-basic groups, preferably polybenzimidazole, and, optionally, a polymer comprising cation exchanger groups such as sulfonic acid groups or phosphonic acid groups. The membranes can be tailor-made in respect of the properties thereof and are suitable, for example, for use as cation exchanger membranes or anion exchanger membranes in low-temperature fuel cells or low-temperature electrolysis or in redox flow batteries, orwhen doped with proton conductors such as phosphoric acid or phosphonic acidfor use in medium-temperature fuel cells or medium-temperature electrolysis.

Claims

1. Membrane characterized in that it is consisting of any mixing ratios from the polymeric membrane components: halomethylated polymer (polymer with CH.sub.2HaI groups, with HaIF, Cl, Br, I) polymer with cation exchange groups SO.sub.3X or PO.sub.3X.sub.2 (counterion arbitrary, preferred XH, metal cation, ammonium cation, imidazolium cation, pyridinium cation, etc.) polymer with tertiary N-basic groups and, if appropriate, any chemical compound or a mixture of chemical low- or high-molecular-weight compounds having tertiary N groups.

2. Membrane according to claim 1, characterized in that the halomethylated polymer(s) is (are) selected from arylene main chain polymers with CH.sub.2-HaI side groups the cation exchange polymer or polymers are selected from sulfonated polymers the tertiary N-basic polymers or polymers are selected from polyimidazoles, polybenzimidazoles, polyimides, polyoxazoles, polyoxadiazoles, polypyridines or aryl polymers having tertiary N-basic functional groups the tertiary N-basic compound(s) is (are) selected from tertiary amines (mono- and diamines) and/or N-monoalkylated and/or N-monoarylated imidazoles, N-monoalkylated or N-monoarylated benzimidazoles, monoalkylated or monoarylated pyrazoles.

3. Membrane according to claim 1, characterized in that the polymeric membrane component containing the cation exchange groups is present in molar excess and is thus a cationic conductor (cation exchange membrane CEM).

4. The membrane as claimed in claim 1, wherein the polymer membrane component containing the anion exchange groups is present in molar excess and is thus an anionic conductor (anion exchange membrane AEM).

5. The membrane as claimed in claim 1, wherein the polymeric membrane component containing N-basic groups is present in molar excess and is thus a proton conductor after doping with phosphoric acid, phosphonic acid, sulfuric acid or other 2- or 3-basic acids which can be used in the temperature range>100 C.

6. A process for producing membranes as claimed in claim 1, wherein all polymeric membrane components are mixed and homogenized in a common solvent, a membrane is sprayed, doctored or cast from the resulting solution, the solvent then evaporating at elevated temperatures, the membrane is thereafter detached from the support and finally treated by various methods in order to activate the membrane.

7. Process according to claim 6, characterized in that dipolar aprotic solvents such as N, N-dimethylacetamide, N-methylpyrrolidinone, N,N-dimethylformamide, dimethylsulfoxide, N-ethylpyrrolidinone, diphenylsulfone, sulfolane are used as solvents for dissolving the polymers.

8. The method as claimed in claim 6, wherein the following post-treatment process is used: (a) soaking in dilute mineral acid at T=room temperature (RT) to 100 C.; (B) soaking in deionized water at room temperature to 100 C.; (C1), if desired, soaking in concentrated phosphoric or phosphonic acid at T=RT up to 150 C. for the preparation of a doped intermediate temperature proton conductor (T=100-220 C.); or (C2), if desired, in dilute alkali metal hydroxide solutions, followed by immersion in demineralized water to produce the OH.sup. form of anion exchange membranes (AEM).

9. Use of the membranes according to claims 1 to 8 in membrane processes, especially in PEM low temperature fuel cells, PEM medium temperature fuel cells, PEM electrolysis, SO.sub.2-depolarized electrolysis, redox flow batteries, electrodialysis, diffusion dialysis, nanofiltration, ultrafiltration, reverse osmosis and pressure-retarded osmosis.

10. Use of the membranes as a component of sensors, electrodes, secondary batteries, fuel cells, alkaline fuel cells or membrane electrode assemblies.

Description

DESCRIPTION OF THE FIGURES

[0062] FIG. 1 depicts the reaction of a PBI with a halomethylated polymer.

[0063] FIG. 2 shows the reaction of a polymeric sulfinate with diiodobutane and DABCO

[0064] FIG. 3 shows the reaction of monomethylated PBIOO with diiodobutane and DABCO

[0065] FIG. 4 shows the reaction of monomethylated PBIOO with a polymeric sulfinate and with diiodobutane.

[0066] FIG. 5 shows the structure of the polymers used in Example 1.

[0067] FIG. 6 depicts the TGA curve of membrane MJK-1885.

[0068] FIG. 7 shows the conductivity as a function of the temperature of a H.sub.3PO.sub.4-doped 1885 membrane.

[0069] FIG. 8 shows the polymer blend components of membrane MJK-1959.

[0070] FIG. 9 shows the covalent and ionic crosslinking in the blinding membrane MJK 1959.

[0071] FIG. 10 shows the polymer blend components of membrane MJK-1932.

[0072] FIG. 11 shows the TGA curve of the membrane MJK-1932.

[0073] FIG. 12 shows the polymeric blend components of membrane MJK-1957.

[0074] FIG. 13 shows the polymer blend components of the NMM/DABCO quaternized membrane 54-PAK18r-60-F6PBI-SAC-15.

[0075] FIG. 14 depicts the degree of crosslinking as a function of the SAC content in the polymer solution for NMM-DABCO quaternized membranes from PAK18r-60-F6PBI

[0076] FIG. 15 shows the comparison of the chloride conductivities (1 M NaCl, RT) of the alkylimidazole-quenched PPO-PBIOO membranes and the commercial Tokuyama membrane A201 (development code A006).

[0077] FIG. 16 shows the TGA curves of alkylimidazole-quaternized membranes.

[0078] FIG. 17 shows the covalent and ionic cross-linking with the 40-PPO-50-F6PBI-SAC-5-NMM-TMEDA blend membrane

[0079] FIG. 18 shows the TGA curves of PPO-F6PBI membranes, which are (37) only covalently and covalent-ionically (40) cross-linked.

[0080] FIG. 19 shows the TGA curves of PPO-F6PBI ionically covalently cross-linked membranes, quaternized and crosslinked with NMM/DABCO.

[0081] FIG. 20 shows the TGA curves of PPO-F6PBI ionically covalently cross-linked membranes quaternized with NMM.

[0082] FIG. 21 shows the structure formula (repeat unit) of PBIOO and PVBCI.

APPLICATION EXAMPLES

Example 1: HIPEM from PBI, Halomethylated Polymer (Covalently Cross-Linked (Membrane MJK 1885)

[0083] 0.75 g of the polybenzimidazole F.sub.6PBI is used as a 4% solution in N, N-dimethylacetamide (DMAc) as a 10 wt % solution in DMAc with 0.321 g of bromomethylated polyphenylene oxide (PPOBr, degree of bromination 1.7 CH.sub.2Br per PPO repeat unit) (the chemical structure of the blend components is depicted in FIG. 5). After homogenization, a membrane is doctored on a glass plate from this solution, and the solvent is evaporated at 140 C. in a convection drying oven. The membrane is then removed under water and after-treated as follows: 48 hours of 10% HCl at 90 C., then 48 hours of deionized water at 60 C.

[0084] The membrane is then characterized as follows: [0085] Thermogravimetry (TGA) in 65% O.sub.2, the TGA curve of the membrane is presented in FIG. 6 [0086] extraction with DMAc at 90 C. (4 days).fwdarw.extraction residue (insolubles 88.9%) [0087] Fenton's test: after 96 hours in Fenton's reagent mass loss of 7.5% [0088] doping with 85% H.sub.3PO.sub.4 (259% doping degree), the conductivity curve is depicted in FIG. 7.

Example 2: HTPEM from P81, Halomethylated Polymer, Tertiary Amine, Sulfonated Polymer (Covalent-Ionically Cross-Linked) (MJK-1959)

[0089] 1.4 g of F.sub.6PBI are mixed as a 5% solution in DMAc with 0.3 g of PARBr1 as a 5% solution in DMAc and 0.3 g of the sulfonated polymer sPPSU as well as 0.488 g of 1-ethyl-2-methylimidazole (the polymer structures are shown in FIG. 8).

[0090] After homogenization, a membrane is doctored on a glass plate from this solution, and the solvent is stripped off at 140 C. in a convection drying oven. The membrane is then peeled off under water and after-treated as follows: 48 hours of 10% HCl at 90 C., then 48 hours of deionized water at 60 C. FIG. 9 shows the blend of the PBI with the quaternized polymer. Reaction of a small part of the CH.sub.2Br groups with the imidazole-NH under alkylation produces covalent crosslinking bridges. The membrane is then characterized as follows: [0091] Thermogravimetry (TGA) in 65% O.sub.2 [0092] extraction with DMAc at 90 C. (4 days).fwdarw.extraction residue (insoluble parts %) [0093] Fenton's test: after 96 hours in Fenton's reagent mass loss of %

[0094] Doping with 85% H.sub.3PO.sub.4 (259% doping degree), the conductivity curve is presented in FIG. 7.

Example 3: AEM from PBI, Halomethylated Polymer, Tertiary Amine, Sulfonated Polymer (Covalent-Ionically Cross-Linked) (Membrane MJK-1932)

[0095] 0.5 g of F.sub.6PBI are mixed as a 5% solution in DMAc with 0.5 g of PPOBr as a 5% solution in DMAc and 0.107 g of the sulfonated polymer sPPSU and 1.08 ml of the tertiary amine N-methylmorpholine (the polymers of the blending componentsare depicted in FIG. 10).

[0096] After homogenization, a membrane is doctored on a glass plate from this solution, and the solvent is stripped off at 140 C. in a convection drying oven. The membrane is then removed under water and after-treated as follows: 48 hours of 10% HCl at 90 C., then 48 hours of deionized water at 60 C. Reaction of a small part of the CH.sub.2Br groups with the imidazole-NH under alkylation produces covalent crosslinking bridges.

[0097] The membrane is then characterized as follows: [0098] Thermogravimetry (TGA) in 65% O.sub.2 (the TGA curve is shown in FIG. 11) [0099] extraction with DMAc at 90 C. (4 days).fwdarw.extraction residue (insoluble parts 93.9%)

[0100] Thickness 105 m [0101] chloride conductivity (RT, 1 M NaCl): 4.88 mS/cm [0102] IEC: 2.8 mmol/g [0103] Chemical stability (90 C., 1 M KOH) [0104] IEC (after 5 d): 84.6% of the original value [0105] IEC (after 10 d): 74.3% of the original value [0106] Conductivity: (after 5 d): 56.1% of the original value.

Example 4: CEM from Sulfonated Polymer, PBI, Halomethylated Polymer, Tertiary Amine (Covalent-Ionically Cross-Linked) (Membrane MJK-1957)

[0107] 0.12 g of F.sub.6PBI are mixed as a 5% solution in DMAc with 0.12 g of PARBr1 as a 5% solution in DMAc and 2 g of the sulfonated polymer sPPSU and 0.195 g of 1-ethyl-2-methylimidazole (the polymers of the blending components are shown in FIG. 12).

[0108] After homogenization, a membrane is doctored on a glass plate from this solution, and the solvent is stripped off at 140 C. in a convection drying oven. The membrane is subsequently removed under water and treated as follows: 48 hours of 10% HCl at 90 C., then 48 hours of demineralized water at 60 C. Covalent cross-linking bridges are formed by reaction of a small part of the CH.sub.2Br groups with the imidazole NH via alkylation.

[0109] The membrane is then characterized as follows: [0110] Thermogravimetry (TGA) in 65% O.sub.2 [0111] extraction with DMAc at 90 C. (4 days).fwdarw.extraction residue (insoluble parts in %) [0112] Fenton's test: after 96 hours in Fenton's reagent mass loss in % [0113] impedance (resistance) [0114] Water absorption at 90 C.

Example 5 AEM from Sulfonated Polymer, PBI, Halomethylated Polymer, Tertiary Amine (Covalent-Ionically Cross-Linked)

[0115] 0.8 g of F.sub.6PBI are mixed as a 5% solution in DMAc with 1.2 g of PARBr1 as a 5% solution in DMAc and 0.12 g of the sulfonated polymer sPPSU and 1.95 g of 1-ethyl-2-methylimidazole (the polymer blend components are depicted in FIG. 13).

[0116] After homogenization, a membrane is doctored on a glass plate from this solution, and the solvent is stripped off at 140 C. in a forced-air drying cabinet. The membrane is then removed under water and after-treated as follows: 48 hours of 10% HCl at 90 C., then 48 hours of deionized water at 60 C. Reaction of a small part of the CH.sub.2Br groups with the imidazole-NH under alkylation produces covalent crosslinking bridges.

[0117] The membrane is then characterized as follows: [0118] Thermogravimetry (TGA) in 65% O.sub.2 [0119] extraction with DMAc at 90 C. (4 days).fwdarw.extraction residue (insoluble parts in %) [0120] Fenton's test: after 96 hours in Fenton's reagent mass loss in % [0121] impedance (resistance) [0122] Water absorption at 90 C.

Example 6 AEM from Sulfonated Polymer, F.SUB.6.PBI, Halomethylated/Partially Fluorinated Polymer, Tertiary Mono- and Diamine (Covalent-Ionically Cross-Linked)

[0123] 0.162 g of F.sub.6PBI are mixed as a 5% solution in DMAc with 0.243 g of PAK 18r as a 5% solution in DMAc and 0.081 g of the sulfonated polymer sPPSU and 0.45 ml of the tertiary monoamine N-methylmorpholine (polymeric acid base blends).

[0124] After homogenization, a membrane is poured from this solution into a petri dish, and the solvent is stripped off at 80 C. in a forced-air drying cabinet. Subsequently, the membrane is removed under water and treated as follows: 48 hours in a mixture of 50/50 DABCO/EtOH at 80 C., then 48 hours in deionised water at 90 C. Reaction of a small part of the CH.sub.2Br groups with the imidazole-NH under alkylation produces covalent crosslinking bridges. The membrane is further covalently cross-linked by the diamine.

TABLE-US-00003 TABLE 2 Characterization parameters of the membrane 54-PAK18r-60-F.sub.6PBI-SAC-15-NMM-DABCO 54-PAK18r-60-F.sub.6PBI-SAC- Membrane 15-NMM-DABCO IEC value, mmol/g: 2.0 thickness, m: 60 Cl.sup.- (1 M, NaCl), mS/cm: 10.1 Alkaline stability, % of the 92.8 original value: (Cl.sup.- after 5 d in 1 M KOH 90 C.) Extraction with DMAc. wt.-% 96.3 (insoluble share, after 4 d at 80 C.) Water uptake (30 C.), wt.-% 66.9

[0125] FIG. 14 shows the cross-linking degree in in dependence of the share of SAC in the polymer solution for membranes quaternized with NMM-DABCO from PAK18r-60-F.sub.6PBI.

Example 7: AEMs from PBIOO, Halomethylated Polymer, Alkylimidazole (Covalently Cross-Linked)

63-PPO-40-PBIOO-Melm

[0126] 0.15 g of F.sub.6PBI are mixed as a 5% solution in DMAc with 0.10 g of PPOBr as a 5% solution in DMAc and 0.26 ml of the imidazole compound 1-methylimidazole (polymer blends)

[0127] 64-PPO-50-PBIOO-Melm:

[0128] 0.125 g of F.sub.6PBI are mixed as a 5% solution in DMAc with 0.125 g of PPOBr as a 5% solution in DMAc and 0.33 ml of the imidazole compound 1-methylimidazole (polymer blends)

[0129] 67-PPO-50-PBIOO-EtMelm:

[0130] 0.125 g of F.sub.6PBI are mixed as a 5% solution in DMAc with 0.125 g of PPOBr as a 5% solution in DMAc and 0.47 ml of the imidazole compound 1-ethyl-2-methylimidazole (polymer blends)

[0131] After homogenization, a membrane is poured onto a petri dish from the polymer solution, and the solvent is stripped off at 80 C. in a circulating air drying cabinet. Subsequently, the membranes are removed under water and rinsed in demineralised water at 90 C. for 48 hours. Reaction of a small part of the CH.sub.2Br groups with the imidazole-NH under alkylation produces covalent crosslinking bridges. The membranes are characterized as follows:

TABLE-US-00004 TABLE 3 Characterization parameters of the alkylimidazole-quaternized PPO-PBIOO membranes 63-PPO- 64-PPO- 67-PPO- 40-PBIOO- 50-PBIOO- 50-PBIOO- Membrane Melm Melm EtMelm IEC value, mmol/g: 4.5 4.1 3.5 thickness, m: 35 33 45 Cl.sup.- (1 M, NaCl), mS/cm: 6.4 16.9 15.1 Alkaline stability, % of the original value: 45.3 50.4 26.8 (Cl.sup.- after 5 d in 1 M KOH 90 C.) Cl.sup.- (90% RF, 30 C.), mS/cm: n. a. 4.8 4.5 Extraction with DMAc. wt.-% 86.1 94.1 96.7 (insoluble share, after 4 d at 80 C.) Water uptake (30 C.), wt.-% 46.4 60.4 56.9

[0132] FIG. 15 shows the comparison of the chloride conductivities (1 M NaCl, RT) of the PPO-PBIOO membranes quenched with alkylimidazole and Tokuyama's commercial A201 (development code A006). Thermogravimetry (TGA) in 65% O.sub.2 (the TGA traces of the membranes in application example 7 are depicted in FIG. 16).

Example 8: AEMs from (Sulfonated Polymer) F.SUB.6.PBI, Halomethylated Polymer, Tertiary Mono- and Diamine (Covalently and or Ionically Cross-Linked (FIG. 17 Shows the Covalent and the Ionic Cross-Linking at the Blend Membrane 40-PPO-50-F.SUB.6.PBI-SAC-5-NMM-TMEDA)

[0133] 37-PPO-50-F.sub.6PBI-NMM-TMEDA:

[0134] 0.2025 g of F.sub.6PBI are mixed as a 5% solution in DMAc with 0.2025 g of PPOBr as a 5% solution in DMAc and 0.44 ml of the tertiary monoamine N-methylmorpholine (covalently cross-linked polymer blends).

[0135] After homogenization, a membrane is poured from the solution onto a petri dish, and the solvent is stripped off at 80 C. in a re-circulated drying cabinet. Subsequently, the membrane is removed under water and after-treated as follows: 48 hours in TMEDA (1 d RT, 1 d 50 C.), then 48 hours in demineralized water at 90 C. Reaction of a small part of the CH.sub.2Br groups with the imidazole-NH under alkylation produces covalent crosslinking bridges. The membrane is further covalently cross-linked by the diamine.

[0136] 40-PPO-50-F.sub.6PBI-SAC-5-NMM-TMEDA:

[0137] 0.2025 g of F.sub.6PBI is added as a 5% solution in DMAc with 0.2025 g of PPOBr as a 5% solution in DMAc and 0.02025 g of the sulfonated polymer as a 5% solution in DMAc and 0.59 ml of the tertiary monoamine N-methylmorpholine (covalently cross-linked polymer blends)

[0138] After homogenization, a membrane is poured from the solution onto a petri dish, and the solvent is stripped off at 80 C. in a re-circulated drying cabinet. Subsequently, the membrane is stripped under water and treated as follows: 48 hours in TMEDA (1 d RT, 1 d 50 C., then 48 hours in demineralised water at 60 C. By reaction of a small part of the CH.sub.2Br groups with the imidazole NH under alkylation, covalent crosslinking bridges are formed.

TABLE-US-00005 TABLE 5 Characterization parameters of PPO-F.sub.6PBI membranes which are (37) crosslinked only covalently and covalently-ionically (40) 37-PPO-50- 40-PPO-50-F.sub.6PBI- F.sub.6PBI-NMM- SAC-5-NMM- Membrane TMEDA TMEDA IEC value, mmol/g: n.a. n.a. Thickness, m: 45 40 Cl.sup.- (1 M, NaCl), mS/cm: 12 5.3 Alkaline stability, % of the 41.6 82.3 original value: (Cl.sup.- after 5 d in 1 M KOH 90 C.) Extraction with DMAc, wt.-% k.A. k.A. (insoluble share, after 4 d at 80 C.) Water uptake (30 C.), wt.-% 46.1 47.2

[0139] The TGA traces of the membranes in 65% O.sub.2 are presented in FIG. 18.

Example 9: AEMs from Sulfonated Polymer, F.SUB.6.PBI, Halomethylated Polymer, Tertiary Mono- and Diamine (Covalently Ionically Cross-Linked)->44, 45, 46

[0140] 0.2025 g of F.sub.6PBI are added as a 5% solution in DMAc with 0.2025 g of PPOBr as a 5% solution in DMAc and, depending on the membrane, with 0.02025 g of SAC (44-PPO-50-F6PBI-SAC-5-NMM DABCO), 0.0405 g SAC (45-PPO-50-F6PBI-SAC-10-NMM-DABCO) or 0.06075 g SAC (46-PPO-50-F6PBI-SAC-15-NMM-DABCO) 5% solution in DMAc and 0.59 ml of the tertiary monoamine N-methylmorpholine (ionic-covalently cross-linked acid-base blends).

TABLE-US-00006 TABLE 6 Characterization parameters of the acid-base blends from PPO-F.sub.6PBI, quaternized and crosslinked with NMM/DABCO 44-PPO-50- 45-PPO-50- 46-PPO-50-F.sub.6PBI- F.sub.6PBI-SAC-5- F.sub.6PBI-SAC-10- SAC-15-NMM- Membrane NMM-DABCO NMM-DABCO DABCO IEC value, mmol/g: 2.5 2.5 2.6 Thickness, m: 85 55 50 Cl.sup.- (1 M, NaCl), mS/cm: 61.4 54.7 21.9 Alkaline stability, % of 78.4 38.6 k.A. the original value: (Cl.sup.- after 5 d in 1 M KOH 90 C.) (Cl.sup.- (90% RF, 30 C.), mS/cm: n.a. n.a. n.a. Extraction with DMAc, 79.8 88.3 88.1 wt.-% (insoluble share, after 4 d at 80 C.) Water uptake (30 C.), wt.-% 159.3 133.9 107.5

[0141] The TGA traces of the membranes in 65% O.sub.2 are presented in FIG. 19.

Example 10: AEMs from Sulfonated Polymer, F.SUB.6.PBI, Halomethylated Polymer, Tertiary Monoamine (Covalently Ionically Cross-Linked)->71, 72, 73, 74, 75

[0142] 0.2025 g of F.sub.6PBI are added as a 5% solution in DMAc with 0.2025 g of PPOBr as a 5% solution in DMAc and, depending on the membrane, with 0.02025 g of SAC (71-PPO-50-F.sub.6PBI-SAC-5-NMM), 0.0805 g SAC (72-PPO-50-F.sub.6PBI-SAC-10-NMM), 0.0605 g SAC PPO-50-F.sub.6PBI-SAC-20-NMM), or 0.5 g of the tertiary monoamine N-methylmorpholine (ionical-covalently crosslinked acid base-blends) After homogenization, a membrane is poured from the solution onto a petri dish, and the solvent is stripped off at 80 C. in a re-circulated drying cabinet. Subsequently, the membrane is stripped under water and treated as follows: 48 hours in 15% NMM in EtOH (1 d RT, 1 d 50 C.), then 48 hours in demineralised water at 90 C. Reaction of a small part of the CH.sub.2Br groups with the imidazole-NH under alkylation produces covalent crosslinking bridges. The oxygen atom belonging to the morpholine also contributes to further chain-crossing hydrogen bonds within the membrane.

TABLE-US-00007 TABLE 7 Characterization parameters of the acid-base blends from PPO-F.sub.6PBI, quaternized with NMM 71-PPO- 72-PPO- 73-PPO- 74-PPO- 50-F.sub.6PBI- 50-F.sub.6PBI- 50-F.sub.6PB1- 50-F.sub.6PBI- 75-PPO- SAC-5- SAC-10- SAC-15- SAC-20- 50-F.sub.6PBI- Membrane NMM NMM NMM NMM NMM IEC value, mmol/g: n.a. n.a. n.a. n.a. n.a. Thickness, m: 50 47 37 40 70 Cl.sup.- (1 M, NaCl), mS/cm: 16.9 11.5 2.5 1.8 18.9 Alkaline stability, % of the 50.5 56.9 86.9 99.0 k.A. original value: (Cl.sup.- after 5 d in 1 M KOH 90 C.) Cl.sup.- (90% RF, 30 C.), mS/cm: 5.2 n.a. n.a n.a. 6.5 Extraction with DMAc. wt.-% 100 100 99.1 93.5 n.a. (insoluble share, after 4 d at 80 C. Water uptake (30 C.), wt.-% 54.0 58.7 39.4 39.0 n.a.

[0143] The TGA traces of the membranes in 65% O.sub.2 are presented in FIG. 20.

Example 11: AEMs from Different Blend Components

[0144] Table 8 shows the compositions of various AEM blends, and Table 9 shows some of their properties.

TABLE-US-00008 TABLE 8 Overview of some AEM blend types Halomethylated Sulfonated polymer PBI polymer Type and Type and Type and Membrane amount amount amount Used tertiary [No.] [g] [g] [g] N-Base MCMA2 PPOBr.sup.1, 0.2025 F.sub.6PBI.sup.1, 0.2025 sPPSU.sup.2, 0.02025 N-methylmorpholine MCMB3 PARBr1.sup.2, 0.243 F.sub.6PBI.sup.1, 0.162 sPPSU.sup.2, 0.02025 N-methylmorpholine MCMC2 PPOBr.sup.1, 0.100 PBIOO.sup.3, 0.150 1-methylimidazole MCMD3 PPOBr.sup.1, 0.125 PBIOO.sup.3, 0.125 1-ethyl-2-methylimidazole MCME1 PPOBr, 0.243 F.sub.6PBI.sup.1, 0.162 sPPSU.sup.2, 0.02025 1-methylimidazole MRP80 PPOBr.sup.1, 0.200 F.sub.6PBI.sup.1, 0.133 sPPSU.sup.2, 0.01675 1-ethyl-2- methylimidazole MRP81 PPOBr.sup.1, 0.200 F.sub.6PBI.sup.1, 0.133 sPPSU.sup.2, 0.01675 1,2-dimethylimidazole MRP83 PPOBr.sup.1, 0.200 F.sub.6PBI.sup.1, 0.133 sPPSU.sup.2, 0.01675 1-butyl-2- methylimidazole MJK2025 PVBCl.sup.3, 0.500 F.sub.6PBI.sup.1, 0.400 sPPSU.sup.2, 0.032 1,2-dimethylimidazole MJK2026 PVBCl.sup.3, 0.500 F.sub.6PBI.sup.1, 0.400 1,2-dimethylimidazole Tokuyama Tertiary amine A201 (unknown) .sup.1Structural formula (repeat unit) of PPOBr and F.sub.6PBI is depicted in Figure 5 .sup.2Structural formula (repeat unit) of PARBr.sup.1 and sPPSU is depicted in Figure 8 .sup.3Structural formula (repeat unit) of PBIOO and PVBCl is depicted in Figure 21

TABLE-US-00009 TABLE 9 Some characterization results of these AEM blends .sub.Cl after Water KOH.sup.1 IEC uptake [% of Membrane [mmol at 30 C. .sub.Cl initial T.sub.onset.sup.2 [No.] OH.sup./g] [%] [mScm.sup.1] value] [ C.] MCMA2 1.8 47 17 62 273 MCMB3 2.5 67 10 58 232 MCMC2 4.5 46 6 36 245 MCMD3 3.3 57 15 41 289 MCME1 2.7 74 8 69 254 MRP80 2.46 56 (25 C.) 16 70.9 n.a. MRP81 2.5 51.5 (25 C.) 17 40.6 n.a. MRP83 2.4 51.8 (25 C.) 10 31.6 n.a. MJK2025 2.31 n.a. 34.1 32.8 n.a. MJK2026 2.59 n.a. 34 47.6 n.a. Tokuyama 1.7 19 2.4 21 166 A201 .sup.1value after storage in 1 molar KOH at 90 C. for 10 days (240 hours) .sup.2Start of decomposition of the polymer (determined by TGA-FTIR coupling)

[0145] It can be clearly seen from Table 9 that all the AEM blend membranes studied have better chemical stability both after the KOH immersion and in the TGA experiment than the commercial benchmark membrane Tokuyama A201.

[0146] Due to their excellent properties, conductivity and long-term stability in alkaline media, the membranes are particularly suitable for sensors, especially ion-selective sensors and ion-selective applications, and for alkaline fuel cells.

REFERENCES

[0147] .sup.1Wainright, J. S.; Wang, J. T.; Savinell, R. F.; Litt, M. J. Electrochem. Soc. 142, L121-L123 (1995) [0148] .sup.2Kreuer, K. D.; Paddison, S.; Spohr, E.; Schuster, M. Chem. Rev. 104, 4637-4678 (2004) [0149] .sup.3Yu, S.; Xiao, L.; Benicewicz, B. C. Fuel Cells 8, 165-174 (2008) [0150] .sup.4Liao, J.; Li, Q.; Rudbeck, H. C.; Jensen, J. O.; Chromik, A.; Bjerrum, N. J.; Kerres, J.; Xing, W. Fuel Cells 11, 745-755 (2011) [0151] .sup.5Kerres, J.; Ullrich, A.; Meier, F.; Hring, T. Solid State Ionics 125, 243-249 (1999) [0152] .sup.6Kerres, J.; Schnberger, F.; Chromik, A.; Hring, T.; Li, Q.; Jensen, J. O.; Pan, C.; Noy, P.; Bjerrum N. J. Fuel Cells 8, 175-187 (2008) [0153] .sup.7Atanasov, V.; Kerres, J. Macromolecules 44, 6416-6423 (2011) [0154] .sup.8Highly phosphonated polypentafluorostyrene: characterization and blends with polybenzimidazole. Atanasov, V.; Gudat, D.; Ruffmann, B.; Kerres, J. Eur. Poly, J., 2013, 49, 3977-3985 [0155] .sup.9Wang, S.; Zhang, G.; Han, M.; Li, H.; Zhang, Y.; Ni, J.; Ma, W.; Li, M.; Wang, J.; Liu, Z.; Zhang, L.; Na, H. Int. J. Hydrogen En. 36, 8412-8421 (2011) [0156] .sup.10Aili, D.; Li, Q.; Christensen, E.; Jensen, J. O.; Bjerrum, N. J. Polym. Int. 60, 1201-1207 (2011) [0157] .sup.11Yang, J.; Li, Q.; Cleemann, L. N.; Jensen, J. O.; Pan, C.; Bjerrum, N. J., He, R. Adv. En. Mater. 3, 622-630 (2013) [0158] .sup.12Wang, S.; Zhao, C.; Ma, W.; Zhang, N.; Liu, Z.; Zhang, G.; Na, H. J. Power Sources 243, 102-109 (2013) [0159] .sup.13Plackett, D.; Siu, A.; Li, Q.; Pa, C.; Jensen, J. O.; Nielsen, S. F.; Permyakova, A. A.; Bjerrum N. J. J. Memb. Sci. 383, 78-87 (2011) [0160] .sup.14Jones, D. J.; Roziere, J. J. Memb. Sci. 185, 41-58 (2001) [0161] .sup.15Peron, J.; Ruiz, E.; Jones, D.; Roziere, J. J. Memb. Sci. 314, 247-256 (2008) [0162] .sup.16Sukumar, P. R.; Wu, W.; Markova, D.; nsal, b.; Klapper, M.; Mllen, K. Macromol. Chem., Phys. 208, 2258-2267 (2007) [0163] .sup.17Sinigersky, V.; Budurova, D.; Penchev, H.; Ublekov, F.; Radev, I. J. Appl. Polym. Sci. 129, 1223-1231 (2013) [0164] .sup.18Kerres, J.; Ullrich, A.; Hring, T. Engineering ionorneric blends and engineering ionomeric blend membranes, U.S. Pat. No. 6,723,757B1, Apr. 20, 2004 [0165] .sup.19Wright, A.; Thomas, O.; Holdcroft, S. Anion-conducting polymer, WO2013149328 (PCT/CA2013/000323) Priority date 4 Apr. 2012 [0166] .sup.20Thomas, O. D.; Soo, K. J. W. Y.; Peckham, T. J.; Kulkami, M. P.; Holdcroft, S. J. Am. Chem. Soc. 134 (2012) 10753-10756 [0167] .sup.21Yanagi, H.; Fukuta, K. ECS Trans. 2008 16(2), S. 257-262 (2008) [0168] .sup.22Yang, C.-C. Materials Science and Engineering: B 131 (1-3), S. 256-262 (2006) [0169] .sup.23Patent: European Patent 1 612 874 A1, El Moussaoui, Rachid; Martin, Roland. applicant: SOLVAY (Socit Anonyme) 1050 Brssel (2006) [0170] .sup.24Varcoe, J. R. Physical Chemistry Chemical Physics 9, S. 1479-1486 (2007) [0171] .sup.25Wu, L.; Xu, T. J Membr Sci; 322:286-92 (2008) [0172] .sup.26Hibbs, M. R.; Fujimoto, C. H.; Cornelius, C. J. Macromolecules 42, S. 8316-8321 (2009) [0173] .sup.27Robertson, Nicholas J.; Kostalik I V, Henry A.; Clark, Timothy J.; Mutolo, Paul F.; Abrua, Hctor D.; Coates, Geoffrey W. (2010): Tunable high performance cross-linked alkaline anion exchange membranes for fuel cell applications. In: Journal of the American Chemical Society 132, S. 3400-3404. DOI: 10.1021/ja908638d8 [0174] .sup.28Kostalik, H. A.; Clark, T. J.; Robertson, N.J.; Mutolo, P. F.; Longo, J. M.; Abrua, H. c. D; Coates, G. W. Macromolecules 43, S. 7147-7150 (2010) [0175] .sup.29Wang, J.; Li, S.; Zhang, S. Macromolecules 43, S. 3890-3896 (2010). [0176] .sup.30Tanaka, M.; Masaki K.; Miyatake, K.; Watanabe, M. Macromolecules 43, S. 2657-2659 (2010). [0177] .sup.31Tanaka, M.; Fukasawa, K.; Nishino, E.; Yamaguchi, S.; Yamada, K.; Tanaka, H.; Bae, B.; Miyatake, K.; Watanabe, M. J. Am. Chem. Soc. 133, S. 10646-10654 (2011) [0178] .sup.32Zhao, Z.; Wang, J.; Li, S-; Zhang, S. Journal of Power Sources 196 (10), S. 4445-4450 (2011) [0179] .sup.33Faraj, M.; Elia, E.; Boccia, M.; Filpi, A.; Pucci, A.; Ciardelli, F. Journal of Polymer Science Part A: Polymer Chemistry, 49, S. 3437-3447 (2011) [0180] .sup.34Ran, J.; Wu, L.; Varcoe, J. R.; Ong, A. L.; Poynton, S. D.; Xu, T. Journal of Membrane Science 415-416, S. 242-249 (2012) [0181] .sup.35Lin, X.; Wu, L.; Liu, Y.; Ong, A. L.; Poynton, S. D.; Varcoe, J. R.; Xu, T. Journal of Power Sources 217, S. 373-380 (2012) [0182] .sup.36Wang, J.; He, G.; Wu, X.; Yan, X.; Zhang, Y.; Wang, Y.; Du, L. Journal of Membrane Science 459, S. 86-95 (2014) [0183] .sup.37Yan, X.; Gu, S.; He, G.; Wu, X.; Zheng, W.; Ruan, X. Journal of Membrane Science 466, S. 220-228 (2014)