EP3155674A2

EP3155674A2 - Combinatorial material system for ion exchange membranes, and use of said material system in electrochemical processes

Info

Publication number: EP3155674A2
Application number: EP15763190.4A
Authority: EP
Inventors: Jochen Kerres; Carlo Morandi
Original assignee: Institut fuer Chemische Verfahrenstechnik Universitaet Stuttgart
Current assignee: HAERING, THOMAS; Institut fuer Chemische Verfahrenstechnik Universitaet Stuttgart
Priority date: 2014-06-12
Filing date: 2015-06-12
Publication date: 2017-04-19
Also published as: WO2015188806A3; WO2015188806A2; JP2017528579A; DE102014009170A1; US20170114196A1

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, or - when doped with proton conductors such as phosphoric acid or phosphonic acid - for use in medium-temperature fuel cells or medium-temperature electrolysis.

Description

Combinatorial material system for

Ion exchange membranes and its

Use in electrochemical processes

Summary

Multi-use embranen (use as AEM, H ₃ P0 ₄ -doped HT membranes, HT-HyS electrolysis membranes, membranes as separators for redox-flow batteries)

Mixture of a halomethylated polymer with a basic polymer (eg PBI: F ₆ PBI or PBIOO) in a dipolar aprotic solvent such as DMSO or DMAc, NM P, etc. Covalent crosslinking by heating to 80-180 ° C for 2- 24 hours (1 or 2 sided imidazolation)

Optional subsequent sulfonation of the polymer films by incorporation in 60-90% H ₂ S0 ₄ at T = 25-180 ° C for 0.5-24 hours (see sulfuric acid-treated HyS electrolysis membranes) -> arise both ionic and also covalently crosslinked blend membranes) mixture of a partially phosphonated polymer (neutralized with amine) (with a polybenzimidazole PBI) (preferably PBIOO, ABPBI, F ₆ PBI or Celazol® / Hozol ^®), addition of a bisphenol or Bisthiophenols (z. B. 4 , 4'-diphenol or TBBT and further addition of an amine to bis (thio) phenol completely neutralized (color change of the solution), squeezing the solution and evaporating solvent at 90-170 ° C, followed by l-24h heating at 100-200 ° C, for the covalent crosslinking of F by thiolate or phenolate groups (nucleophilic substitution)

Mixture of a halomethylated polymer with a PBI (preferably ABPBI, F ₆ PBI or PBIOO) in DMAc, cooling to 0-5 ° C., addition of any tertiary amine (eg TEA, DABCO, ABCO), rapid homogenization and knife coating, Evaporation at 60-150 ° C, post-treatment in sulfuric acid (60-90% H ₂ S0 ₄ ), washing the film -> covalently ionically cross-linked acid-base blend membrane

Mixture of a halomethylated polymer with a PBI (F ₆ PBI or PBIOO) in DMAc, cooling to -20 to + 5 ° C., addition of an amine (eg TEA, DABCO, ABCO) and a diiodoalkane, rapid homogenization and knife coating, Evaporation at 90-130 ° C, post-treatment in sulfuric acid (60-90% H ₂ S0 ₄ ), washing the film -> covalently ionically cross-linked acid-base blend membrane

Mixture of a halomethylated polymer with a PBI (F ₆ PBI or PBIOO) in DMAc, cooling to 0-5 ° C, addition of a sulfonated polymer and a monoamine (NMM), rapid homogenization and knife coating or pouring, evaporation at 80-150 ° C. , Aftertreatment in diamine (TM EDA, DABCO) or in monoamine (NMM) at RT-100 ° C, washing of the film -> covalently ionically cross-linked acid-base blend membranes.

Mixture of a halomethylated polymer with a PBI (F ₆ PBI or PBIOO) in DMAc, cooling to 0-5 ° C, admixture (of a sulfonated polymer and) of an N-alkylated or arylated (benz) imidazole (Melm or EtMelm), fast Homogenization and Squeegee or pour, evaporate at 80-150 ° C, wash the film covalently ionically cross-linked acid-base blends.

State of the art

Phosphoric acid-doped polybenzimidazole (PBI) for use in fuel cells is the work of Savinell et al. back ¹ . The advantage of the PBI / H ₃ P0 ₄ composite membranes is that instead of water, the phosphoric acid takes over the H ^{+ line} ² , which makes this type of membrane suitable for use at fuel cell operating temperatures between 100 and 200 ° C. Disadvantage of this type of membrane is the possible bleeding of the phosphoric acid from the composite membrane when the fuel cell temperature drops below 100 ° C, and condensing product water from the membrane flours phosphoric acid ³ . The liberated phosphoric acid can then cause severe corrosion damage in the fuel cell system. Another disadvantage of H ₃ P0 ₄ -doped PBI membranes is the chemical degradation of the PBI in the fuel cell ⁴ . Some strategies have been implemented in the R & D of this type of membrane to reduce the degradation of PBI in fuel cell operation. One strategy is the preparation of acid-base blend membranes from PBI and acidic polymers, wherein the acidic polymer takes on the role of an ionic crosslinker by proton transfer from the acidic polymer to the PBI-imidazole. Acid-base blend membranes were researched and developed in the inventor's working group ⁵ and, in part, modified in collaboration with Q. Li's research group at the Danish Technical University (DTU) for medium-temperature membranes in an EU project. It was shown that the base excess acid-base blend membranes had better chemical stabilities than pure PBI, which can be attributed to the ionic cross-linking sites in the blend membranes ⁶ . In the working group, base-acid blend membranes were prepared from different PBIs such as PBIOO and F ₆ PBI with phosphonated poly (pentafluorostyrene) ⁷ and doped with H ₃ P0 ₄ ⁸ . It was found that the blend membranes had excellent chemical stabilities: one of the membranes (blend of 50 wt% PBIOO and 50 wt% PWN) showed a mass loss of only 2% even after 144 h in Fenton's reagent, whereas pure PBIOO after the same storage time in Fenton's reagent had a mass loss of 8%. Another way to increase the chemical stability of PBI-type membranes is to prepare covalently cross-linked PBI membranes described by Q. Li et al. and other research groups. In this case, the PBI can be crosslinked with a low molecular weight crosslinker such as bisphenol A bisepoxide ⁹ , divinyl sulfone ¹⁰ or a high molecular weight crosslinker such as chloromethylated PSU ¹¹ or bromomethylated polyether ketone ¹² . Further attempts to increase the stability of PBI membranes relate to the preparation of nanoparticle-modified PBI membranes ¹³ , or the preparation of partially sulfonated PBI, which crosslinks intra- or intermolecularly ionically by proton transfer from the acidic group to the imidazole group ^{14 15} . It has also been reported by PBI to which side chains containing phosphonic acid groups are grafted, forming ionic crosslinking sites between the basic PBI main chain and the acidic side chains ^{16 17} . Of the PBI membranes of the prior art, the blend membranes of PBI and poly (2,3,5,6-tetrafluorostyrene-4-phosphonic acid) synthesized by us have the best stability against radical degradation (determined ex-situ by means of the Fenton reaction). Tests ⁸ ). In the There are also references to blends of polybenzimidazole and dialkylated polybenzimidazole which are used as stable anion exchange membranes. ^{18 19,20} . A variety of polymers are currently used as backbonead polymers for the production of novel AEMs, including ethylene-tetrafluoroethylene, polyetheretherketones, polyethersulfone, poly (ether sulfone ketone). , Polyethylene, polyphenylene oxide, polystyrene, polyvinyl acetate, poly (vinylbenzyl chloride), polyvinylidene fluoride. Table 1 gives a comprehensive compilation of relevant non-commercial AEMs, which are also juxtaposed with the Tokuyama A201 benchmark membrane. The 28 μΓΤΐ thick commercial Tokuyama membrane A201 (development kit A006) has, according to the manufacturer ^21, a hydroxide conductivity of about 40 mS-cm ^-1 (23 ° C. and RF = 90%). The corresponding IEC value is 1.7 meq-g ^-1 . The benchmark membrane was characterized in the context of this invention under the same measuring conditions.

Table 1: Relevant membranes for use in fuel cells

-

Description of the invention

Covalently and / or ionically crosslinked PBI blend membranes, which are prepared with halomethylated and optionally sulfonated and / or phosphonated polymers and tailored in terms of their properties, are described in the context of this invention based on the state of R & D. Optionally, the blend membranes are additionally crosslinked covalently, for example by adding a low and / or a macromolecular crosslinker. Depending on the selected composition, the membranes can be used in electrochemical processes as low-temperature cation exchange membranes, low-temperature anion exchange membranes (temperature range without pressure up to 100 ° C. or under pressure up to 150 ° C.), or doped with proton conductors such as phosphoric acid and / or phosphonic acids , usable in the middle temperature range up to 220 ° C. Examples of electrochemical processes in which these membranes are to be used are: a) low-temperature H ₂ fuel cells or electrolysis (0-100 ° C without pressure or 0-130 ° C under pressure)

b) low-temperature direct fuel cells with fuels from the chemical group of alcohols such as methanol, ethanol, ethanediol, glycerol or ether fuels such as dimethyl ether or diethyl ether or various glymes (glyme, diglyme, triglyme ...) c) medium temperature fuel cells or electrolysis (0 -220 ° C)

d) Medium temperature depolarized electrolyses (eg SGyelectrolysis)

e) redox flow batteries (for example all-vanadium, iron-chromium, etc.)

In the following, exemplary membrane types which are suitable for the respective electrochemical applications will be described.

Anion exchange blend membranes for Ph fuel cells, DMFC, redox flow batteries, alkaline electrolysis

The anion exchange membranes consist of the following components: a) Any polybenzimidazole (PBI) as a matrix polymer, examples of which are as follows: Polyphenzimidazoles as ABPBI, PBI Celazol, p-PBI, F ₆ PBI, SO ₂ PBI, and PBIOO. Characteristic of the polybenzimidazoles used is the recurring occurrence of the benzimidazole unit in the main chain or side chain of the polymer.

b) A halomethylated polymer (backbone randomly selected from the group of polystyrenes and polystyrene copolymers, aryl backbone polymers (for example, polyether sulfones, polyether ketones, polysulfones, polybenzimidazoles, polyimides, polyphenylene oxides, polyphenylene sulfides, and any combinations as random copolymers, block copolymers, alternating copolymers ) carrying the functional group -CR ₂ Hal with R = Hal, alkyl, aryl and Hal = Cl, Br, I

c) An alkyl halide (monohaloalkane, dihaloalkane, oligohaloalkane, monobenzyl halide, dibenzyl halide, tribenzyl halide, etc.), for example, diiodoalkane such as diiodopropane, diiodobutane, diiodopentane, diiodohexane, diiodoheptane, diiodooctane, diiodononane, diiododecane, etc. d) optionally a monoalkylated polybenzimidazole

e) Any polymer having cation exchange groups, e.g. B. S0 ₃ X, P0 ₃ X ₂ , COOX, S0 ₂ X and X = H, alkali metal, alkaline earth metal, ammonium, imidazolium, pyridinium

The anion exchange groups of the blend are in molar excess compared to the other functional groups such. B. cation exchange groups. The anion exchange polymer blend membranes can thereby obtain the anion exchange groups in the following ways: a) The solution of the mixture of the above polymers in a dipolar aprotic solvent (NM P, DMAc, DMF, DMSO, NEP, sulfolane, etc.) becomes a basic nitrogen compound such as For example, tertiary amine NR ₃ (R = alkyl, aryl), pyridine, (tetralkyl) guanidine, alkyl or aryl imidazole added. In this case, the chemical compound containing tertiary nitrogen may contain one, two or more tertiary nitrogen atoms. The tertiary nitrogen compound may also be an oligomer (eg a polyvinylpyridine). Thereafter, the polymer solution is laced on a substrate, sprayed or poured and the solvent evaporated. Thereafter, the resulting membrane is aftertreated:

- After treatment in water to remove residual chemicals and solvents

- If necessary, post-treatment in dilute alkali or alkaline earth metal hydroxide solution to replace the Hal counterions against OH ^~ ions

optionally alkylating the remaining tertiary N groups (imidazole, guanidine) with a non-carcinogenic alkylating agent

- Wash with water to remove residual chemicals and solvents

b) The mixture of the above polymers in a dipolar aprotic solvent is laced or cast and the solvent removed. Thereafter, the nitrogen groups of the resulting membrane are quaternized by immersion in a tertiary amine, in an amine solution or in a mixture of various tertiary amines. Thereafter, the aftertreatment of the membrane is carried out in the following manner:

- After treatment in water to remove residual chemicals and solvents

- If necessary, aftertreatment in dilute alkali or alkaline earth metal hydroxide solution to replace the Hal counterions against OH ^" ions

optionally alkylating the remaining tertiary N groups (imidazole, guanidine) with a noncancerogenic alkylating agent

- Wash with water to remove residual chemicals and solvents.

It has surprisingly been found that homogeneous, mechanically and chemically very stable anion exchange membranes can be produced by means of the processes described, which are substantially more stable than anion exchange membranes of the prior art. Base excess PBI blend membranes (covalently or covalently-ionically crosslinked) for doping with phosphoric acid or phosphonic acids or any other mineral acids for use in electrochemical processes in the temperature range 100 to 220 ° C

These membranes consist of a molar excess of a polybenzimidazole, where the polybenzimidazole may be differentially crosslinked to limit its mineral acid or water uptake. The membranes may consist of the following components: a) a polybenzimidazole (PBI) as matrix polymer (as example ABPBI, PBI Celazol, p-PBI, F ₆ PBI, SO ₂ PBI, PBIOO and other polybenzimidazoles)

c) An alkyl halide (monohaloalkane, dihaloalkane, oligohaloalkane, monobenzyl halide, dibenzyl halide, tribenzyl halide, etc.), for example, diiodoalkane such as diiodopropane, diiodobutane, diiodopentane, diiodohexane, diiodoheptane, diiodooctane, diiodononane, diiododecane, etc.

d) optionally a monoalkylated polybenzimidazole

Covalently cross-linked PBI blend membranes can consist of the components a), b), c), d) and optionally a polymeric sulfinate RSO ₂ X, covalently-ionically cross-linked membranes additionally contain cation exchange polymers listed under e).

After membrane preparation, the membranes are doped with phosphoric acid or phosphonic acid. The Phosphorsäure- / Phosphonsäureaufnahme by the concentration of the acid, by the bath temperature and by the residence time of the membrane in the mineral acid such. B. phosphoric acid / Phosphonsäurebad be controlled.

A covalently cross-linked PBI is obtained, for example, by: a) mixing the PBI with a halomethylated polymer, the halomethylated polymer reacting with one or both N atoms of the imidazole group of the PBI by alkylation (Figure 1).

b) Blending the PBI with a monoalkylated PBI, a tertiary diamine (eg DABCO), a diiodoalkane (eg diiodobutane) and a polymeric sulfinate. There are several ways of forming a polymeric network of these components, as shown in Figure 2, Figure 3, and Figure 4.

A covalently ionically crosslinked membrane is obtained by a) Before the evaporation of the solvent, a phosphonated and / or sulfonated polymer is added to the polymer mixture.

b) The polymer components of the membrane are subsequently sulfonated by aftertreatment of the membrane in a sulfuric acid bath of different concentration (30-100% H ₂ S0, depending on the reactivity of the polymers in the blend). By protonation of the imidazole groups of the PBI by the subsequently introduced sulfonic acid groups, ionic crosslinking sites are formed.

c) If the polymer mixture also contains highly fluorinated aromatic polymers whose F atoms can be replaced nucleophilically by phosphonic acid groups (for example by the phosphonation reaction of ⁷ ), the membrane is placed in a solution containing tris (trimethylsilyl) phosphite. In this case, part of the aromatic F is replaced by Phosphonsäuresilylester groups, which can be easily hydrolyzed by boiling with water to free phosphonic acid groups. Nucleophilic replaceable aromatic F bonds can also be replaced by other functional groups, for example by thiol groups, which can be used in a further step after for crosslinking.

Surprisingly, it has been found that homogeneous, mechanically and chemically very stable medium-temperature cation exchange membranes can be produced by means of the processes described, which are more stable than medium-temperature cation exchange membranes of the prior art (for example doped pure polybenzimidazoles).

Acid-excess blend membranes (cation-exchange membranes) for H ₂ fuel cells, DMFC, PEM electrolysis, redox-flow batteries

These membranes consist of the following blend components: a) cation exchange membranes with the sulfonic acid group S0 ₃ X or the phosphonic acid group P0 ₃ X ₂ (X = H, alkali metal, alkaline earth metal, ammonium, imidazolium, pyridinium)

b) a polybenzimidazole (PBI) as a matrix polymer (as example ABPBI, PBI Celazol, p-PBI, F ₆ PBI, SO ₂ PBI, PBIOO and other polybenzimidazoles)

c) A halomethylated polymer (backbone randomly selected from the group of polystyrenes and polystyrene copolymers, aryl backbone polymers (for example, polyether sulfones, polyether ketones, polysulfones, polybenzimidazoles, polyimides, polyphenylene oxides, polyphenylene sulfides, and any combinations as random copolymers, block copolymers, alternating copolymers ) carrying the functional group -CR ₂ Hal with R = Hal, alkyl, aryl and Hal = Cl, Br, I

d) optionally an alkyl halide (monohaloalkane, dihaloalkane, oligohaloalkane, monobenzyl halide, dibenzyl halide, tribenzyl halide, etc.), for example diiodoalkane such as diiodopropane, diiodobutane, diiodopentane, diiodohexane diiodoheptane, diiodooctane, diiodononane, diiododecane, etc.

e) optionally a monoalkylated polybenzimidazole

In these membranes, the acidic groups are in molar excess, so that these membranes are cation-conductive. The blend membranes are covalently-ionically crosslinked when they the components a), b) c) and optionally d) and e). Reaction of the blend components b) and c) with each other (and optionally also d) and e)) results in quaternary positively charged nitrogen groups which form ionic crosslinking sites with the acid anions: [S0 ₃ ^' ] ⁺ [NR ₄ ] (R = alkyl, aryl ), which form stronger electrostatic interactions with one another than when only ionic crosslinks form between the acidic groups and protonated benzimidazolium groups, as would be the case for the mixture between the acidic polymer and the non-alkylated PBI. It is expected that the crosslinking sites [S0 ₃ ^' ] ⁺ [NR ₄ ] (R = alkyl, aryl) together with the covalent crosslinking of the blend components b) and c) (and optionally still d) and e)), in particular in use These membranes in redox-flow batteries (RFB) reduce the permeability of the membranes for metal cations, which minimizes the efficiency losses of the RFB application.

Surprisingly, it has been found that homogeneous, mechanically and chemically very stable low-temperature cation exchange membranes can be produced by the described processes which are more stable than low-temperature cation exchange membranes of the prior art (for example acid-base blend membranes of cation exchange polymers with weak polymeric bases). In particular, it is surprising that the membranes of the invention are more stable than conventional aromatic acidic polymers, especially when used in redox flow batteries in which the membranes are exposed to highly oxidizing conditions.

Summary of the components of the 3 membrane types

Membranes are claimed which, depending on the proportion of the respective main blend components, can be used in various electrochemical processes. The tabular overview lists the main membrane types and their respective fields of application.

Table 2: Summary of the components of the 3 types of membranes

+ molar excess

optional

molar deficit

cation Head

Anionenleiter

Proton conductor via (poly) phosphoric and / or phosphonic acid Surprisingly, it was found that the membranes, depending on the proportion of the different blend components listed in Table 2, can be used either as cation exchange, anion exchange or middle temperature membranes. In particular, it is surprising that it is also possible to produce multilayer membranes (from alternating cation exchanger and anion exchanger layers), which have outstanding properties, such as extremely high chemical stabilities and very low cation permeabilities, in particular when used in redox flow batteries.

The membranes according to the invention have excellent mechanical and chemical stability and, at the same time, excellent ionic conductivities. For comparison, Table 1 shows the values of comparative membranes from the prior art.

In the following examples, the membranes are laced on glass plates for the sake of simplicity. Alternatively, as is conventional in the art, the membranes may also be applied to other substrates and substrates, e.g. on foils or metal strips to be produced from roll to roll or in suspended dryers.

The membranes can also be deposited on substrates without them necessarily having to be removed from them again. An example is graphite felts, nonwovens, fabrics or porous materials, such as films with pores or felts. All listed aftertreatments then take place with the substrate on which the membrane was deposited or was formed after removal of the solvent. In this case, the membrane no longer separates from the carrier material, which is wanted.

In the following examples specific conditions for implementation are given. It is obvious to the person skilled in the art that these are not exclusive. So, for example, the solvent is removed. This happens here by evaporation at 140 ° C. Of course, the solvent will also evaporate at lower or higher temperatures, e.g. in the temperature range from 30 ° C to 180 ° C.

The same applies to the aftertreatment conditions in water, acid and lye, where the indication of the temperature and the indication of the concentration of the acid or lye gives the laboratory reliable value. The information is not restrictive.

AewemdMmgsbeispiele

Example 1: HTPEM from PBI, halomethylated polymer (covalently crosslinked) (membrane MJK 1885)

0.75 g of the polybenzimidazole F ₅ PBI are dissolved as a 4% solution in Ν, Ν-dimethylacetamide (DMAc) with 0.321 g of bromomethylated polyphenylene oxide (PPOBr, degree of bromination 1.7 CH ₂ Br per PPO). Repeat unit) (blend components see Figure 5) mixed as a 10% solution in DMAc. After homogenization, a membrane is straightened from this solution on a glass plate, and the solvent is removed in a convection oven at 140 ° C. Thereafter, the membrane is dissolved under water and post-treated as follows: 48 hours 10% HCl at 90 ° C, then 48 hours DI water at 60 ° C.

Thereafter, the membrane is characterized as follows:

- Thermogravimetry (TGA) in 65% 0 ₂ , TGA curve see Figure 6

Extraction with DMAc at 90 ° C. (4 days) Extraction residue (insoluble fraction 88.9%) Fentons test: after 96 hours in Fenton's reagent mass loss of 7.5%

- Doping with 85% H3P04 (259% doping level), conductivity curve see Figure 7

Example 2: HTPEM of PBI, Halomethylated Polymer, Tertiary Amine, Sulfonated Polymer (Covalently-Ionically Crosslinked) (MJK-1959)

1.4 g of F ₆ PBI are mixed as a 5% solution in DMAc with 0.3 g of PARBrl as a 5% solution in DMAc and 0.3 g of the sulfonated polymer sPPSU and 0.488 g of 1-ethyl-2-methylimidazole (polymers Blend components see Figure 8).

After homogenization, a membrane is straightened from this solution on a glass plate, and the solvent is removed in a convection oven at 140 ° C. Thereafter, the membrane is dissolved under water and post-treated as follows: 48 hours 10% HCl at 90 ° C, then 48 hours DI water at 60 ° C. Figure 9 shows the blend of the PBI with the quaternized polymer. By reaction of a small part of the CH ₂ Br groups with the imidazole NH under alkylation, covalent cross-linking bridges are formed.

Thereafter, the membrane is characterized as follows:

Thermogravimetry (TGA) in 65% 0 ₂

Extraction with DMAc at 90 ° C (4 days) -> Extraction residue (insolubles%) Fentons test: after 96 hours in Fenton's reagent% mass loss

Doping with 85% H ₃ P0 ₄ (259% doping level), conductivity curve Figure 7

Example 3: AEM from PBI, halomethylated polymer, tertiary amine, sulfonated polymer (covalently ionically crosslinked] (membrane MJK-1932)

0.5 g of F ₆ PBI are mixed as a 5% solution in DMAc with 0.5 g of PPOBr as 5% solution in DMAc and 0.107 g of the sulfonated polymer sPPSU and 1.08 ml of the tertiary amine N-methylmorpholine (polymeric blend components see Figure 10).

After homogenization, a membrane is straightened from this solution on a glass plate, and the solvent is removed in a convection oven at 140 ° C. Thereafter, the membrane is dissolved under water and post-treated as follows: 48 hours 10% HCl at 90 ° C, then 48 hours DI water at 60 ° C. By reaction of a small part of the CH ₂ Br groups with the imidazole NH under alkylation, covalent cross-linking bridges are formed. Thereafter, the membrane is characterized as follows:

Thermogravimetry (TGA) in 65% 0 ₂ (Figure 11)

Extraction with DMAc at 90 ° C (4 days) -> extraction residue (insolubles 93.9%)

Thickness: 105 μιτι

- Chloride conductivity (RT, 1 M NaCl): 4.88 mS / cm

- IEC: 2.8 mmol / g

- Chemical stability (90 ° C, 1 M KOH)

IEC (after 5 days): 84.6 of the original value

- IEC (after 10 days): 74.3 of the original value

Conductivity: (after 5 d): 56.1% of the original value

Example 4: CEM of Sulfonated Polymer, PBI, Halomethylated Polymer, Tertiary Amine (Covalently-Ionically Crosslinked) (Membrane MJK-1957)

0.12 g of F ₆ PBI are mixed as a 5% solution in DMAc with 0.12 g of PARBrl as a 5% solution in DMAc and 2 g of the sulfonated polymer sPPSU and 0.195 g of 1-ethyl-2-methylimidazole (see Polymer Blend Components Figure 12).

After homogenization, a membrane is straightened from this solution on a glass plate, and the solvent is removed in a convection oven at 140 ° C. Thereafter, the membrane is dissolved under water and post-treated as follows: 48 hours 10% HCl at 90 ° C, then 48 hours DI water at 60 ° C. By reaction of a small part of the CH ₂ Br groups with the imidazole NH under alkylation, covalent cross-linking bridges are formed.

Thereafter, the membrane is characterized as follows:

Thermogravimetry (TGA) in 65% 0 ₂

Extraction with DMAc at 90 ° C (4 days) -> Extraction residue (insolubles in%) Fentons test: after 96 hours in Fenton's reagent mass loss in%

Impedance (resistance)

Water absorption at 90 ° C

Example 5: AEM from sulfonated polymer, PBI, halomethylated polymer, tertiary amine (covalently-ionically crosslinked)

0.8 g of F ₆ PBI are mixed as a 5% solution in DMAc with 1.2 g of PARBrl as a 5% solution in DMAc and 0.12 g of the sulfonated polymer sPPSU and 1.95 g of 1-ethyl-2-methylimidazole (For polymeric blend components, see Figure 13).

Thermogravimetry (TGA) in 65% 0 ₂

Extraction with DMAc at 90 ° C (4 days) -> Extraction residue (insoluble ante

Fenton's test: after 96 hours in Fenton's reagent mass loss in%

Impedance (resistance)

Water absorption at 90 ° C

Example 6: AEM from sulfonated polymer, F ₆ PBI, halomethylated / partially fluorinated polymer, tertiary mono- and diamine (covalently-ionically crosslinked)

0.162 g of F ₅ PBI 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 (acid-base polymer). blends)

After homogenization, a membrane is poured from this solution onto a Petri dish, and the solvent in a convection oven at 80 ° C withdrawn. Subsequently, the membrane is dissolved under water and aftertreated as follows: 48 hours in a mixture of 50/50 DABCO / EtOH at 80 ° C, then 48 hours in demineralized water at 90 ° C. By reaction of a small part of the CH ₂ Br groups with the imidazole NH under alkylation, covalent cross-linking bridges are formed. The diamine further covalently cross-links the membrane.

Table 3: Characterization parameters of the membrane 54-PAK18r-60-F6PBI-SAC-IS-NMM-DABCO

Membrane 54-PAK18r-60-F ₆ PBI-SAC-15-NMM-DABCO

lEC value, mmol / g: 2.0

Thickness μπι: 60

Cr-σ (1 M, NaCl), mS / cm: 10.1

Alkaline stability,% of

Original value: 92.8

(Cr-σ after 5 d in I M KOH 90 ° C)

Extraction with DMAc, wt.%

96.3

(insoluble fractions, after 4 d at 80 ° C)

Water absorption (30 ° C), wt .-% 66.9

Figure 14 shows the degree of crosslinking as a function of the SAC content in the polymer solution for NMM-DABCO quaternized membranes from PAK18r-60-F ₆ PBI.

Example 7: AEMs of PBIOO, Halomethylated Polymer, Alkylimidazole (Covalently Crosslinked)

63- PPO-40-PBIOO-Melm: 0.15 g of F ₆ PBI 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)

64- PPO-50-PBIOO-Melm: 0.125 g of F ₆ PBI 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) 67-PPO-50-PBIOO-EtMelm: 0.125 g of F ₅ PBI 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)

After homogenization, a membrane is poured in each case from the polymer solution onto a Petri dish, and the solvent is removed in a circulating air drying oven at 80.degree. Subsequently, the membranes are removed under water and rinsed for 48 hours in deionized water at 90 ° C. By reaction of a small part of the CH ₂ Br groups with the imidazole NH under alkylation, covalent cross-linking bridges are formed.

The membranes are characterized as follows:

Table 4: Characterization parameters of alkylimidazole quaternized PPO-PBIOO membranes

Membrane 63-PPO-40-64-PPO-50-67-PPO-50-

PBIOO-Melm PBIOO-Melm PBIOO-Etmel

IEC value, mmol / g: 4.5 4.1 3.5

Thick, \ im: 35 33 45

Cr-σ (1 M, NaCl), mS / cm: 6.4 16.9 15.1

Alkaline stability,% of

Original value: 45.3 50.4 26.8

(Cr-σ after 5 d in 1 M KOH 90 ° C)

Cr-σ (90% RH, 30 ° C), mS / cm: k. A. 4,8 4,5

Extraction with DMAc, wt.%

86.1 94.1 96.7

(insoluble fractions, after 4 d at 80 ° C)

Water absorption (30 ° C), wt.% 46.4 60.4 56.9

Figure 15 shows the comparison of the chloride conductivities (1 M NaCl, RT) of the alkylimidazole quaternized PPO-PBIOO membranes and the commercial Tokuyama membrane A201 (development code A006). Thermogravimetry (TGA) in 65% 0 ₂ (Figure 16)

Example 8: AEMs of (sulfonated polymer,) F ₆ PBI, halomethylated polymer, tertiary mono- and diamine (covalently and / or ionically crosslinked (Figure 17)

37-PPO-50-F6PBI-NMM-TMEDA: 0.2025 g of F ₆ PBI are dissolved 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 mixed (covalently crosslinked polymer blends)

After homogenization, a membrane is poured from the solution onto a Petri dish, and the solvent in a convection oven at 80 ° C withdrawn. The membrane is then removed under water and after-treated as follows: 48 hours in TMEDA (1 d RT, ld 50 ° C), then 48 hours in deionized water at 90 ° C. By reaction of a small part of the CH ₂ Br groups with the imidazole NH under alkylation, covalent cross-linking bridges are formed. The diamine further covalently cross-links the membrane.

40-PPO-50-F6PBI-SAC-5-NMM-TMEDA: 0.2025 g of F ₆ PBI 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 mixed (covalently crosslinked polymer blends)

After homogenization, a membrane is poured from the solution onto a Petri dish, and the solvent in a convection oven at 80 ° C withdrawn. The membrane is then dissolved under water and after-treated as follows: 48 hours in TMEDA (1 d RT, id 50 ° C, then 48 hours in demineralized water at 60 ° C.) By reaction of a small portion of CH ₂ Br groups with The imidazole NH under alkylation gives rise to covalent cross-linking bridges.

Table 5: Characterization parameters of PPO-F6PBI membranes, which are (37) covalently and covalently (40) cross-linked

Membrane 37-PPO-50-F6PBI-40-PPO-50-F6PBI-SAC-5

NMM-TMEDA NMM-TMEDA

IEC value, mmol / g: k. A. k. A.

Thickness, μην. 45 40

Cr-σ (1 M, NaCl), mS / cm: 12 5.3

Alkaline stability,% of

Original value: 41.6 82.3

(Cr-σ after 5 d in I M KOH 90 ° C)

Extraction with DMAc, wt.%

K. A. K. A.

(insoluble fractions, after 4 d at 80 ° C)

Water absorption (30 ° C), wt.% 46.1 47.2

Thermogravimetry (TGA) in 65% 0 ₂ (Figure 18)

Example 9: AEMs of sulfonated polymer F ₆ PBI, halomethylated polymer, tertiary mono- and diamine (covalently ionically crosslinked) -> 44, 45, 46

0.2025 g of F ₆ PBI is 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 ) as a 5% solution in DMAc and 0.59 ml of the tertiary monoamine N-methylmorpholine mixed (ionic-covalently cross-linked acid-base blends)

Table 6: Characterization parameters of the PPO-F6PBI acid-base blends quaternized and cross-linked with NMM / DABCO

44-PPO-50-45-PPO-50-46-PPO-50-

membrane

F6PBI-SAC-5-F6PBI-SAC-10 F6PBI-SAC-15

NMM-DABCO NMM-DABCO NMM-DABCO

IEC value, mmol / g: 2.5 2.5 2.6

Thickness, [in: 85 55 50

cr-σ (1 M, NaCl), mS / cm: 61.4 54.7 21.9

Alkaline stability,% of

Original value: 78.4 38.6 k. A.

(Cr-σ after 5 d in I M KOH 90 ° C)

cr-a (90% RH, 30 ° C), mS / cm: k. A. k. A k. A.

Extraction with DMAc, wt.% 79.8 88.3 88.1 (insoluble fractions, after 4 d at 80 ° C)

Water absorption (30 ° C), wt .-% 159.3 133.9 107.5

Thermogravimetry (TGA) in 65% 0 ₂ (Figure 19)

Example 10: AEMs of sulfonated polymer FePBI, halomethylated polymer, tertiary monoamine [covalently ionic crosslinked] -> 71, 72, 73, 74, 75

0.2025 g of F ₆ PBI are dissolved 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-F6PBI-SAC-5). NMM), 0.0405 g SAC (72-PPO-50-F6PBI-SAC-10-NMM), 0.06075 g SAC (73-PPO-50-F6PBI-SAC-15-NMM), 0.081 g SAC (74 -PPO-50-F6PBI-SAC-20-NMM) or 0.0 g of SAC (75-PPO-50-F6PBI-NMM) and 0.59 ml of the tertiary monoamine N-methylmorpholine (ionic covalently crosslinked acid-base blends)

After homogenization, a membrane is poured from the solution onto a Petri dish, and the solvent in a convection oven at 80 ° C withdrawn. The membrane is then removed under water and after-treated as follows: 48 hours in 15% NMM in EtOH (1 d RT, 1 d 50 ° C), then 48 hours in demineralized water at 90 ° C. By reaction of a small part of the CH ₂ Br groups with the imidazole NH under alkylation, covalent cross-linking bridges are formed. Also, the oxygen atom belonging to the morpholine contributes to further cross-chain hydrogen bonding within the membrane.

Table 7: Characterization parameters of the acid-base blends of PPO-F6PBI quaternized with NMM

Membrane 71-PPO-50-72-PPO-SO-73-ΡΡΟ-50-74-ΡΡΟ-50-

75 ΡΡΟ 50 F6PBI SAC F6PBI SAC F6PBI SAC F6PBI SAC F6PBI NMM

5-NM 10-NM 15-NM 20-NMM

lEC value, mmol / g: k. A. k. A. k. A. k. A. k. A.

Thickness, in: 50 47 37 40 70

Cr-a (1M, NaCl), mS / cm: 16.9 11.5 2.5 1.8 18.9

Alkaline stability,% of

Original value: 50.5 56.9 86.9 99.0 k. A.

(Cr-σ after 5 d in I M KOH 90 ° C)

cr-σ (90% RH, 30 ° C), mS / cm: 5.2 k. A. k. A. k. A. 6.5

Extraction with DMAc, wt.%

100 100 99.1 93.5 k. A.

(insoluble fractions, after 4 d at 80 ° C)

Water absorption (30 ° C), wt.% 54.0 58.7 39.4 39.0 k. A.

Thermogravimetry (TGA) in 65% 0 ₂ (Figure 20) Example 11: AEMs from Different Blend Components

Table 8 lists the compositions of various AEM blends, and Table 9 lists some of their properties.

-Blendmembrantypen

(unknown)

Structural formula (repeating unit) of PPOBr and F ₆ PBI see Figure 5

Structural formula (repeating unit) of PARBrl and sPPSU see Figure 8 Structural formula (repeating unit) of PBIOO and PVBCI see Figure 21 Table 9: Some characterization results of these AEM blends

Start of decomposition of the polymer (determined by TGA-FTIR coupling)

It is clearly evident from Table 9 that all tested AEM blend membranes have better chemical stabilities both after KOH incorporation and in the TGA experiment than the Tokuyama A201 commercial benchmark membrane.

The membranes are due to their excellent properties, conductivity and

Long-term stability in alkaline media, particularly suitable for sensors, particularly ion-selective sensors and ion-selective applications, and for alkaline fuel cells. literature

¹ Wainright, JS; Wang, JT; Savinell, RF; Litt, MJ Electrochem. Soc. 142, L121-L123 (1995)

² Kreuer, KD; Paddison, S .; Spohr, E .; Schuster, M. Chem. Rev. 104, 4637-4678 (2004)

³ Yu, S .; Xiao, L; Benicewicz, BC Fuel Cells 8, 165-174 (2008)

Liao, J .; Li, Q .; Rudbeck, H. C .; Jensen, J.O .; Chromik, A .; Bjerrum, N.J .; Kerres, J .; Xing, W. Fuel Cells 11, 745-755 (2011)

⁵ Kerres, J .; Ullrich, A .; Meier, F .; Haring, T. Solid State Ionics 125, 243-249 (1999)

⁶ Kerres, J .; Schönberger, F .; Chromik, A .; Haring, T .; Li, Q.; Jensen, JO; Pan, C; Noye, P .; Bjerrum NJ Fuel Cells 8, 175-187 (2008)

⁷ Atanasov, V .; Kerres, J. Macromolecules 44, 6416-6423 (2011)

⁸ Highly phosphonated polypentafluorostyrene: characterization and blends with polybenzimidazole. Atanasov, V .; Gudat, D .; Ruffmann, B .; Kerres, J. Eur. Poly. J., 2013, 49, 3977-3985

⁹ Wang, 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)

¹⁰ Aili, D .; Li, Q .; Christensen, E .; Jensen, JO; Bjerrum, NJ Polym. Int. 60, 1201-1207 (2011)

¹¹ Yang, J .; Li, Q .; Cleemann, LN; Jensen, JO; Pan, C; Bjerrum, NJ, He, R. Adv. En. Mater. 3, 622-630 (2013)

¹² Wang, S .; Zhao, C; Ma, W .; Zhang, N .; Liu, Z .; Zhang, G .; Well, HJ Power Sources 243, 102-109 (2013)

¹³ Plackett, D .; Siu, A .; Li, Q .; Pa, C; Jensen, JO; Nielsen, SF; Permyakova, AA; Bjerrum NJJ Memb. Be. 383, 78-87 (2011)

¹⁴ Jones, DJ; Roziere, JJ Memb. Be. 185, 41-58 (2001)

¹⁵ Peron, J .; Ruiz, E .; Jones, D .; Roziere, JJ Memb. Be. 314, 247-256 (2008)

¹⁶ Sukumar, PR; Wu, W .; Markova, D .; Ünsal, Austria; Klapper, M .; Müllen, K. Macromol. Chem ,. Phys. 208, 2258-2267 (2007)

¹⁷ Sinigersky, V .; Budurova, D .; Penchev, H .; Ublekov, F .; Radev, IJ Appl. Polym. Be. 129, 1223-1231 (2013)

¹⁸ Kerres, J .; Ullrich, A .; Haring, T. Engineering ionomeric blends and engineering ionomeric blend membranes, US 6,723,757B1, Apr. 20, 2004

¹⁹ Wright, A .; Thomas, O .; Holdcroft, S. Anion-conducting polymer, WO2013149328 (PCT / CA2013 / 000323) Priority date 04 April 2012

²⁰ Thomas, OD; Soo, KJWY; Peckham, TJ; Kulkami, MP; Holdcroft, SJ Am. Chem. Soc. 134 (2012) 10753-10756

²¹ Yanagi, H .; Fukuta, K. ECS Trans. 2008 16 (2), pp. 257-262 (2008)

²² Yang, C.-C. Materials Science and Engineering: B 131 (1-3), p. 256-262 (2006)

²³ Industrial Property: European Patent 1 612 874 AI. El Moussaoui, Rachid; Martin, Roland. Applicant: SOLVAY (Societe Anonyme) 1050 Brussels (2006)

²⁴ Varcoe, JR Physical Chemistry Chemical Physics 9, pp. 1479-1486 (2007)

²⁵ Wu, L; Xu, T. J Membr Sei; 322: 286-92 (2008)

6 Hibbs, M.R .; Fujimoto, C.H .; Cornelius, C.J. Macromolecules 42, S. 8316-8321 (2009)

²⁷ Robertson, Nicholas J .; Kostalik IV, Henry A .; Clark, Timothy J .; Mutolo, Paul F .; Abruna, Hector 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, pp. 3400-3404. DOI: 10.1021 / ja908638d8 ⁸ Kostalik, HA; Clark, TJ; Robertson, NJ; Mutolo, PF; Longo, JM ;. Abruna, HcD; Coates, GW

Macromolecules 43, pp. 7147-7150 (2010)

9 Wang, J .; Li, S .; Zhang, S. Macromolecules 43, pp. 3890-3896 (2010).

0Tanaka, M .; Masaki K .; Miyatake, K .; Watanabe, M. Macromolecules 43, pp. 2657-2659 (2010).

1 Tanaka, M .; Fukasawa, K .; Nishino, E .; Yamaguchi, S .; Yamada, K .; Tanaka, H .; Bae, B .; Miyatake, K .;

Watanabe, M.J. Am. Chem. Soc. 133, pp. 10646-10654 (2011)

2 Zhao, Z .; Wang, J .; Li, S-; Zhang, S. Journal of Power Sources 196 (10), pp. 4445-4450 (2011)

3 Faraj, M .; Elijah, E .; Boccia, M .; Filpi, A .; Pucci, A .; Ciardelli, F. Journal of Polymer Science Part A: Polymer Chemistry, 49, pp. 3437-3447 (2011)

4 Ran, J .; Wu, L; Varcoe, JR; Ong, A.L .; Poynton, SD; Xu, T. Journal of Membrane Science 415-416, pp. 242-249 (2012) Lin, X .; Wu, L; Liu, Y .; Ong, A.L .; Poynton, SD; Varcoe, JR; Xu, T. Journal of Power Sources 217, pp. 373-380 (2012)

Wang, J .; He, G .; Wu, X .; Yan, X .; Zhang, Y .; Wang, Y .; Du, L. Journal of Membrane Science 459, pp. 86-95 (2014)

Yan, X .; Gu, S .; He, G .; Wu, X .; Zheng, W .; Ruan, X. Journal of Membrane Science, In Press, Accepted Manuscript, available online May 9, 2014.

Claims

claims

1. Membrane characterized in that it in any mixing ratios of the polymeric membrane components:

any halomethylated polymer (polymer with CH ₂ Hal groups, with Hal = F, Cl, Br, I)

any polymer with cation exchange groups S0 ₃ X or P0 ₃ X ₂ (counter ion as desired, but preferably X = H, metal cation, ammonium cation, imidazolium cation, pyridinium cation, etc.)

- Any polymer with tertiary N-basic groups

- And optionally any chemical compound or a mixture of any chemical low or high molecular weight compounds with tertiary N groups.

2. Membrane according to claim 1, characterized in that

the halomethylated polymer or polymers are selected from arylene main chain polymers having CH ₂ -Hal side groups (Hal = Cl, Br, I)

- The cation exchange or the polymers are selected from sulfonated polymers

the tertiary or N-basic polymers are selected from polyimidazoles,

Polybenzimidazoles, polyimides, polyoxazoles, polyoxadiazoles, polypyridines or

Aryl polymers with tertiary N-basic functional groups

the tertiary N-basic compound or compounds 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 in it the

Is present in molar excess cation-exchange-containing polymeric membrane component and thus is a cationic conductor (cation exchange membrane KAM)

4. Membrane according to claim 1, characterized in that in it the

Is present in molar excess and thus an anion conductor (anion exchange membrane AAM) containing anion exchange groups polymeric membrane component.

5. Membrane according to claim 1, characterized in that in it the N-basic groups

containing polymeric membrane component is in molar excess and thus after doping with phosphoric acid, phosphonic acid, sulfuric acid or other 2- or 3-basic acids is a proton conductor, which can be used in the temperature range> 100 ° C.

6. A process for the preparation of membranes according to claims 1 to 5, characterized

characterized in that all polymeric membrane components in a common

Solvents are mixed together and homogenized, sprayed from the resulting solution, a membrane is geräkelt or poured, the solvent is then evaporated at elevated temperatures, the membrane is then detached from the pad and finally aftertreated by various methods to activate the membrane.

7. The method according to claim 6, characterized in that as a solvent for dissolving the polymers dipolar aprotic solvents such as Ν, Ν-dimethylacetamide, N-methylpyrrolidinone, Ν, Ν-dimethylformamide, dimethyl sulfoxide, N-ethylpyrrolidinone, diphenyl sulfone, sulfolane can be used.

8. The method according to claim 6, characterized in that the following

Aftertreatment is applied: (a) storage in dilute mineral acid at T = room temperature (RT) to 100 ° C; (b) Store in deionized water at room temperature to 100 ° C; (c1) if appropriate, storage in concentrated phosphoric or phosphonic acid at T = RT up to 150 ° C. to produce doped middle-temperature proton conductors (T = 100-220 ° C.) or (c2)

optionally storing in dilute alkali metal hydroxide solutions, followed by storage in deionized water to produce the OH form of anion exchange membranes (AAM).

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, S0 ₂ -depolarized electrolysis, redox flow batteries, electrodialysis,

Diffusion dialysis, nanofiltration, ultrafiltration, reverse osmosis and pressure-retarded osmosis.

10. Use of the membranes as part of sensors, electrodes, secondary batteries, fuel cells, alkaline fuel cells or membrane electrode units.