COMPOSITE ANION EXCHANGE MEMBRANE AND CATALYST COATED MEMBRANE FOR ELECTROCHEMICAL DEVICES
20260022481 ยท 2026-01-22
Inventors
- Chunqing Liu (Arlington Heights, IL)
- Nicole Karns (Des Plaines, IL, US)
- Saad Intikhab (Lombard, IL, US)
- Stacey Deptuch (Norhfield, IL, US)
- Xueliang Dong (Schaumburg, IL, US)
- Shurong Yang (Naperville, IL, US)
Cpc classification
C25B11/053
CHEMISTRY; METALLURGY
H01M8/103
ELECTRICITY
C25B9/23
CHEMISTRY; METALLURGY
C25B11/054
CHEMISTRY; METALLURGY
International classification
C25B11/053
CHEMISTRY; METALLURGY
C25B11/054
CHEMISTRY; METALLURGY
Abstract
Composite anion exchange membranes are described. The composite anion exchange membranes comprise an anion exchange polymer containing a hydrogen recombination catalyst dispersed in the anion exchange polymer. The anion exchange membrane may also include a radical scavenger. The anion exchange polymer comprises a plurality of repeating units of formula (I)
##STR00001##
Catalyst coated membranes and membrane electrode assemblies made using the composite anion exchange membranes are also described.
Claims
1. An anion exchange membrane comprising: an anion exchange polymer, and a hydrogen recombination catalyst dispersed in the anion exchange polymer, wherein the anion exchange polymer comprises a plurality of repeating units of formula (I) ##STR00056## wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of: ##STR00057## ##STR00058## ##STR00059## ##STR00060## and mixtures thereof; wherein X.sub.1 is selected from the group consisting of: ##STR00061## and mixtures thereof; wherein X.sub.2 is selected from the group consisting of: ##STR00062## or a mixture of ##STR00063## wherein Ar.sub.1 and Ar.sub.2 are the same or different from each other; wherein Y.sub.1.sup. and Y.sub.2.sup. are anions; wherein R.sub.1-R.sub.28 are each independently hydrogen, a halide, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein R.sub.29-R.sub.31 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein R.sub.32 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl group is optionally substituted with a halide or a positively charged functional group; wherein A is O, S, or NR.sub.100; wherein R.sub.100 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein n is an integer from 10 to 100,000; wherein m is an integer from 5 to 50,000 and the molar ratio of n/m is in a range of 1:1 to 99:1; wherein p is 1, 2, 3, or 4; wherein q is 0, 1, 2, or 3; and wherein t is 1, 2, 3, 4, 5, or 6.
2. The anion exchange membrane of claim 1 wherein the hydrogen recombination catalyst comprises Pt, Pt supported on carbon, silica, titania, or zirconia, PtCo, PtCo supported on carbon, silica, titania, or zirconia, Pd, Pd supported on carbon, silica, titania, or zirconia, PdCo, PdCo supported on carbon, silica, titania, or zirconia, Ru, Ru supported on carbon, silica, titania, or zirconia, RuCo, RuCo supported on carbon, silica, titania, or zirconia, or mixtures thereof.
3. The anion exchange membrane of claim 1 further comprising a radical scavenger.
4. The anion exchange membrane of claim 3 wherein the radical scavenger comprises CeO.sub.2, Ce(OH).sub.4, NbO.sub.2, NbO, CeO.sub.2/ZrO.sub.2, CeO.sub.2/NbO.sub.2, TiO.sub.2, HfO.sub.2, BizO.sub.3, BeO, Ta.sub.2O.sub.5, Ce(OH).sub.4/ZrO.sub.2, CeO.sub.2TiC, MnO, MnO.sub.2, MnO.sub.2/SiO.sub.2SO.sub.3H, boehmite, silica-supported Cr, Co or Mn, or mixtures thereof.
5. The anion exchange membrane of claim 1 wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of ##STR00064## and mixtures thereof; wherein R.sub.25, R.sub.26, R.sub.27, and R.sub.28 are each independently H or CH.sub.3; wherein p is 1 or 2; and wherein q is 0 or 1.
6. The anion exchange membrane of claim 1 wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of ##STR00065## and mixtures thereof.
7. The anion exchange membrane of claim 1 wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of ##STR00066## and mixtures thereof.
8. The anion exchange membrane of claim 1 wherein X.sub.1 is ##STR00067## wherein R.sub.30 and R.sub.31 are each independently H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2; wherein Y.sub.1.sup. is HCO.sub.3.sup., OH.sup., I.sup., CF.sub.3SO.sub.3; or ##STR00068## and wherein R.sub.50 is CH.sub.3, CF.sub.3, CH.sub.3CH.sub.2, or CH.sub.3CH.sub.2CH.sub.2.
9. The anion exchange membrane of claim 1 wherein X.sub.2 is ##STR00069## wherein R.sub.30 is H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2.
10. The anion exchange membrane of claim 1 wherein X.sub.2 is a mixture of ##STR00070## wherein R.sub.30 is H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2; and wherein R.sub.32 is C.sub.6H.sub.5.
11. The anion exchange membrane of claim 1, wherein the anion exchange membrane is used in a fuel cell, an electrolyzer, a flow battery, an electrodialyzer, a waste metal recovery system, an electrocatalytic hydrogen production system, a desalinator, a water purifier, a waste water treatment system, an ion exchanger, or a CO.sub.2 separator.
12. The anion exchange membrane of claim 1 wherein the anion exchange membrane comprises a nonporous symmetric dense film membrane, an integrally-skinned asymmetric membrane, a reinforced composite membrane, or a thin film composite membrane.
13. The anion exchange membrane of claim 12 wherein the integrally-skinned asymmetric membrane, the reinforced composite membrane, or the thin film composite membrane comprises a porous substrate material impregnated or coated with the anion exchange polymer.
14. A membrane electrode assembly, comprising: an anion exchange membrane comprising: an anion exchange polymer; and a hydrogen recombination catalyst dispersed in the anion exchange polymer; a cathode comprising a cathode catalyst on a first surface of the anion exchange membrane; and optionally an anode comprising an anode catalyst on a second surface of the anion exchange membrane; wherein the anion exchange polymer comprises a plurality of repeating units of formula (I) ##STR00071## wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of: ##STR00072## ##STR00073## ##STR00074## and mixtures thereof; wherein X.sub.1 is selected from the group consisting of: ##STR00075## and mixtures thereof; wherein X.sub.2 is selected from the group consisting of: ##STR00076## or a mixture of ##STR00077## wherein Ar.sub.1 and Ar.sub.2 are the same or different from each other; wherein Y.sub.1.sup. and Y.sub.2.sup. are anions; wherein R.sub.1-R.sub.28 are each independently hydrogen, a halide, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein R.sub.29-R.sub.31 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein R.sub.32 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl group is optionally substituted with a halide or a positively charged functional group; wherein A is O, S, or NR.sub.100; wherein R.sub.100 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein n is an integer from 10 to 100,000; wherein m is an integer from 5 to 50,000 and the molar ratio of n/m is in a range of 1:1 to 99:1; wherein p is 1, 2, 3, or 4; wherein q is 0, 1, 2, or 3; and wherein tis 1, 2, 3, 4, 5, or 6.
15. The membrane electrode assembly of claim 14 wherein the hydrogen recombination catalyst comprises Pt, Pt supported on carbon silica, titania, or zirconia, PtCo, PtCo supported on carbon, silica, titania, or zirconia, Pd, Pd supported on carbon, silica, titania, or zirconia, PdCo, PdCo supported on carbon, silica, titania, or zirconia, Ru, Ru supported on carbon, silica, titania, or zirconia, RuCo, RuCo supported on carbon, silica, titania, or zirconia, or mixtures thereof.
16. The membrane electrode assembly of claim 14 further comprising a radical scavenger.
17. The membrane electrode assembly of claim 16 wherein the radical scavenger comprises CeO.sub.2, Ce(OH).sub.4, NbO.sub.2, NbO, CeO.sub.2/ZrO.sub.2, CeO.sub.2/NbO.sub.2, TiO.sub.2, HfO.sub.2, Bi.sub.2O.sub.3, BeO, Ta.sub.2O.sub.5, Ce(OH).sub.4/ZrO.sub.2, CeO.sub.2TiC, MnO, MnO.sub.2, MnO.sub.2/SiO.sub.2SO.sub.3H, boehmite, silica-supported Cr, Co or Mn, or mixtures thereof.
18. The membrane electrode assembly of claim 14 further comprising: a cathode porous transport layer adjacent to the cathode; and an anode porous transport layer or an anode catalyst-coated anode porous transport layer adjacent to the second surface of the anion exchange membrane.
19. The membrane electrode assembly of claim 14 wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of ##STR00078## and mixtures thereof.
20. The membrane electrode assembly of claim 14 wherein X.sub.1 is ##STR00079## wherein R.sub.30 and R.sub.31 are each independently H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2; wherein Y.sub.1.sup. is HCO.sub.3.sup., OH.sup., I.sup., CF.sub.3SO.sub.3.sup., or ##STR00080## and wherein R.sub.50 is CH.sub.3, CF.sub.3, CH.sub.3CH.sub.2, or CH.sub.3CH.sub.2CH.sub.2; and wherein X.sub.2 is ##STR00081## wherein R.sub.30 is H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0008]
[0009]
[0010]
[0011]
DESCRIPTION OF THE INVENTION
[0012] Novel composite anion exchange membranes and catalyst coated membranes (CCM) comprising the composite anion exchange membranes for electrolysis, fuel cell, energy storage, and other electrochemical applications have been developed. The H.sub.2 in O.sub.2 content at the anode of the water electrolyzer can be significantly reduced by incorporating the composite anion exchange membrane comprising H.sub.2 recombination catalysts such as Pt particles and optionally a radical scavenger such as CeO.sub.2 into the CCM. The permeating H.sub.2 and O.sub.2 forms H.sub.2O inside the membrane catalyzed by the H.sub.2 recombination catalysts, leading to higher O.sub.2 byproduct gas purity at the anode of the AEM electrolyzer and resolving safety issues. The radical scavenger improves the membrane chemical/electrochemical stability.
[0013] The new type of composite anion exchange membrane comprising H.sub.2 recombination catalysts, including, but not limited to, Pt, Pt supported on carbon, silica, titania, or zirconia, PtCo, PtCo supported on carbon, silica, titania, or zirconia, Pd, Pd supported on carbon, silica, titania, or zirconia, PdCo, PdCo supported on carbon, silica, titania, or zirconia, Ru, Ru supported on carbon, silica, titania, or zirconia, RuCo, RuCo supported on carbon, silica, titania, or zirconia, or mixtures thereof. The composite anion exchange membrane may optionally include a radical scavenger, including, but not limited to, CeO.sub.2, Ce(OH).sub.4, NbO.sub.2, NbO, CeO.sub.2/ZrO.sub.2, CeO.sub.2/NbO.sub.2, TiO.sub.2, HfO.sub.2, Bi.sub.2O.sub.3, BeO, Ta.sub.2O.sub.5, Ce(OH).sub.4/ZrO.sub.2, CeO.sub.2TiC, MnO, MnO.sub.2, MnO.sub.2/SiO.sub.2SO.sub.3H, boehmite, silica-supported Cr, Co or Mn, or mixtures thereof.
[0014] A CCM comprising the composite anion exchange membrane can be prepared by dispersing the H.sub.2 recombination catalysts, such as Pt particles, and optionally a radical scavenger, such as CeO.sub.2, in the anion exchange polymer coating solution to form a composite anion exchange polymer coating solution using high shear mixing and ultrasonication. A thin layer of the composite anion exchange polymer coating solution is coated on one surface of a supporting substrate using any suitable coating methods, for example, knife-coating, Mayer rod-coating, slot-die-coating, gravure coating, inkjet printing, screen printing, curtain printing, spray coating, and the like. The supporting substrate is insoluble in the composite anion exchange polymer coating solution and can be made from any suitable polymer material. Suitable polymer materials include, but are not limited to, polyester such as polyethylene terephthalate (PET), polyimide, poly (ether ether ketone) (PEEK), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer, fluorinated ethylene propylene, polyolefins such as polyethylene (PE), polypropylene (PP), and copolymers of PE and PP, copolymers of tetrafluoroethylene and ethylene, copolymers of tetrafluoroethylene and propylene, polychlorotrifluoroethylene, copolymers of chlorotrifluoroethylene and vinylidene fluoride, copolymers of chlorotrifluoroethylene and ethylene, or combinations thereof. The coated layer is dried to evaporate the solvents and form the composite anion exchange membrane. The drying can be done at any suitable temperature including, but not limited to, at 50 C. to 150 C., or at 50 C. to 120 C., or at 80 C. to 120 C.
[0015] As shown in
[0016] The composite AEM 305 may optionally include a radical scavenger (not shown). Any suitable radical scavenger can be used. Suitable radical scavengers include, but are not limited to, CeO.sub.2, Ce(OH).sub.4, NbO.sub.2, NbO, CeO.sub.2/ZrO.sub.2, CeO.sub.2/NbO.sub.2, TiO.sub.2, HfO.sub.2, Bi.sub.2O.sub.3, BeO, Ta.sub.2O.sub.5, Ce(OH).sub.4/ZrO.sub.2, CeO.sub.2TiC, MnO, MnO.sub.2, MnO.sub.2/SiO.sub.2SO.sub.3H, boehmite, silica-supported Cr, Co or Mn, or mixtures thereof. The catalytic H.sub.2 recombination reaction in the composite AEM 305 and the catalytic reactions in the cathode catalyst layer 325 as shown in in
[0017] The catalyst coated membrane 320 can be made by coating a thin layer of anode catalyst ink 330 on one surface and a thin layer of cathode catalyst ink 325 on the other surface of the composite AEM 305. The anode catalyst ink layer 330 and the cathode catalyst ink layer 325 are dried to form the catalyst coated membrane 320 comprising the composite AEM 305, an anode catalyst layer 330 and a cathode catalyst layer 325. The anode catalyst ink layer and the cathode catalyst ink layer can be dried at any suitable temperature including, but not limited to, at about 30 C. to about 150 C., or at about 30 C. to about 120 C., or at about 40 C. to 120 C.
[0018] In some embodiments, the anode and the cathode catalysts in the anode catalyst layer 330 and the cathode catalyst layer 325 are platinum group metal (PGM) electrocatalysts or PGM-free electrocatalysts. The anode and the cathode catalysts are for oxygen evolution reaction and hydrogen evolution reaction, respectively. The anode and the cathode catalysts should have good electrical conductivity, and good electrocatalytic activity and stability. Suitable PGM cathode catalysts can be selected from, but are not limited to, platinum, ruthenium, osmium, rhodium, palladium, alloys thereof, oxides thereof, carbides thereof, phosphides thereof, their supported catalysts, or combinations thereof. Suitable PGM anode catalysts can be selected from, but are not limited to, iridium, platinum, ruthenium, osmium, rhodium, palladium, alloys thereof, oxides thereof, carbides thereof, phosphides thereof, their supported catalysts, or combinations thereof. Suitable PGM-free cathode catalysts can be selected from, but are not limited to, tin, tungsten, vanadium, cobalt, silver, gold, copper, nickel, molybdenum, iron, chromium, Ni-based alloys such as NiMo, NiAl, NiCr, NiSn, NiCo, NiW, and NiAlMo, metal carbides such as Mo.sub.2C, metal phosphides such as CoP, metal dichalcogenides such as MoSe.sub.2, and mixtures thereof. Suitable PGM-free anode catalysts can be selected from, but are not limited to, tin, tungsten, vanadium, cobalt, silver, gold, copper, nickel, molybdenum, iron, chromium, NiFe alloy, NiMo alloy, spinel Cu.sub.xCo.sub.3xO.sub.3, NiFe layered double hydroxides, NiFe layered double hydroxides on carbon nanotubes, immobilized metal catalyst on conductive supports, NiFeWB layered double hydroxides, NiFeWB layered double hydroxides supported on carbon nanotubes, immobilized metal catalyst on conductive supports, NiFeCeB layered double hydroxides, NiFeCeB layered double hydroxides supported on carbon nanotubes, immobilized metal catalyst on conductive supports, and mixtures thereof.
[0019] An anode porous transport layer 335 and cathode porous transport layer 340 are positioned on the anode catalyst layer 330 and the cathode catalyst layer 325, respectively to form the membrane electrode assembly 300. The anode porous transport layer 335 and the cathode porous transport layer 340 simultaneously transport electrons, heat, and products with minimum voltage, current, thermal, interfacial, and fluidic losses. The cathode porous transport layer 340 can be made from, but is not limited to, stainless steel, nickel meshes, nickel forms, titanium meshes, titanium felts, titanium foams, or carbon-based materials such as non-woven carbon paper, non-woven carbon cloth, or woven carbon cloth. The anode porous transport layer 335 can be made from, but is not limited to, stainless steel, nickel meshes, nickel forms, titanium meshes, titanium felts, or titanium foams.
[0020] The elimination or mitigation of the indirect energy losses arising from gas crossover in the electrolyzers would provide significant energy savings for water electrolysis. Gas permeation through the water electrolyzer will lead to H.sub.2 in O.sub.2 at the anode side of the electrolyzer, which causes a safety hazard and the reduction of the electrolyzer efficiency. The composite AEM in the present invention effectively lowered the H.sub.2 crossover from the cathode stream to the anode stream and prevented the formation of an explosive H.sub.2/O.sub.2 mixture in the anode stream. The H.sub.2 recombination reaction of H.sub.2 and O.sub.2 in the composite AEM results in the formation of water and therefore lowers the H.sub.2 concentration in O.sub.2 in the anode stream.
[0021] One aspect of the invention is an anion exchange membrane. In one embodiment, the anion exchange membrane comprises: an anion exchange polymer; and a hydrogen recombination catalyst dispersed in the anion exchange polymer; wherein the anion exchange polymer comprises a plurality of repeating units of formula (I)
##STR00004##
[0022] wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of:
##STR00005## ##STR00006## ##STR00007## ##STR00008##
[0023] and mixtures thereof;
[0024] wherein X.sub.1 is selected from the group consisting of:
##STR00009##
[0025] and mixtures thereof;
[0026] wherein X.sub.2 is selected from the group consisting of:
##STR00010##
[0027] or a mixture of
##STR00011##
[0028] wherein Ar.sub.1 and Ar.sub.2 are the same or different from each other;
[0029] wherein Y.sub.1.sup. and Y.sub.2.sup. are anions;
[0030] wherein R.sub.1-R.sub.28 are each independently hydrogen, a halide, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group;
[0031] wherein R.sub.29-R.sub.31 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with a halide or a positively charged functional group;
[0032] wherein R.sub.32 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl group is optionally substituted with a halide or a positively charged functional group;
[0033] wherein A is O, S, or NR.sub.100;
[0034] wherein R.sub.100 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group;
[0035] wherein n is an integer from 10 to 100,000;
[0036] wherein m is an integer from 5 to 50,000 and the molar ratio of n/m is in a range of 1:1 to 99:1;
[0037] wherein p is 1, 2, 3, or 4;
[0038] wherein q is 0, 1, 2, or 3; and
[0039] wherein t is 1, 2, 3, 4, 5, or 6.
[0040] In some embodiments, the hydrogen recombination catalyst comprises Pt, Pt supported on carbon, silica, titania, or zirconia, PtCo, PtCo supported on carbon, silica, titania, or zirconia, Pd, Pd supported on carbon, silica, titania, or zirconia, PdCo, PdCo supported on carbon, silica, titania, or zirconia, Ru, Ru supported on carbon, silica, titania, or zirconia, RuCo, RuCo supported on carbon, silica, titania, or zirconia, or mixtures thereof. In some embodiments, the anion exchange membrane further comprises a radical scavenger. Any suitable radical scavenger can be used. Suitable radical scavengers include, but are not limited to, CeO.sub.2, Ce(OH).sub.4, NbO.sub.2, NbO, CeO.sub.2/ZrO.sub.2, CeO.sub.2/NbO.sub.2, TiO.sub.2, HfO.sub.2, Bi.sub.2O.sub.3, BeO, Ta.sub.2O.sub.5, Ce(OH).sub.4/ZrO.sub.2, CeO.sub.2TiC, MnO, MnO.sub.2, MnO.sub.2/SiO.sub.2SO.sub.3H, boehmite, silica-supported Cr, Co or Mn, or mixtures thereof.
[0041] In some embodiments, Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00012##
[0042] and mixtures thereof;
[0043] wherein R.sub.25, R.sub.26, R.sub.27, and R.sub.28 are each independently H or CH.sub.3;
[0044] wherein p is 1 or 2; and
[0045] wherein q is 0 or 1.
[0046] In some embodiments, Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00013##
and mixtures thereof.
[0047] In some embodiments, Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00014##
[0048] and mixtures thereof.
[0049] In some embodiments, X.sub.1 is
##STR00015##
wherein R.sub.30 and R.sub.31 are each independently H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2
[0050] wherein Y.sub.1.sup. is HCO.sub.3.sup., OH.sup., I.sup., CF.sub.3SO.sub.3, or
##STR00016##
[0051] and
[0052] wherein R.sub.50 is CH.sub.3, CF.sub.3, CH.sub.3CH.sub.2, or CH.sub.3CH.sub.2CH.sub.2.
[0053] In some embodiments, X.sub.2 is
##STR00017##
[0054] wherein R.sub.30 is H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2.
[0055] In some embodiments, X.sub.2 is a mixture of
##STR00018##
[0056] wherein R.sub.30 is H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2; and wherein R.sub.32 is C.sub.6H.sub.5.
[0057] The anion exchange polymer comprising a plurality of repeating units of formula (I) may be synthesized by two steps: 1) a superacid catalyzed polyhydroxyalkylation reaction of monomers Ar.sub.1 and Ar.sub.2 with X.sub.1, such as p-terphenyl as Ar.sub.1 and phenanthrene as Ar.sub.2 with N-methyl-.sub.4-piperidone as X.sub.1, to form a neutral precursor polymer; and 2) a Menshutkin reaction to convert the neutral precursor polymer comprising piperidine-based groups to the anion exchange polymer comprising a plurality of repeating units of formula (I) with both piperidinium-based cation groups and piperidine-based groups. Optionally, the anion exchange polymer comprising a plurality of repeating units of formula (I) with piperidine-based groups, piperidinium-based cation groups and negatively charged halide ions is converted to an anion exchange polymer comprising a plurality of repeating units of formula (I) with piperidine-based groups, piperidinium-based cation groups and negatively charged bicarbonate ions by soaking the polymer in sodium bicarbonate or potassium bicarbonate solution before the polymer is made into a membrane.
[0058] The polyhydroxyalkylation reaction of monomers Ar.sub.1 and Ar.sub.2 with monomer X.sub.1 followed by the Menshutkin reaction provides an anion exchange polymer with a polymer backbone free of ether bonds, which results in high chemical stability of the polymer. The incorporation of electron-rich monomers Ar.sub.1 and Ar.sub.2 into the anion exchange polymer provides a hydrophobic polymer backbone, and the incorporation of monomer X.sub.1 into the anion exchange polymer provides the polymer with piperidinium or piperidinium salt-based anion exchange property that helps to achieve stable high OH.sup. conductivity, as well as piperidine-based functional group that is important to reduce the polymer swelling and reduce the gas crossover. The combination of the hydrophobic polymer backbone, the piperidine-based functional group, and alkaline stable piperidinium or piperidinium salt-based cation functional groups provides the novel anion exchange polymer with high OH.sup. conductivity, high chemical stability, high mechanical strength, low swelling in alkaline conditions, low gas crossover, and long-term performance stability. The molar ratio of Ar.sub.1 monomer to Ar.sub.2 monomer can be in a range of 20:1 to 1:20, or in a range of 10:1 to 1:10, or in a range of 5:1 to 1:5. The molar ratio of X1 monomer to Ar.sub.1 and Ar.sub.2 monomers can be in a range of 1.2:1 to 1:1.2, or in a range of 1.1:1 to 1:1.1, or in a range of 1.05:1 to 1:1.05.
[0059] The superacid catalyzed polyhydroxyalkylation reaction can be carried out at 0 C. to 50 C., or at 10 C. to 30 C., or at 20 C. to 30 C. for 2 h to 72 h, or 10 h to 48 h, or 12 to 24 h. Suitable superacid catalysts include, but are not limited to, trifluoromethanesulfonic acid (CF.sub.3SO.sub.3H (TFSA)), methanesulfonic acid (MSA), fluorosulfuric acid (FSO.sub.3H), or mixtures thereof. Solvents for the polyhydroxyalkylation reaction are those that can dissolve one or more of the monomers. Suitable solvents include, but are not limited to, methylene chloride, chloroform, trifluoroacetic acid (TFA), or mixtures thereof.
[0060] The Menshutkin reaction is used to react the neutral precursor polymer comprising piperidine-based groups with an alkyl halide to convert about 50 mol % to 99 mol % of the neutral piperidine-based groups to piperidinium-based cation groups to form the anion exchange polymer comprising a plurality of repeating units of formula (I) with both piperidinium-based cation groups and piperidine-based groups. Suitable alkyl halides include, but are not limited to, alkyl iodides or alkyl bromides. The Menshutkin reaction can be carried out at 10 C. to 80 C., or at 20 C. to 30 C. for 2 h to 72 h, or 10 h to 48 h, or 12 to 24 h. Solvents for the Menshutkin reaction are those that can dissolve the neutral precursor polymer comprising piperidine-based groups. Suitable solvents include, but are not limited to, N-methylpyrrolidone (NMP), N, N-dimethyl acetamide (DMAC), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), 1,3-dioxolane, or mixtures thereof. To synthesize the anion exchange polymer comprising a plurality of repeating units of formula (I) with both piperidinium-based cation groups and piperidine-based groups, the molar ratio of the alkyl halide to the piperidine-based groups of the neutral precursor polymer should be controlled in a range of 0.5/1 to 1:1 for the Menshutkin reaction.
[0061] The anion exchange polymer comprising a plurality of repeating units of formula (I) has a weight average molecular weight in a range of 10,000 to 50,000,000 Daltons, or in a range of 50,000 to 40,000,000 Daltons.
[0062] The anion exchange membrane can be used in fuel cells, electrolyzers, flow batteries, electrodialyzers, waste metal recovery systems, electrocatalytic hydrogen production systems, desalinators, water purifiers, waste water treatment systems, ion exchangers, or CO.sub.2 separators.
[0063] In some embodiments, the anion exchange membrane comprises a nonporous symmetric dense film membrane, an integrally-skinned asymmetric membrane, a reinforced composite membrane, or a thin film composite membrane. By dense we mean that the membrane does not have pores larger than 1 nm.
[0064] In some embodiments, the integrally-skinned asymmetric membrane, the reinforced composite membrane, or the thin film composite membrane comprises a porous substrate material impregnated or coated with the anion exchange polymer. The porous substrate membrane may be prepared from a polymer different from the anion exchange polymer.
[0065] In some embodiments, the nonporous symmetric dense film membrane, the integrally-skinned asymmetric membrane, the reinforced composite membrane, or the thin film composite membrane may be a flat sheet membrane.
[0066] In some embodiments, the nonporous symmetric dense film anion exchange membrane is prepared using a method comprising: 1) preparing a composite anion exchange membrane casting solution by dissolving the anion exchange polymer comprising a plurality of repeating units of formula (I) in a solvent or a solvent mixture, dispersing a H.sub.2 recombination catalyst and optionally a radical scavenger in a solvent or a solvent mixture, and mixing the anion exchange polymer solution with the dispersed H.sub.2 recombination catalyst suspension to form the composite anion exchange membrane casting solution; 2) casting the composite anion exchange membrane casting solution on a nonporous substrate to form a uniform layer of the composite anion exchange membrane casting solution; 3) drying the composite anion exchange membrane casting solution layer to form a dried membrane on the nonporous substrate at 50 C. to 180 C., or at 50 C. to 120 C., or at 80 C. to 120 C.; and optionally 4) ion exchanging the halide anions of the anion exchange polymer in the membrane with hydroxide, bicarbonate, carbonate ions, or a combination thereof if the anion exchange polymer has halide anions before membrane fabrication to form the nonporous symmetric dense film composite anion exchange membrane. The nonporous substrate is removed from the membrane when the membrane is used in a desired application. The solvent used to dissolve the anion exchange polymer can be selected from, but is not limited to, NMP, DMAc, DMF, DMSO, 1,3-dioxolane, acetic acid, trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TFSA), or mixtures thereof. The nonporous substrate used for the fabrication of the nonporous symmetric dense film membrane can be selected from, but is not limited to, glass plate, polymer films made from polymers that are insoluble in the solvent used to dissolve the anion exchange polymer, such as polyester such as polyethylene terephthalate (PET), polyimide, poly (ether ether ketone) (PEEK), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer, fluorinated ethylene propylene, polyolefins such as polyethylene (PE), polypropylene (PP), and copolymers of PE and PP, copolymers of tetrafluoroethylene and ethylene, copolymers of tetrafluoroethylene and propylene, polychlorotrifluoroethylene (PCTFE), copolymers of chlorotrifluoroethylene and vinylidene fluoride, copolymers of chlorotrifluoroethylene and ethylene, or combinations thereof.
[0067] In some embodiments, the integrally-skinned asymmetric anion exchange membrane is prepared using a method comprising: 1) making a composite anion exchange membrane casting solution comprising the anion exchange polymer with formula (I), solvents which are miscible with water and can dissolve the anion exchange polymer, and non-solvents which cannot dissolve the anion exchange polymer, a H.sub.2 recombination catalyst, and optionally a radical scavenger; 2) casting a layer of the composite anion exchange membrane casting solution onto a supporting substrate; 3) evaporating the solvent and non-solvent from the surface of the coated layer and then coagulating the coated layer in a coagulating bath to form the integrally-skinned asymmetric membrane structure; 4) drying the membrane at 50 C. to 150 C., or at 50 C. to 120 C., or at 80 C. to 120 C.; and optionally 5) ion exchanging the halide anions of the anion exchange polymer in the membrane with hydroxide, bicarbonate, carbonate ions, or a combination thereof if the anion exchange polymer has halide anions before membrane fabrication to form the integrally-skinned asymmetric anion exchange membrane. In some embodiments, the supporting substrate is removed from the membrane when the membrane is used in a desired application. In some embodiments, the supporting substrate is part of the final integrally-skinned asymmetric anion exchange membrane. The supporting substrate may comprise polymer films made from polymers that are insoluble in the solvent used to dissolve the anion exchange polymer, such as polyester such as polyethylene terephthalate (PET), polyimide, poly (ether ether ketone) (PEEK), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer, fluorinated ethylene propylene, polyolefins such as polyethylene (PE), polypropylene (PP), and copolymers of PE and PP, copolymers of tetrafluoroethylene and ethylene, copolymers of tetrafluoroethylene and propylene, polychlorotrifluoroethylene (PCTFE), copolymers of chlorotrifluoroethylene and vinylidene fluoride, copolymers of chlorotrifluoroethylene and ethylene, or combinations thereof. The solvents for the preparation of the integrally-skinned asymmetric membrane include, but are not limited to, NMP, DMAc, DMF, DMSO, dioxanes, 1,3-dioxolane, acetic acid, trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TFSA), and mixtures thereof. The non-solvents for the preparation of the integrally-skinned asymmetric membrane include, but are not limited to, acetone, methanol, ethanol, tetrahydrofuran (THF), toluene, n-octane, n-decane, lactic acid, citric acid, isopropanol, and mixtures thereof. The integrally-skinned asymmetric membrane may have a thin nonporous dense layer less than 500 nm on a microporous support layer.
[0068] In some embodiments, the reinforced composite anion exchange membrane is prepared using a method comprising: 1) making a composite anion exchange membrane solution comprising the anion exchange polymer with formula (I), solvents which are miscible with water and can dissolve the anion exchange polymer, and non-solvents which cannot dissolve the anion exchange polymer, a H.sub.2 recombination catalyst, and optionally a radical scavenger; 2) impregnating a porous matrix support membrane with the composite anion exchange membrane to fill the pores with the solution via dip-coating, soaking, spraying, painting, or other known conventional solution impregnating method; 3) drying the impregnated membrane at 50 C. to 150 C., or at 50 C. to 120 C., or at 80 C. to 120 C.; and optionally 4) ion exchanging the halide anions of the anion exchange polymer in the pores of the reinforced membrane with hydroxide, bicarbonate, carbonate ions, or a combination thereof if the anion exchange polymer has halide anions before membrane fabrication to form the reinforced composite anion exchange membrane with interconnected anion exchange polymer domains in a porous matrix. The solvents for the preparation of the thin film composite anion exchange membrane include, but are not limited to, NMP, DMAc, DMF, DMSO, dioxanes, 1,3-dioxolane, acetic acid, trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TFSA), and mixtures thereof. The porous matrix should have good thermal stability (stable up to at least 120 C.), high stability under high pH condition (e.g., pH greater than 8), high resistance to oxidizing and reducing conditions (insoluble and no performance drop under oxidizing and reducing conditions), high mechanical strength (no dimensional change under the system operation conditions), as well as other factors dictated by the operating conditions for electrochemical reactions. The porous matrix must be compatible with the electrochemical cell chemistry and meet the mechanical demands of cell stacking or winding assembly operations.
[0069] The polymers suitable for the preparation of the porous matrix can be selected from, but not limited to, polyolefins such as polyethylene and polypropylene, polyamide such as Nylon 6 and Nylon 6,6, polyester, cellulose acetate, polybenzimidazole, fluorocarbon-based polymer such as PTFE, PCTFE, and PVDF, polycarbonate, cellulose, or combinations thereof. These polymers provide a range of properties such as low cost, high stability in alkaline water, good mechanical stability, and ease of processability for porous matrix fabrication.
[0070] The porous matrix can either a non-woven matrix or a woven matrix and have either a symmetric porous structure or an asymmetric porous structure. The porous matrix can be formed by an electrospinning process, a phase inversion membrane fabrication approach followed by direct air drying, or by phase inversion followed by solvent exchange methods. The porous matrix also can be fabricated via a dry processing of thermoplastic polyolefins or a wet processing of thermoplastic olefins. The dry processing of thermoplastic polyolefins utilizes extrusion to bring the polymer above its melting point and form it into the desired shape. Subsequent annealing and stretching processes may also be done to increase the crystallinity and orientation and dimension of the pores. The wet processing of polyolefin porous matrix is done with the aid of a hydrocarbon liquid or low molecular weight oil mixed with the polymer resin or a mixture of the polymer resin and inorganic nanoparticles in the melt phase. The melt mixture is extruded through a die similar to the dry processed separators.
[0071] The thickness of the porous matrix can be in a range of 10-400 micrometers, or a range of 10-200 micrometers, or a range of 10-100 micrometers, or a range of 20-100 micrometers. The pore size of the porous matrix can be in a range of 1 micrometer to 500 micrometers, or a range of 10 micrometer to 200 micrometers, or a range of 50 micrometers to 100 micrometer.
[0072] Another aspect of the invention is a membrane electrode assembly. In one embodiment, the membrane electrode assembly comprises: an anion exchange membrane comprising: an anion exchange polymer; and a hydrogen recombination catalyst dispersed in the anion exchange polymer; a cathode comprising a cathode catalyst on a first surface of the anion exchange membrane; and optionally an anode comprising an anode catalyst on a second surface of the anion exchange membrane; wherein the anion exchange polymer comprises a plurality of repeating units of formula (I)
##STR00019##
[0073] wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of:
##STR00020## ##STR00021## ##STR00022##
[0074] and mixtures thereof;
[0075] wherein X.sub.1 is selected from the group consisting of:
##STR00023##
[0076] and mixtures thereof;
[0077] wherein X.sub.2 is selected from the group consisting of:
##STR00024##
[0078] or a mixture of
##STR00025##
[0079] wherein Ar.sub.1 and Ar.sub.2 are the same or different from each other;
[0080] wherein Y.sub.1.sup. and Y.sub.2.sup. are anions;
[0081] wherein R.sub.1-R.sub.28 are each independently hydrogen, a halide, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group;
[0082] wherein R.sub.29-R.sub.31 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with a halide or a positively charged functional group;
[0083] wherein R.sub.32 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl group is optionally substituted with a halide or a positively charged functional group;
[0084] wherein A is O, S, or NR.sub.100;
[0085] wherein R.sub.100 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group;
[0086] wherein n is an integer from 10 to 100,000;
[0087] wherein m is an integer from 5 to 50,000 and the molar ratio of n/m is in a range of 1:1 to 99:1;
[0088] wherein p is 1, 2, 3, or 4;
[0089] wherein q is 0, 1, 2, or 3; and
[0090] wherein tis 1, 2, 3, 4, 5, or 6.
[0091] In some embodiments, the hydrogen recombination catalyst comprises Pt, Pt supported on carbon, silica, titania, or zirconia, PtCo, PtCo supported on carbon, silica, titania, or zirconia, Pd, Pd supported on carbon, silica, titania, or zirconia, PdCo, PdCo supported on carbon, silica, titania, or zirconia, Ru, Ru supported on carbon, silica, titania, or zirconia, RuCo, RuCo supported on carbon, silica, titania, or zirconia, or mixtures thereof.
[0092] In some embodiments, the anion exchange membrane further comprises a radical scavenger. Any suitable radical scavenger can be used. Suitable radical scavengers include, but are not limited to, CeO.sub.2, Ce(OH).sub.4, NbO.sub.2, NbO, CeO.sub.2/ZrO.sub.2, CeO.sub.2/NbO.sub.2, TiO.sub.2, HfO.sub.2, Bi.sub.2O.sub.3, BeO, Ta.sub.2O.sub.5, Ce(OH).sub.4/ZrO.sub.2, CeO.sub.2TiC, MnO, MnO.sub.2, MnO.sub.2/SiO.sub.2SO.sub.3H, boehmite, silica-supported Cr, Co or Mn, or mixtures thereof.
[0093] In some embodiments, the membrane electrode assembly further comprises: a cathode porous transport layer adjacent to the cathode; and an anode porous transport layer or an anode catalyst-coated anode porous transport layer adjacent to the second surface of the anion exchange membrane.
[0094] In some embodiments, Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00026##
[0095] and mixtures thereof.
[0096] In some embodiments, X.sub.1 is
##STR00027##
[0097] wherein R.sub.30 and R.sub.31 are each independently H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2;
[0098] wherein Y.sub.1.sup. is HCO.sub.3.sup., OH.sup., I.sup., CF.sub.3SO.sub.3.sup., or
##STR00028##
[0099] and
[0100] wherein R.sub.50 is CH.sub.3, CF.sub.3, CH.sub.3CH.sub.2, or CH.sub.3CH.sub.2CH.sub.2;
[0101] and wherein X.sub.2 is
##STR00029##
[0102] wherein R.sub.30 is H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2.
[0103] In some embodiments, the anode and the cathode catalysts are platinum group metal (PGM) electrocatalysts or PGM-free electrocatalysts. The anode and the cathode catalysts are for oxygen evolution reaction and hydrogen evolution reaction, respectively. The term platinum group metal (PGM) means the six noble, precious metallic elements including ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt).
[0104] In some embodiments, unsupported or supported iridium (Ir) based PGM electrocatalysts are used for the oxygen evolution reaction (OER) on the anode and platinum (Pt) or carbon supported platinum electrocatalyst (Pt/C) is used for the hydrogen evolution reaction (HER) on the cathode for AEM water electrolysis. Both Ir and Pt based PGM catalysts are very expensive and scarce. The anode and the cathode catalysts should have good electrical conductivity, and good electrocatalytic activity and stability. In some embodiments, PGM-free electrocatalysts are used for OER and/or HER for AEM water electrolysis. Suitable cathode catalysts can be selected from, but are not limited to, Ni-based alloys such as NiMo, NiAl, NiCr, NiSn, NiCo, NiW, and NiAlMo, metal carbides such as Mo.sub.2C, metal phosphides such as CoP, metal dichalcogenides such as MoSe.sub.2, and mixtures thereof. Suitable anode catalysts can be selected from, but are not limited to, NiFe alloy, Ni-Mo alloy, spinel Cu.sub.xCo.sub.3xO.sub.3, NiFeWB layered double hydroxide, NiFeCeB layered double hydroxide, NiFeCoB layered double hydroxide, NiFe layered double hydroxide nanoplates on carbon nanotubes, immobilized metal catalyst on conductive supports, and mixtures thereof.
[0105] In some embodiments, the anode comprising an anode catalyst on a first surface of the anion exchange membrane is formed by coating an anode catalyst ink on the first surface of the anion exchange membrane via meniscus coating, knife coating, spray coating, slot die coating, Mayer rod coating, gravure coating, comma coating, painting, inkjet printing, curtain printing, or other known conventional ink coating technologies, followed by drying the coated anion exchange membrane.
[0106] In some embodiments, the cathode comprising a cathode catalyst on a second surface of the anion exchange membrane is formed by coating a cathode catalyst ink on the second surface of the anion exchange membrane via meniscus coating, knife coating, spray coating, slot die coating, Mayer rod coating, gravure coating, comma coating, painting, inkjet printing, curtain printing, or other known conventional ink coating technologies, followed by drying the coated anion exchange membrane.
[0107] In some embodiments, the anode catalyst ink comprises the anode catalyst, an OH.sup. exchange ionomer as a binder, and a solvent. In some embodiments, the cathode catalyst ink comprises the cathode catalyst, an OH.sup. exchange ionomer as a binder, and a solvent. The OH exchange ionomer binder creates OH.sup. transport pathways between the membrane and the reaction sites within the electrodes and thus drastically improves the utilization of the electrocatalyst particles while reducing the internal resistance. The OH.sup. exchange ionomer binder can have a chemical structure similar to the anion exchange polymer described above, so that the binder will allow low interfacial resistance and similar expansion in contact with water to avoid catalyst delamination, but OH.sup. conductivity and high oxygen and hydrogen permeance. The solvent can be selected from, but is not limited to, water, alcohol, or a mixture thereof.
[0108] The anode gas diffusion layer and the cathode gas diffusion layer simultaneously transport electrons, heat, and products with minimum voltage, current, thermal, interfacial, and fluidic losses. The cathode gas diffusion layer can be made from, but is not limited to, stainless steel, titanium meshes, titanium felts, titanium foams, or carbon-based materials such as non-woven carbon paper, non-woven carbon cloth, or woven carbon cloth. The anode gas diffusion layer can be made from, but is not limited to, stainless steel, titanium meshes, titanium felts, or titanium foams.
EXAMPLES
[0109] The following examples are provided to illustrate one or more preferred embodiments of the invention but are not limited embodiments thereof. Numerous variations can be made to the following examples that lie within the scope of the invention.
Example 1
[0110] Preparation of composite anion exchange membrane (abbreviated as PTPPB-PTPP/Pt/CeO.sub.2 composite AEM) comprising poly (p-terphenyl-phenanthrene-N,N-dimethyl-4-piperidinium bicarbonate)-co-poly (p-terphenyl-phenanthrene-N-methyl-4-piperidine) anion exchange polymer (abbreviated as PTPPB-PTPP), Pt black H.sub.2 recombination catalyst, and CeO.sub.2 radical scavenger
[0111] Terphenyl (103.6 g, 450 mmol), phenanthrene (8.9 g, 50 mmol) and 1-methyl-4-piperidone (62.2 g, 550 mmol) were mixed with 400 mL of dichloromethane and cooled in icy water to 0 C. To the stirred mixture, trifluoroacetic acid (60 mL) and trifluoromethanesulfonic acid (400 mL) were added dropwise consecutively under stirring. The mixture was stirred for 11 hours while kept at 0 C. The reaction mixture was blended with water to generate a slurry. The slurry was filtered and rinsed with water, after which the filter cake was soaked in water containing sodium hydroxide overnight. The mixture was again filtered, and the filter cake was washed with water until pH neutral. The obtained solid poly (p-terphenyl-phenanthrene-N-methyl-4-piperidine) (abbreviated as PTPP) precursor polymer was then dried at 60 C. overnight, followed by drying under vacuum at 80 C. overnight.
[0112] The obtained PTPP polymer (about 500 mmol of N-methyl-4-piperidine units) was dissolved in 1.6 L of dimethyl sulfoxide containing 40 mL of trifluoroacetic acid. To the solution, iodomethane (750 mmol) and anhydrous potassium carbonate were added. While protected from light, the mixture was stirred for 24 hours. The reaction mixture was poured in KHCO.sub.3 aqueous solution. The obtained mixture was filtered, and the filter cake was washed with KHCO.sub.3 aqueous solution and water several times until pH neutral. The obtained solid was dried at 60 C. for at least 24 h to obtain dried poly (p-terphenyl-phenanthrene-N,N-dimethyl-4-piperidinium bicarbonate)-co-poly (p-terphenyl-phenanthrene-N-methyl-4-piperidine) (abbreviated as PTPPB-PTPP) anion exchange polymer. .sup.1H NMR analysis result for the
[0113] PTPPB-PTPP polymer confirmed that the polymer had 83 mol % of N,N-dimethyl-4-piperidinium bicarbonate functional groups converted from the N-methyl-4-piperidine functional groups on the PTPP precursor polymer and had 17 mol % of unconverted N-methyl-4-piperidine functional groups.
[0114] 12.5 g PTPPB-PTPP polymer was dissolved in 50 g of dimethyl sulfoxide (DMSO) and 5.0 g of trifluoroacetic acid (TFA) by stirring for about 5-6 h at 60 C. to form a PTPPB-PTPP polymer solution. 0.50 g of Pt black, 0.089 g of CeO.sub.2 nanoparticles, and 75.0 g of DMSO solvent were mixed together in a glass jar using a sonic bath for about 5 min to form a Pt/CeO.sub.2 suspension. Then PTPPB-PTPP polymer solution prepared above was added to the Pt/CeO.sub.2 suspension and the mixture of PTPPB-PTPP/Pt/CeO.sub.2 was further mixed using a high shear mixer and a sonication probe. 48.0 g of additional PTPPB-PTPP polymer, 30.0 g of ethanol and 10.0 g of TFA were added to the mixture of PTPPB-PTPP/Pt/CeO.sub.2 and stirred for 1-2 h at 60 C., and then 12 h at RT to form the PTPPB-PTPP/Pt/CeO.sub.2 composite anion exchange membrane casting solution. The casting solution was filtered through a 400 m filter kept overnight to degas.
[0115] The degassed PTPPB-PTPP/Pt/CeO2 composite anion exchange membrane casting solution was cast onto a nonporous polyester substrate using a casting knife and dried at 80 C. to form PTPPB-PTPP/Pt/CeO.sub.2 composite anion exchange membrane (abbreviated as PTPPB-PTPP/Pt/CeO.sub.2 composite AEM).
Example 2
[0116] Preparation of 2-layer catalyst coated membrane (CCM) comprising 40% Pt/C cathode catalyst coating layer on one surface of the PTPPB-PTPP/Pt/CeO.sub.2 composite AEM (abbreviated as Pt-C/PTPPB-PTPP/Pt/CeO.sub.2 CCM)
[0117] A 2-layer CCM comprising 40% Pt/C cathode catalyst coating layer on one surface of the PTPPB-PTPP/Pt/CeO.sub.2 composite AEM was prepared by a direct wet coating method using a Mayer rod to coat a 40% Pt/C cathode hydrogen evolution reaction (HER) catalyst ink directly on one surface of the PTPPB-PTPP/Pt/CeO.sub.2 composite AEM. A 40% Pt/C cathode catalyst ink was prepared by mixing the 40% Pt/C catalyst and PTPPB-PTPP anion exchange polymer as an ionomer in ultra-pure water and alcohol such as ethanol. The mixture was finely dispersed using a combination of mixing and ultrasonicating. The Pt/C ink was coated onto one surface of the PTPPB-PTPP/Pt/CeO.sub.2 composite AEM using the Mayer rod for only about 5-10 min and then dried at 60-100 C. to form the 2-layer CCM comprising 40% Pt/C cathode catalyst coating layer on one surface of the PTPPB-PTPP/Pt/CeO.sub.2 composite AEM.
Comparative Example 1
[0118] Preparation of anion exchange membrane (abbreviated as PTPPB-PTPP AEM) comprising poly (p-terphenyl-phenanthrene-N,N-dimethyl-4-piperidinium bicarbonate)-co-poly (p-terphenyl-phenanthrene-N-methyl-4-piperidine) anion exchange polymer (abbreviated as PTPPB-PTPP)
[0119] 12.5 g PTPPB-PTPP polymer was dissolved in 50 g of dimethyl sulfoxide (DMSO) and 5.0 g of trifluoroacetic acid (TFA) by stirring for about 5-6 h at 60 C. to form a PTPPB-PTPP polymer casting solution. The casting solution was filtered through a 400 m filter kept overnight to degas.
[0120] The degassed PTPPB-PTPP anion exchange membrane casting solution was cast onto a nonporous polyester substrate using a casting knife and dried at 80 C. to form PTPPB-PTPP anion exchange membrane (abbreviated as PTPPB-PTPP AEM).
Comparative Example 2
[0121] Preparation of 2-layer catalyst coated membrane (CCM) comprising 40% Pt/C cathode catalyst coating layer on one surface of the PTPPB-PTPP AEM (abbreviated as Pt-C/PTPPB-PTPP CCM)
[0122] A 2-layer CCM comprising 40% Pt/C cathode catalyst coating layer on one surface of the PTPPB-PTPP AEM prepared in Comparative Example 1 was prepared by a direct wet coating method using a Mayer rod to coat a 40% Pt/C cathode hydrogen evolution reaction (HER) catalyst ink directly on one surface of the PTPPB-PTPP AEM. A 40% Pt/C cathode catalyst ink was prepared by mixing the 40% Pt/C catalyst and PTPPB-PTPP anion exchange polymer as an ionomer in ultra-pure water and alcohol such as ethanol. The mixture was finely dispersed using a combination of mixing and ultrasonicating. The Pt/C ink was coated onto one surface of the PTPPB-PTPP AEM using the Mayer rod for only about 5-10 min and then dried at 60-100 C. to form the 2-layer CCM comprising 40% Pt/C cathode catalyst coating layer on one surface of the PTPPB-PTPP AEM.
Example 3
[0123] Water electrolysis performance and H.sub.2 crossover study on Pt-C/PTPPB-PTPP/Pt/CeO.sub.2 CCM and PTPPB-PTPP CCM
[0124] The water electrolysis performance and H.sub.2 crossover of the 2-layer Pt-C/PTPPB-PTPP/Pt/CeO.sub.2 CCM comprising 40% Pt/C cathode catalyst coating layer on one surface of the PTPPB-PTPP/Pt/CeO.sub.2 composite AEM prepared in Example 2 and the 2-layer Pt-C/PTPPB-PTPP CCM comprising 40% Pt/C cathode catalyst coating layer on one surface of the PTPPB-PTPP AEM prepared in Comparative Example 2 were evaluated using a single water electrolysis cell at atmospheric pressure in a Scribner unit. The 2-layer Pt-C/PTPPB-PTPP/Pt/CeO.sub.2 CCM and the 2-layer Pt-C/PTPPB-PTPP CCM were sandwiched between a carbon paper (cathode PTL) and a 2-layer NiFeCeBO.sub.x anode O.sub.2 evolution catalyst-coated porous transport layer (PTL), respectively, to form membrane electrode assemblies (MEAs) inside the testing cell.
[0125] A water electrolysis test station (Scribner 600 electrolyzer test system), modified for testing with potassium hydroxide feed, was used to evaluate the water electrolysis performance of the membrane electrode assemblies (MEAs) comprising the 2-layer Pt-C/PTPPB-PTPP/Pt/CeO.sub.2 CCM or 2-layer Pt-C/PTPPB-PTPP CCM in a single electrolyzer cell with an active membrane area of 5 cm.sup.2. The test station included an integrated power supply, a potentiostat, an impedance analyzer for electrochemical impedance spectroscopy (EIS) and high-frequency resistance (HFR), and real-time sensors for product flow rate and cross-over monitoring. The testing was conducted at 55 C. under 15 psig pressure with a 1 wt % KOH feed supplied to the anode side of the test cell. The polarization curves as shown in
SPECIFIC EMBODIMENTS
[0126] While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.
[0127] A first embodiment of the invention is a composition comprising an anion exchange polymer; and a hydrogen recombination catalyst dispersed in the anion exchange polymer; wherein the anion exchange polymer comprises a plurality of repeating units of formula (I)
##STR00030##
[0128] wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00031## ##STR00032## ##STR00033##
[0129] and mixtures thereof; wherein X.sub.1 is selected from the group consisting of
##STR00034##
[0130] and mixtures thereof; wherein X.sub.2 is selected from the group consisting of
##STR00035##
[0131] or a mixture of
##STR00036##
[0132] wherein Ar.sub.1 and Ar.sub.2 are the same or different from each other; wherein Y.sub.1.sup. and Y.sub.2.sup. are anions; wherein R.sub.1-R.sub.28 are each independently hydrogen, a halide, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein R.sub.29-R.sub.31 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein R.sub.32 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl group is optionally substituted with a halide or a positively charged functional group; wherein A is O, S, or NR.sub.100; wherein R.sub.100 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein n is an integer from 10 to 100,000; wherein m is an integer from 5 to 50,000 and the molar ratio of n/m is in a range of 11 to 991; wherein p is 1, 2, 3, or 4; wherein q is 0, 1, 2, or 3; and wherein t is 1, 2, 3, 4, 5, or 6. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the hydrogen recombination catalyst comprises Pt, Pt supported on carbon, silica, titania, or zirconia, PtCo, PtCo supported on carbon, silica, titania, or zirconia, Pd, Pd supported on carbon, silica, titania, or zirconia, PdCo, PdCo supported on carbon, silica, titania, or zirconia, Ru, Ru supported on carbon, silica, titania, or zirconia, RuCo, RuCo supported on carbon, silica, titania, or zirconia, or mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising a radical scavenger. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the radical scavenger comprises CeO.sub.2, Ce(OH).sub.4, NbO.sub.2, NbO, CeO.sub.2/ZrO.sub.2, CeO.sub.2/NbO.sub.2, TiO.sub.2, HfO.sub.2, Bi.sub.2O.sub.3, BeO, Ta.sub.2O.sub.5, Ce(OH).sub.4/ZrO.sub.2, CeO.sub.2TiC, MnO, MnO.sub.2, MnO.sub.2/SiO.sub.2SO.sub.3H, boehmite, silica-supported Cr, Co or Mn, or mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00037##
[0133] and mixtures thereof;
[0134] wherein R.sub.25, R.sub.26, R.sub.27, and R.sub.28 are each independently H or CH.sub.3; wherein p is 1 or 2; and wherein q is 0 or 1. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00038##
[0135] and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00039##
[0136] and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein X.sub.1 is
##STR00040##
[0137] wherein R.sub.30 and R.sub.31 are each independently H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2; wherein Y.sub.1.sup. is HCO.sub.3.sup., OH.sup., I.sup., CF.sub.3SO.sub.3.sup., or
##STR00041##
[0138] and wherein R.sub.50 is CH.sub.3, CF.sub.3, CH.sub.3CH.sub.2, or CH.sub.3CH.sub.2CH.sub.2. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein X.sub.2 is
##STR00042##
[0139] wherein R.sub.30 is H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein X.sub.2 is a mixture of
##STR00043##
[0140] wherein R.sub.30 is H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2; and wherein R.sub.32 is C.sub.6H.sub.5. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the anion exchange membrane is used in a fuel cell, an electrolyzer, a flow battery, an electrodialyzer, a waste metal recovery system, an electrocatalytic hydrogen production system, a desalinator, a water purifier, a waste water treatment system, an ion exchanger, or a CO.sub.2 separator. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the anion exchange membrane comprises a nonporous symmetric dense film membrane, an integrally-skinned asymmetric membrane, a reinforced composite membrane, or a thin film composite membrane. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the integrally-skinned asymmetric membrane, the reinforced composite membrane, or the thin film composite membrane comprises a porous substrate material impregnated or coated with the anion exchange polymer.
[0141] A second embodiment of the invention is a system comprising an anion exchange membrane comprising an anion exchange polymer; and a hydrogen recombination catalyst dispersed in the anion exchange polymer; a cathode comprising a cathode catalyst on a first surface of the anion exchange membrane; and optionally an anode comprising an anode catalyst on a second surface of the anion exchange membrane; wherein the anion exchange polymer comprises a plurality of repeating units of formula (I)
##STR00044##
[0142] wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00045## ##STR00046## ##STR00047## ##STR00048##
[0143] and mixtures thereof; wherein X.sub.1 is selected from the group consisting of
##STR00049##
[0144] and mixtures thereof; wherein X.sub.2 is selected from the group consisting of
##STR00050##
[0145] or a mixture of
##STR00051##
[0146] wherein Ar.sub.1.sup. and Ar.sub.2.sup. are the same or different from each other; wherein Y.sub.1.sup. and Y.sub.2.sup. are anions; wherein R.sub.1-R.sub.28 are each independently hydrogen, a halide, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein R.sub.29-R.sub.31 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein R.sub.32 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl group is optionally substituted with a halide or a positively charged functional group; wherein A is O, S, or NR.sub.100; wherein R.sub.100 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group; wherein n is an integer from 10 to 100,000; wherein m is an integer from 5 to 50,000 and the molar ratio of n/m is in a range of 11 to 991; wherein p is 1, 2, 3, or 4; wherein q is 0, 1, 2, or 3; and wherein t is 1, 2, 3, 4, 5, or 6. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the hydrogen recombination catalyst comprises Pt, Pt supported on carbon silica, titania, or zirconia, PtCo, PtCo supported on carbon, silica, titania, or zirconia, Pd, Pd supported on carbon, silica, titania, or zirconia, PdCo, PdCo supported on carbon, silica, titania, or zirconia, Ru, Ru supported on carbon, silica, titania, or zirconia, RuCo, RuCo supported on carbon, silica, titania, or zirconia, or mixtures thereof.
[0147] An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising a radical scavenger. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the radical scavenger comprises CeO.sub.2, Ce(OH).sub.4, NbO.sub.2, NbO, CeO.sub.2/ZrO.sub.2, CeO.sub.2/NbO.sub.2, TiO.sub.2, HfO.sub.2, Bi.sub.2O.sub.3, BeO, Ta.sub.2O.sub.5, Ce(OH).sub.4/ZrO.sub.2, CeO.sub.2TiC, MnO, MnO.sub.2, MnO.sub.2/SiO.sub.2SO.sub.3H, boehmite, silica-supported Cr, Co or Mn, or mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising a cathode porous transport layer adjacent to the cathode; and an anode porous transport layer or an anode catalyst-coated anode porous transport layer adjacent to the second surface of the anion exchange membrane. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of
##STR00052##
[0148] and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein X.sub.1 is
##STR00053##
[0149] wherein R.sub.30 and R.sup.31 are each independently H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2; wherein Y.sub.1.sup. is HCO.sub.3.sup., OH.sup., I.sup., CF.sub.3SO.sub.3.sup., or
##STR00054##
[0150] and wherein R.sub.50 is CH.sub.3, CF.sub.3, CH.sub.3CH.sub.2, or CH.sub.3CH.sub.2CH.sub.2; and wherein X.sub.2 is
##STR00055##
[0151] wherein R.sub.30 is H, CH.sub.3, CH.sub.2CH.sub.3, CH(CH.sub.3).sub.2, C(CH.sub.3).sub.3, CH.sub.2C.sub.6H.sub.5, or CH.sub.2CH(CH.sub.3).sub.2.
[0152] Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.
[0153] In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.