CA2431055A1 - Cation/proton-conducting ceramic membrane based on a hydroxysilyl acid, its production and use - Google Patents
Cation/proton-conducting ceramic membrane based on a hydroxysilyl acid, its production and use Download PDFInfo
- Publication number
- CA2431055A1 CA2431055A1 CA002431055A CA2431055A CA2431055A1 CA 2431055 A1 CA2431055 A1 CA 2431055A1 CA 002431055 A CA002431055 A CA 002431055A CA 2431055 A CA2431055 A CA 2431055A CA 2431055 A1 CA2431055 A1 CA 2431055A1
- Authority
- CA
- Canada
- Prior art keywords
- membrane
- acid
- hydroxysilyl
- conducting
- proton
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 113
- 239000000919 ceramic Substances 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 title claims description 54
- -1 hydroxysilyl Chemical group 0.000 title claims description 53
- 150000001768 cations Chemical class 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000446 fuel Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract 3
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 39
- 239000002131 composite material Substances 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- 239000004020 conductor Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 150000004703 alkoxides Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- WYTQXLFLAMZNNZ-UHFFFAOYSA-N 3-trihydroxysilylpropane-1-sulfonic acid Chemical compound O[Si](O)(O)CCCS(O)(=O)=O WYTQXLFLAMZNNZ-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 150000001462 antimony Chemical class 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical class [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 4
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 claims description 3
- FNSCAVNJPDIARO-UHFFFAOYSA-N 4-trihydroxysilylbutylphosphonic acid Chemical compound O[Si](O)(O)CCCCP(O)(O)=O FNSCAVNJPDIARO-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000000909 electrodialysis Methods 0.000 claims description 3
- 239000005445 natural material Substances 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 2
- 229910052593 corundum Inorganic materials 0.000 claims 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims 2
- 230000003100 immobilizing effect Effects 0.000 claims 2
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 claims 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims 2
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 claims 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 2
- 239000007787 solid Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- GLHZKJCFBILGDI-UHFFFAOYSA-N O[SiH2]S(O)(=O)=O Chemical compound O[SiH2]S(O)(=O)=O GLHZKJCFBILGDI-UHFFFAOYSA-N 0.000 abstract 1
- BNPYHLZBQKRNDI-UHFFFAOYSA-N hydroxysilylphosphonic acid Chemical compound O[SiH2]P(O)(O)=O BNPYHLZBQKRNDI-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- TTZYZLZAQZRYFC-UHFFFAOYSA-N 3-trihydroxysilylpropane-1-thiol Chemical compound O[Si](O)(O)CCCS TTZYZLZAQZRYFC-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Inorganic materials [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 1
- HPGNWTADBNFFOQ-UHFFFAOYSA-N trihydroxysilylmethylphosphonic acid Chemical compound O[Si](O)(O)CP(O)(O)=O HPGNWTADBNFFOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical class [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0048—Inorganic membrane manufacture by sol-gel transition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/0215—Silicon carbide; Silicon nitride; Silicon oxycarbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/04—Glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B01J35/39—
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- B01J35/58—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/02—Polysilicates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a cation-conducting or proton-conducting ceramic membrane, a method for the production thereof and the use of the same. The inventive membrane represents a novel category of solid proton-conducting membranes, and is based on a porous and flexible ceramic membrane described in patent application PCT/EP98/05939. Said membrane is infiltrated by a proton-conducting substance, and is then dried and consolidated in such away that the end result is an impermeable, cation-conducting or proton-conducting membrane.
The proton-conducting substance is a hydroxysilylsulfonic acid or a hydroxysilylphosphonic acid which is integrated into an inorganic network, e.g. SiO2. The ceramic membrane thus remains flexible and can be used without a problem as a membrane in a fuel cell.
The proton-conducting substance is a hydroxysilylsulfonic acid or a hydroxysilylphosphonic acid which is integrated into an inorganic network, e.g. SiO2. The ceramic membrane thus remains flexible and can be used without a problem as a membrane in a fuel cell.
Description
:*°- CA 02431055 2003-06-12 "0.Z. 5696 Cation/~proton-conducting ceramic membrane based on a hvdroxvsilyl acid, its production and use The present invention relates to a cation- and/or proton-conducting membrane which comprises an immobilized hydroxysilyl acid or salt thereof, to a process for producing it, and to its use.
At the present time in the field of fuel cells for the automotive application sector, i.e., for fuel cell operating temperatures of below 200 °C, the materials used comprise exclusively polymers to or filled polymers (composites). The membranes used most frequently are those made from polymers, such as Nafion~ (DuPont, fluorinated framework with a sulfonic acid functionality), and related systems. Another example of a purely organic, proton-conducting polymer are the sulfonated polyether ketones that are described, inter alia, by Hoechst in EP
0 574 791 B1. All of these polymers have the disadvantage that the proton conductivity decreases sharply as the air humidity falls. Accordingly, these membranes have to be swollen in water before being used in the fuel cell. At high temperatures, which are unavoidable in the reformate fuel cell or direct methanol fuel cell (DMFC), these systems can no longer be used, or can be used only with restrictions, since the membrane may easily dry out, with the stated consequences for the proton conductivity.
A further problem arising in connection with the use of polymer membranes in a DMFC is their great permeability for methanol. Because of the crossover of methanol through the membrane to the cathode side, the fuel cell frequently suffers severe performance detractions.
For all these reasons the use of organic polymer membranes for the reformate fuel cell or DMFC is not ideal, and for any widespread use of fuel cells it is necessary to find new solutions.
Although inorganic proton conductors as well are known from the literature (see, for example, "Proton Conductors", P. Colomban, Cambridge University Press, 1992), the majority of them have conductivities which are too low (such as, for example, the zirconium phosphates) or else the conductivity reaches technically useful levels only at high temperatures, typically at ', ~" CA 02431055 2003-06-12 b.Z. 5696-WO
At the present time in the field of fuel cells for the automotive application sector, i.e., for fuel cell operating temperatures of below 200 °C, the materials used comprise exclusively polymers to or filled polymers (composites). The membranes used most frequently are those made from polymers, such as Nafion~ (DuPont, fluorinated framework with a sulfonic acid functionality), and related systems. Another example of a purely organic, proton-conducting polymer are the sulfonated polyether ketones that are described, inter alia, by Hoechst in EP
0 574 791 B1. All of these polymers have the disadvantage that the proton conductivity decreases sharply as the air humidity falls. Accordingly, these membranes have to be swollen in water before being used in the fuel cell. At high temperatures, which are unavoidable in the reformate fuel cell or direct methanol fuel cell (DMFC), these systems can no longer be used, or can be used only with restrictions, since the membrane may easily dry out, with the stated consequences for the proton conductivity.
A further problem arising in connection with the use of polymer membranes in a DMFC is their great permeability for methanol. Because of the crossover of methanol through the membrane to the cathode side, the fuel cell frequently suffers severe performance detractions.
For all these reasons the use of organic polymer membranes for the reformate fuel cell or DMFC is not ideal, and for any widespread use of fuel cells it is necessary to find new solutions.
Although inorganic proton conductors as well are known from the literature (see, for example, "Proton Conductors", P. Colomban, Cambridge University Press, 1992), the majority of them have conductivities which are too low (such as, for example, the zirconium phosphates) or else the conductivity reaches technically useful levels only at high temperatures, typically at ', ~" CA 02431055 2003-06-12 b.Z. 5696-WO
2 temperatures of more than 500 °C, as is the case, for example, with the defect perovskites.
Finally, another class of purely inorganic proton conductors, the MHS04 family, where M is Rb, Cs or NHa, although being good proton conductors, are at the same time readily soluble in water, so that they are ruled out of fuel cell applications on account of the fact that water is formed as a product on the cathode side and hence the membrane would be destroyed over time.
Another problem associated with the use of the inorganic proton conductors cited here within the fuel cell is that these inorganic proton conductors are difficult if not completely impossible to to produce in the form of a thin membrane film. Since the proton conductor must therefore automatically be manufactured in a very thick form, the overall resistance of the cell, even with high specific conductivity, is still very high. Accordingly, the high fuel cell power densities which are vital to industrial applications, in the automobile, for example, are difficult to realize.
W099/62620 was first to describe the production of an ion-conducting pervious composite material based on a ceramic, and its use. The steel weave described as the preferred support in W099/62620 is completely inappropriate, however, for the application of the composite material as a membrane in fuel cells, since when the fuel cell is operated short circuits occur very readily between the electrodes. For use in a fuel cell, moreover, this composite material 2o appears unsuitable on account of the fact that it is referred to as being pervious. For use in a fuel cell, the membrane must be impervious at least for the reaction gases, l.
e., H2, CH30H, and 02.
It is an object of the present invention to provide a membrane having ion conduction properties 2s which combines the advantages of membrane films (high flexibility, low membrane thickness) with those of more or less inorganic proton-conducting systems . and which can be used in particular in fuel cells.
Surprisingly it has been found that a membrane comprising as ion-conducting material 3o immobilized hydroxysilyl acids possesses the stated properties, such as high proton conductivity, low membrane thickness, and flexibility, and further possesses a high thermal load-bearing capacity and a low permeability for methanol.
, ~, ' CA 02431055 2003-06-12 O.Z. 5696-WO
Finally, another class of purely inorganic proton conductors, the MHS04 family, where M is Rb, Cs or NHa, although being good proton conductors, are at the same time readily soluble in water, so that they are ruled out of fuel cell applications on account of the fact that water is formed as a product on the cathode side and hence the membrane would be destroyed over time.
Another problem associated with the use of the inorganic proton conductors cited here within the fuel cell is that these inorganic proton conductors are difficult if not completely impossible to to produce in the form of a thin membrane film. Since the proton conductor must therefore automatically be manufactured in a very thick form, the overall resistance of the cell, even with high specific conductivity, is still very high. Accordingly, the high fuel cell power densities which are vital to industrial applications, in the automobile, for example, are difficult to realize.
W099/62620 was first to describe the production of an ion-conducting pervious composite material based on a ceramic, and its use. The steel weave described as the preferred support in W099/62620 is completely inappropriate, however, for the application of the composite material as a membrane in fuel cells, since when the fuel cell is operated short circuits occur very readily between the electrodes. For use in a fuel cell, moreover, this composite material 2o appears unsuitable on account of the fact that it is referred to as being pervious. For use in a fuel cell, the membrane must be impervious at least for the reaction gases, l.
e., H2, CH30H, and 02.
It is an object of the present invention to provide a membrane having ion conduction properties 2s which combines the advantages of membrane films (high flexibility, low membrane thickness) with those of more or less inorganic proton-conducting systems . and which can be used in particular in fuel cells.
Surprisingly it has been found that a membrane comprising as ion-conducting material 3o immobilized hydroxysilyl acids possesses the stated properties, such as high proton conductivity, low membrane thickness, and flexibility, and further possesses a high thermal load-bearing capacity and a low permeability for methanol.
, ~, ' CA 02431055 2003-06-12 O.Z. 5696-WO
3 The ion-conducting membrane of the invention is substantially more hydrophilic than the fluorinated hydrophobic polymer membranes customary at the present time. As a result, the water formed on the cathode side can easily diffuse back to the anode, so preventing dryout of the membrane, even at relatively high power densities and service temperatures.
The present invention accordingly provides a cation/proton-conducting membrane which comprises as cation- and/or proton-conducting material immobilized hydroxysilyl acid and/or salts thereof. Particularly preferred salts used are the ammonium, alkali metal, and alkaline to earth metal salts.
The present invention likewise provides a process in which a membrane is infiltrated with a hydroxysilyl acid and said acid is immobilized on and in the membrane.
The present invention further provides for the use of such a membrane as a catalyst for acid- or base-catalyzed reactions, as a membrane in fuel cells, or as a membrane in electrodialysis, membrane electrolysis or other electrolysis.
The present invention finally provides a fuel cell comprising as electrolyte membrane a 2o cationlproton-conducting membrane in accordance with the invention or as claimed in claim 1.
The membranes of the invention are distinguished by high cation/proton conductivity even at low water partial pressures and high temperatures. In particular the membranes of the invention can be used even at temperatures above 100 °C, preferably from 100 to 200 °C.
Through the use of the membranes of the invention it is possible to obtain reformate fuel cells and DMFCs which feature high power densities even at low water partial pressures and high temperatures.
3o The membrane of the invention and, respectively, a process for producing it, and its use are described in exemplary form below, without being restricted to the embodiments described.
b.z. s696-wo
The present invention accordingly provides a cation/proton-conducting membrane which comprises as cation- and/or proton-conducting material immobilized hydroxysilyl acid and/or salts thereof. Particularly preferred salts used are the ammonium, alkali metal, and alkaline to earth metal salts.
The present invention likewise provides a process in which a membrane is infiltrated with a hydroxysilyl acid and said acid is immobilized on and in the membrane.
The present invention further provides for the use of such a membrane as a catalyst for acid- or base-catalyzed reactions, as a membrane in fuel cells, or as a membrane in electrodialysis, membrane electrolysis or other electrolysis.
The present invention finally provides a fuel cell comprising as electrolyte membrane a 2o cationlproton-conducting membrane in accordance with the invention or as claimed in claim 1.
The membranes of the invention are distinguished by high cation/proton conductivity even at low water partial pressures and high temperatures. In particular the membranes of the invention can be used even at temperatures above 100 °C, preferably from 100 to 200 °C.
Through the use of the membranes of the invention it is possible to obtain reformate fuel cells and DMFCs which feature high power densities even at low water partial pressures and high temperatures.
3o The membrane of the invention and, respectively, a process for producing it, and its use are described in exemplary form below, without being restricted to the embodiments described.
b.z. s696-wo
4 The cation/proton-conducting membranes of the invention can be ceramic or vitreous membranes and are typified by comprising as cation- and/or proton-conducting material at least one immobilized acid from the group of the hydroxysilyl acids or salts thereof. Particularly preferred salts are the ammonium salts, alkali metal salts, and alkaline earth metal salts. The membrane may comprise a composite material based on at least one perforate and pervious support comprising on and inside the support at least one inorganic component essentially comprising at least one compound of a metal, semimetal, mixed metal or phosphorus with at least one element from main groups 3 to 7. With particular preference the composite material comprises on and in the support at least one oxide of the elements Zr, Ti, Al or Si.
to In order for the membranes of the invention to be able to be used as electrolyte membranes in fuel cells it is absolutely necessary for the composite material to have ion-conducting layers both on the inside and on both surfaces, since contact between electrolyte and electrodes in what is known as the membrane electrode assembly (MEA) must exist in order to complete the current circuit of the fuel cell. This ion conduction may be undertaken by the immobilized hydroxysilyl acid and/or by the other materials, which are described below.
The support may therefore be composed of an electrically insulating material, such as minerals, glasses, plastics, ceramics or natural substances, for example. Preferably the support comprises 2o special wovens or nonwovens of high-temperature-resistant and highly acid-resistant quartz or glass. The glass preferably comprises at least one compound from the group consisting of SiOz, A1203 and MgO. In another version the support is composed of a woven or nonwoven A1z03, Zr02, Ti02, Si3N4, or SiC ceramic. In order to minimize the overall resistance of the electrolyte membrane this support preferably combines a very high porosity with a law thickness of less than 100 pm, preferably less than s0 pm, and very preferably less than 20 um.
In a first step in accordance with w0 99/15262, for example, the perforate support can be converted into a mechanically and thermally stable, pervious ceramic composite material which conducts neither electricity nor ions.
Composite materials in accordance with WO 99/15262 feature, for example, supports made of at least one material selected from glasses, ceramics, minerals, plastics, amorphous substances, O.Z. 5696-WO
natural products, composites, or from at least one combination of said materials. The supports which may comprise the aforementioned materials may have been modified by a chemical, thermal or mechanical treatment method or by a combination of the treatment methods. The membrane preferably comprises a support comprising at least interwoven, interbonded, felted s or ceramically bound fibers or at least sintered or bonded shapes, spheres or particles. It may be advantageous for the support to comprise fibers of at least one material selected from ceramics, glasses, minerals, plastics, amorphous substances, composites, and natural products or fibers of at least one combination of said materials, such as asbestos, glass fibers, rockwool fibers, polyamide fibers, coconut fibers or coated fibers, for example. It is preferred to use to supports comprising interwoven fibers of glass or quartz, the woven preferably being composed of 11-tex yarns having 5 - 50 warp and weft threads and preferably 20 - 28 warp threads and 28 - 36 weft threads. Very preferably use is made of 5.5-tex yarns having 10 - 50 warp and weft threads and preferably 20 - 28 warp and 28 - 36 weft threads.
The composite materials comprise at least one inorganic component on and in the support.
This inorganic component may comprise at least one compound of at least one metal, semimetal or mixed metal with at least one element from main groups 3 to 7 of the Periodic Table, or at least one mixture of said compounds. The compounds of the metals, semimetals or mixed metals may comprise at least elements from the transition group elements and from main 2o groups 3 to 5 or at least elements from the transition group elements or from main groups 3 to
to In order for the membranes of the invention to be able to be used as electrolyte membranes in fuel cells it is absolutely necessary for the composite material to have ion-conducting layers both on the inside and on both surfaces, since contact between electrolyte and electrodes in what is known as the membrane electrode assembly (MEA) must exist in order to complete the current circuit of the fuel cell. This ion conduction may be undertaken by the immobilized hydroxysilyl acid and/or by the other materials, which are described below.
The support may therefore be composed of an electrically insulating material, such as minerals, glasses, plastics, ceramics or natural substances, for example. Preferably the support comprises 2o special wovens or nonwovens of high-temperature-resistant and highly acid-resistant quartz or glass. The glass preferably comprises at least one compound from the group consisting of SiOz, A1203 and MgO. In another version the support is composed of a woven or nonwoven A1z03, Zr02, Ti02, Si3N4, or SiC ceramic. In order to minimize the overall resistance of the electrolyte membrane this support preferably combines a very high porosity with a law thickness of less than 100 pm, preferably less than s0 pm, and very preferably less than 20 um.
In a first step in accordance with w0 99/15262, for example, the perforate support can be converted into a mechanically and thermally stable, pervious ceramic composite material which conducts neither electricity nor ions.
Composite materials in accordance with WO 99/15262 feature, for example, supports made of at least one material selected from glasses, ceramics, minerals, plastics, amorphous substances, O.Z. 5696-WO
natural products, composites, or from at least one combination of said materials. The supports which may comprise the aforementioned materials may have been modified by a chemical, thermal or mechanical treatment method or by a combination of the treatment methods. The membrane preferably comprises a support comprising at least interwoven, interbonded, felted s or ceramically bound fibers or at least sintered or bonded shapes, spheres or particles. It may be advantageous for the support to comprise fibers of at least one material selected from ceramics, glasses, minerals, plastics, amorphous substances, composites, and natural products or fibers of at least one combination of said materials, such as asbestos, glass fibers, rockwool fibers, polyamide fibers, coconut fibers or coated fibers, for example. It is preferred to use to supports comprising interwoven fibers of glass or quartz, the woven preferably being composed of 11-tex yarns having 5 - 50 warp and weft threads and preferably 20 - 28 warp threads and 28 - 36 weft threads. Very preferably use is made of 5.5-tex yarns having 10 - 50 warp and weft threads and preferably 20 - 28 warp and 28 - 36 weft threads.
The composite materials comprise at least one inorganic component on and in the support.
This inorganic component may comprise at least one compound of at least one metal, semimetal or mixed metal with at least one element from main groups 3 to 7 of the Periodic Table, or at least one mixture of said compounds. The compounds of the metals, semimetals or mixed metals may comprise at least elements from the transition group elements and from main 2o groups 3 to 5 or at least elements from the transition group elements or from main groups 3 to
5, these compounds being used with preference in a particle size of from 0.001 to 25 p.m. The inorganic component preferably comprises at least one compound of an element from transition groups 3 to 8 or at least one element from main groups 3 to 5 with at least one of the elements Te, Se, S, O, Sb, As, P, N, Ge, Si, C, Ga, Al or B or at least one compound of an element 2s from transition groups 3 to 8 and at least one element from main groups 3 to 5 with at least one of the element Te, Se, S, O, Sb, As, P, N, Ge, Si, C, Ga, A1 or B, or a mixture of said compounds. With particular preference the inorganic component comprises at least one compound of at least one of the elements Sc, Y, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Fe, Co, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, Sb or Bi with at least one of the elements Te, Se, S, O, Sb, As, P, 3o N, C, Si, Ge or Ga, such as, for example, Ti02, A12O3, Si02, Zr02, Y2O3, BaC, SiC, Fe304, Si3Nø, BN, SiP, nitrides, sulfates, phosphides, silicides, spinets or perovskites.
O.Z. 5696-WO
O.Z. 5696-WO
6 Prior to processing to the composite material it is preferred for at Least one inorganic component to be present in the form of a particle size fraction having a particle size of from 1 to 250 nm and/or having a particle size of from 260 to 10 000 nm, In one special embodiment the composite material comprises at least one inorganic component in the form of a three-s dimensional network having a specific surface area of up to 1 000 m2/g and having pore radii of 0.5 - 10 nm. This component preferably comprises at least one compound from the group consisting of A1203, Zr02, Si02, Ti02, and P20s.
It may be advantageous if the composite material used has at least two particle size fi~actions of to at least one inorganic component. It may also be advantageous if the composite material has at least two particle size fractions of at least two inorganic components. The particle size ratio may be from 1 : 1 to 1 : 10 000, preferably from 1 : 1 to 1 : 100. The proportion of the particle size fractions in the composite material may amount preferably to from 0.01 :
1. to 1 : 0.01.
15 The hydroxysilyl acid can be used directly or in the form of a precursor, i.e., of a derivative (e.g., alkoxide).
Useful hydroxysilyl acids, their salts or their precursors, such as alkoxides, are organosilicon compounds of the general formula WOY~Z~zSI- f R1-SOs }a]xM"+ (I) or L~~)Y(RZ)z"S~-{R1-Ob-P(O~R3)O2 ~.~xM"+ (II) where R' is a linear or branched alkyl or alkylene group having from 1 to 12 carbon atoms, a cycloalkyl group having from 5 to 8 carbon atoms or a unit of the general formula - (CHz)n -~C ~ m~ (I~
or "" ~ CA 02431055 2003-06-12 O.Z. 5696-WO
It may be advantageous if the composite material used has at least two particle size fi~actions of to at least one inorganic component. It may also be advantageous if the composite material has at least two particle size fractions of at least two inorganic components. The particle size ratio may be from 1 : 1 to 1 : 10 000, preferably from 1 : 1 to 1 : 100. The proportion of the particle size fractions in the composite material may amount preferably to from 0.01 :
1. to 1 : 0.01.
15 The hydroxysilyl acid can be used directly or in the form of a precursor, i.e., of a derivative (e.g., alkoxide).
Useful hydroxysilyl acids, their salts or their precursors, such as alkoxides, are organosilicon compounds of the general formula WOY~Z~zSI- f R1-SOs }a]xM"+ (I) or L~~)Y(RZ)z"S~-{R1-Ob-P(O~R3)O2 ~.~xM"+ (II) where R' is a linear or branched alkyl or alkylene group having from 1 to 12 carbon atoms, a cycloalkyl group having from 5 to 8 carbon atoms or a unit of the general formula - (CHz)n -~C ~ m~ (I~
or "" ~ CA 02431055 2003-06-12 O.Z. 5696-WO
7 - (CHZ)n -(C HZ) m (I~
where n and m are each a number from 0 to 6, 1VI is an H+, an NH,~+ or a metal cation having a valence x of from 1 to 4, y is from 1 to 3, z is from 0 to 2, and a is from 1 to 3, with the proviso that y + z = 4 - a, b and c are 0 or 1, R and R2 are identical or different and are methyl, ethyl, propyl or butyl radicals or H, and R3 is the same as M or is a methyl, ethyl, propyl or butyl radical.
Preferred hydroxysilyl acids and their precursors (derivatives) are trihydroxysilylpropylsulfonic to acid, trihydroxysilylpropylmethylphosphonic acid, or dihydroxysilylpropyldisulfonic acid, or salts thereof.
The existing hydroxyl groups or hydroxyl groups produced by hydrolysis serve to attach the silyl acids to the inorganic composite material. As a result of this attachment the acid or salt thereof is immobilized, i.e., made insoluble. Through an appropriate choice of the tri- (networl~
formers), di- (chain formers), and mono-hydroxysilyl acid (terminal chain member) and through the addition of further sol ~r~:.ers it is possible to set with precision the structure of the ion-conducting material under construction. Examples of suitable sol formers are the hydrolyzed precursors of Si02, A12O3, P20s, Ti02 or Zr02.
2o EP 0 771 589, EP 0 765 897, and EP 0 582 879 disclose trihydroxysilyl acids. Those publications described the preparation of shaped acid catalysts based on trihydroxysilylpropylsulfonic acid and trihydroxysilylpropyl mercaptan.
It may be advantageous if the membrane of the invention comprises at least one further ion-conducting compound selected from the group consisting of iso- and heteropolyacids, zeolites, mordenites, aluminosilicates, ~3-aluminas, zirconium, titanium, and cerium phosphates, phosphonates or sulfoarylphosphonates, antimony acids, phosphorus oxides, sulfuric acid, perchloric acid, and salts thereof. In one particularly preferred variant the membrane also comprises nanoscale powders from the group consisting of Si02, A1z03, Zr02, and Ti02.
' ~. CA 02431055 2003-06-12 - b.Z.5696-WO
where n and m are each a number from 0 to 6, 1VI is an H+, an NH,~+ or a metal cation having a valence x of from 1 to 4, y is from 1 to 3, z is from 0 to 2, and a is from 1 to 3, with the proviso that y + z = 4 - a, b and c are 0 or 1, R and R2 are identical or different and are methyl, ethyl, propyl or butyl radicals or H, and R3 is the same as M or is a methyl, ethyl, propyl or butyl radical.
Preferred hydroxysilyl acids and their precursors (derivatives) are trihydroxysilylpropylsulfonic to acid, trihydroxysilylpropylmethylphosphonic acid, or dihydroxysilylpropyldisulfonic acid, or salts thereof.
The existing hydroxyl groups or hydroxyl groups produced by hydrolysis serve to attach the silyl acids to the inorganic composite material. As a result of this attachment the acid or salt thereof is immobilized, i.e., made insoluble. Through an appropriate choice of the tri- (networl~
formers), di- (chain formers), and mono-hydroxysilyl acid (terminal chain member) and through the addition of further sol ~r~:.ers it is possible to set with precision the structure of the ion-conducting material under construction. Examples of suitable sol formers are the hydrolyzed precursors of Si02, A12O3, P20s, Ti02 or Zr02.
2o EP 0 771 589, EP 0 765 897, and EP 0 582 879 disclose trihydroxysilyl acids. Those publications described the preparation of shaped acid catalysts based on trihydroxysilylpropylsulfonic acid and trihydroxysilylpropyl mercaptan.
It may be advantageous if the membrane of the invention comprises at least one further ion-conducting compound selected from the group consisting of iso- and heteropolyacids, zeolites, mordenites, aluminosilicates, ~3-aluminas, zirconium, titanium, and cerium phosphates, phosphonates or sulfoarylphosphonates, antimony acids, phosphorus oxides, sulfuric acid, perchloric acid, and salts thereof. In one particularly preferred variant the membrane also comprises nanoscale powders from the group consisting of Si02, A1z03, Zr02, and Ti02.
' ~. CA 02431055 2003-06-12 - b.Z.5696-WO
8 The membrane of the invention conducts cations andlor protons at a temperature of from -40 °C to 300 °C, preferably from - 10 to 200 °C. If a flexible composite material is used in producing the membrane of the invention, the membrane of the invention itself is flexible and depending on the composite material used can be bent down to a smallest radius of 25 mm, preferably 10 mm, very preferably S mm.
In a further embodiment of the process the membrane is infiltrated with a solution or suspension which in addition to the hydroxylsilyl acid, its salts or precursors further comprises to at least one other proton- or cation-conducting material.
The composite material may also be infiltrated with a solution, sol or suspension which in addition to the hydroxysilyl acid, its salts or precursors further comprises at least one further material based on a hydrolyzed or hydrolyzable compound of a metal or semimetal, which contributes to immobilization of the hydroxysilyl acid.
Again in dependence on the composite material employed, the membrane has a thickness of less than 200 pm, preferably less than 100 pm, and very preferably less than 50 or 20 pm.
2o The production of mechanically and thermally stable and yet pervious ceramic composite materials is described in detail, for example, in WO 99115262. In contrast to the composite materials described therein, however, the composite materials suitable for the process of this invention only include those which are not electrically conducting.
In order to immobilize the hydroxysilyl acid in and on the membrane said membrane is treated or infiltrated at least with the hydroxysilyl acid, where appropriate in aqueous or alcoholic solution. In addition it is also possible to include the ion-conducting compounds already mentioned. They can be present in dissolved form or in suspension in the solution used for the coating.
In any case the hydroxysilyl acid at least must be immobilized in and on a membrane. In accordance with the process of the invention this can be accomplished thermally, in which case '' CA 02431055 2003-06-12 - O.Z.5696-WO
In a further embodiment of the process the membrane is infiltrated with a solution or suspension which in addition to the hydroxylsilyl acid, its salts or precursors further comprises to at least one other proton- or cation-conducting material.
The composite material may also be infiltrated with a solution, sol or suspension which in addition to the hydroxysilyl acid, its salts or precursors further comprises at least one further material based on a hydrolyzed or hydrolyzable compound of a metal or semimetal, which contributes to immobilization of the hydroxysilyl acid.
Again in dependence on the composite material employed, the membrane has a thickness of less than 200 pm, preferably less than 100 pm, and very preferably less than 50 or 20 pm.
2o The production of mechanically and thermally stable and yet pervious ceramic composite materials is described in detail, for example, in WO 99115262. In contrast to the composite materials described therein, however, the composite materials suitable for the process of this invention only include those which are not electrically conducting.
In order to immobilize the hydroxysilyl acid in and on the membrane said membrane is treated or infiltrated at least with the hydroxysilyl acid, where appropriate in aqueous or alcoholic solution. In addition it is also possible to include the ion-conducting compounds already mentioned. They can be present in dissolved form or in suspension in the solution used for the coating.
In any case the hydroxysilyl acid at least must be immobilized in and on a membrane. In accordance with the process of the invention this can be accomplished thermally, in which case '' CA 02431055 2003-06-12 - O.Z.5696-WO
9 the membrane infiltrated with hydroxysilyl acid is treated first at a temperature of from 0 to 50 °C and subsequently the hydroxysilyl acid is immobilized at a temperature of from 20 to 250 °C.
The immobilization of the hydroxysilyl acid - together where appropriate with the other ion-conducting compounds - is frequently accompanied by the formation first of sol and then of gel. Accordingly, infiltration can be carried out not only with a solution but also with a sol.
The porous composite material may also be infiltrated with a sol which in addition to the to hydroxysilyl acid sol former further comprises at least one hydrolyzed compound selected from the group consisting of metal nitrates, metal chlorides, metal carbonates, metal alkoxides, and semimetal oxides. A particularly preferred sol former used is at least one hydrolyzed compound selected from the alkoxides, acetylacetonates, nitrates, and chlorides of the elements Ti, Zr, Al, and Si.
The sots can be obtained by hydrolyzing at least one of the aforementioned liydrolyzable compounds, preferably at least one metal compound, semimetal compound or mixed metal compound, with at least one liquid, solid or gas, in which case it can be advantageous if the liquid used comprises, for example, water, alcohol, a base or an acid, the solid used comprises 2o ice, or the gas used comprises water vapor or at least one combination of these liquids, solids or gases. It may also be advantageous to introduce the compound to be hydrolyzed into alcohol, a base or an acid or a combination of these liquids prior to the hydrolysis.
It may be advantageous to conduct the hydrolysis of the compounds to be hydrolyzed using at least half the molar ratio of water, water vapor or ice, based on the hydrolyzable group of the compound to be hydrolyzed.
The hydrolyzed compound can be peptized by treatment with at least one organic or inorganic acid, preferably with an organic or inorganic acid having a concentration of from 10 to 60 %, 3o more preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, and nitric acid, or a mixture of these acids.
f ' ~ CA 02431055 2003-06-12 O.Z. 5696-WO
It is possible not only to use sols prepared as described above but also commercially customary sots, such as titanium or zirconium nitrate sol, zirconium acetate sol or silica sol, for example.
It may be advantageous if either instead of the sol former or in addition thereto at least one 5 solid inorganic, preferably proton-conducting, component is suspended in the sol comprising the hydroxysilyl acid. Preference is given to suspending an inorganic component which comprises at least one compound selected from metal compounds, semimetal compounds, mixed metal compounds, and metal mixed compounds with at least one of the elements from main groups 3 to 7, or at least one mixture of these compounds. Particular preference is given to to suspending in the sol at least one inorganic proton-conducting component selected from the group of the iso- or heteropolyacids, such as 12-tungstophosphoric acid (WPA), silicotungstic acid, zirconium, titanium or cerium phosphates, phosphonates or sulfoarylphosphonates, antimony acids, phosphorus oxides, Aerosil (SiOz), nanoscale A12O3, Ti02 or Zr02 powders, zeolites, mordenites, aluminosilicates, and (3-aluminas.
Through the appropriate choice of the particle size of the suspended compounds as a function of size of the pores, holes or interstices in the porous ceramic composite material it is possible to optimize the cracklessness in the membrane of the invention.
2o In another variant of the process of the invention the sol further comprises a strong liquid acid, such as sulfuric acid or perchloric acid, which can likewise be immobilized by being bound into the inorganic network.
The infiltration of the sol in and on the membrane can take place, for example, by printing on, pressing on, pressing in, rolling on, roller application, knife coating, spreading on, dipping, spraying, spray application or pouring of the sol onto the membrane or composite material. It is, however, also possible to infiltrate the composite material or membrane with the sol by dipping or vacuum infiltration.
3o The sol infiltrated into the composite material is heated to the stated temperatures, at which it gels. This operation may last for from 0.1 to 72 hours. Preferably the sol is gelled in the composite material within from 0.1 to 0.5 hours. The resultant gel is subsequently immobilized y ' , CA 02431055 2003-06-12 O.Z. 5696-WO
- i.e., solidified and, in extreme cases, made water-insoluble - at a temperature of from 20 to 250 °C, preferably from 150 to 200 °C.
The proton/cation-conducting membrane of the invention can be employed widely in industry and can be utilized for a very wide variety of applications. Mention may be made in particular here of applications in electrodialysis as cation exchange membranes, and also of application as a membraneldiaphragm in electrolysis cells, including membrane electrolysis cells.
Further fields of application are situated in the sector of energy generation using fuel cells. The to membrane of the invention can be used as an electrolyte membrane in a fuel cell. Such fuel cells can be operated at a higher temperature than fuel cells having an electrolyte membrane based on a polymer membrane. Accordingly the fuels can be, for example, alcohols or hydrocarbons (directly or indirectly via a reforming step). CO poisoning of the electrode which is catalytically active on the anode side does not occur at these elevated temperatures (> 120 °C).
However, there are also a whole range of electrochemical or catalyzed reactions which take place on and/or are catalyzed by ion-conducting materials. The membrane of the invention is therefore also suitable for use as a catalyst for acid- or base-catalyzed reactions.
2o The proton/cation-conducting membrane of the invention and the process for producing it are described by means of the following examples, without being restricted to them.
Example 1 Non-ion-conducting composite material 120 g of zirconium tetraisopropoxide are stirred with 140 g of deionized ice with vigorous stirring until the precipitate which forms is very finely divided. Following the addition of 100 g of 25% strength hydrochloric acid the mixture is stirred until the phase becomes clear, 280 g of a,-alumina of type CT3000SG from Alcoa, Ludwigshafen, DE are added and the mixture is stirred for several days until the aggregates have been broken up.
This suspension is subsequently applied in a thin layer to a glass weave (11-tex yarn with 28 3o warp threads and 32 weft threads) and solidified at 550 °C witlun S
seconds.
O.Z. 5696-WO
Example 2 Production of a proton-conducting membrane ml of anhydrous trihydroxysilylpropylsulfonic acid, 30 ml of ethanol and 5 ml of water are mixed by stirring. 40 ml of TEOS (tetraethyl orthosilicate) are slowly added dropwise to this mixture with stirring. In order to bring about a certain degree of condensation this sol is stirred 5 in a closed vessel for 24 hours. The composite material from Example 1 is immersed in this sol for 15 minutes. Thereafter the sol in the saturated membrane is gelled in air for 60 minutes and dried.
The gel-filled membrane is dried at a temperature of 200 °C for 60 minutes, so that the gel solidifies and is made water-insoluble. In this way an impervious membrane is obtained which to has a proton conductivity at room temperature and normal ambient air of about 2~ 10'3 S/cm.
Example 3: Production of a proton-conducting membrane 25 g of tungstophosphoric acid are dissolved in 50 ml of the sol from Example 2. The composite material from Example 1 is immersed in this sol for 15 minutes. The subsequent is procedure is then as in Example 2.
Example 4: Production of a proton-conducting membrane 100 ml of titanium isopropoxide are added dropwise with vigorous stirring to 1 200 ml of water. The resulting precipitate is aged for 1 hour, then 8.5 ml of concentrated HN03 are 2o added and the precipitate is peptized at boiling for 24 hours. 50 g of tungstophosphoric acid are dissolved in 25 ml of the sol. A further 25 ml of trihydroxysilylpropylsulfonic acid are added to this solution, which is stirred at room temperature for 1 hour more.
The composite material from Example 1 is immersed in this sol for 15 minutes. The subsequent procedure is as in Example 2.
Example 5: Production of a proton-conducting membrane Trihydroxysilylmethylphosphonic acid dissolved in a little water is diluted with ethanol. The same amount of TEOS is added to the solution, and stirring is continued briefly. The composite material from Example 1 is immersed in this sol for 15 minutes. The subsequent 3o procedure is as in Example 2.
The immobilization of the hydroxysilyl acid - together where appropriate with the other ion-conducting compounds - is frequently accompanied by the formation first of sol and then of gel. Accordingly, infiltration can be carried out not only with a solution but also with a sol.
The porous composite material may also be infiltrated with a sol which in addition to the to hydroxysilyl acid sol former further comprises at least one hydrolyzed compound selected from the group consisting of metal nitrates, metal chlorides, metal carbonates, metal alkoxides, and semimetal oxides. A particularly preferred sol former used is at least one hydrolyzed compound selected from the alkoxides, acetylacetonates, nitrates, and chlorides of the elements Ti, Zr, Al, and Si.
The sots can be obtained by hydrolyzing at least one of the aforementioned liydrolyzable compounds, preferably at least one metal compound, semimetal compound or mixed metal compound, with at least one liquid, solid or gas, in which case it can be advantageous if the liquid used comprises, for example, water, alcohol, a base or an acid, the solid used comprises 2o ice, or the gas used comprises water vapor or at least one combination of these liquids, solids or gases. It may also be advantageous to introduce the compound to be hydrolyzed into alcohol, a base or an acid or a combination of these liquids prior to the hydrolysis.
It may be advantageous to conduct the hydrolysis of the compounds to be hydrolyzed using at least half the molar ratio of water, water vapor or ice, based on the hydrolyzable group of the compound to be hydrolyzed.
The hydrolyzed compound can be peptized by treatment with at least one organic or inorganic acid, preferably with an organic or inorganic acid having a concentration of from 10 to 60 %, 3o more preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, and nitric acid, or a mixture of these acids.
f ' ~ CA 02431055 2003-06-12 O.Z. 5696-WO
It is possible not only to use sols prepared as described above but also commercially customary sots, such as titanium or zirconium nitrate sol, zirconium acetate sol or silica sol, for example.
It may be advantageous if either instead of the sol former or in addition thereto at least one 5 solid inorganic, preferably proton-conducting, component is suspended in the sol comprising the hydroxysilyl acid. Preference is given to suspending an inorganic component which comprises at least one compound selected from metal compounds, semimetal compounds, mixed metal compounds, and metal mixed compounds with at least one of the elements from main groups 3 to 7, or at least one mixture of these compounds. Particular preference is given to to suspending in the sol at least one inorganic proton-conducting component selected from the group of the iso- or heteropolyacids, such as 12-tungstophosphoric acid (WPA), silicotungstic acid, zirconium, titanium or cerium phosphates, phosphonates or sulfoarylphosphonates, antimony acids, phosphorus oxides, Aerosil (SiOz), nanoscale A12O3, Ti02 or Zr02 powders, zeolites, mordenites, aluminosilicates, and (3-aluminas.
Through the appropriate choice of the particle size of the suspended compounds as a function of size of the pores, holes or interstices in the porous ceramic composite material it is possible to optimize the cracklessness in the membrane of the invention.
2o In another variant of the process of the invention the sol further comprises a strong liquid acid, such as sulfuric acid or perchloric acid, which can likewise be immobilized by being bound into the inorganic network.
The infiltration of the sol in and on the membrane can take place, for example, by printing on, pressing on, pressing in, rolling on, roller application, knife coating, spreading on, dipping, spraying, spray application or pouring of the sol onto the membrane or composite material. It is, however, also possible to infiltrate the composite material or membrane with the sol by dipping or vacuum infiltration.
3o The sol infiltrated into the composite material is heated to the stated temperatures, at which it gels. This operation may last for from 0.1 to 72 hours. Preferably the sol is gelled in the composite material within from 0.1 to 0.5 hours. The resultant gel is subsequently immobilized y ' , CA 02431055 2003-06-12 O.Z. 5696-WO
- i.e., solidified and, in extreme cases, made water-insoluble - at a temperature of from 20 to 250 °C, preferably from 150 to 200 °C.
The proton/cation-conducting membrane of the invention can be employed widely in industry and can be utilized for a very wide variety of applications. Mention may be made in particular here of applications in electrodialysis as cation exchange membranes, and also of application as a membraneldiaphragm in electrolysis cells, including membrane electrolysis cells.
Further fields of application are situated in the sector of energy generation using fuel cells. The to membrane of the invention can be used as an electrolyte membrane in a fuel cell. Such fuel cells can be operated at a higher temperature than fuel cells having an electrolyte membrane based on a polymer membrane. Accordingly the fuels can be, for example, alcohols or hydrocarbons (directly or indirectly via a reforming step). CO poisoning of the electrode which is catalytically active on the anode side does not occur at these elevated temperatures (> 120 °C).
However, there are also a whole range of electrochemical or catalyzed reactions which take place on and/or are catalyzed by ion-conducting materials. The membrane of the invention is therefore also suitable for use as a catalyst for acid- or base-catalyzed reactions.
2o The proton/cation-conducting membrane of the invention and the process for producing it are described by means of the following examples, without being restricted to them.
Example 1 Non-ion-conducting composite material 120 g of zirconium tetraisopropoxide are stirred with 140 g of deionized ice with vigorous stirring until the precipitate which forms is very finely divided. Following the addition of 100 g of 25% strength hydrochloric acid the mixture is stirred until the phase becomes clear, 280 g of a,-alumina of type CT3000SG from Alcoa, Ludwigshafen, DE are added and the mixture is stirred for several days until the aggregates have been broken up.
This suspension is subsequently applied in a thin layer to a glass weave (11-tex yarn with 28 3o warp threads and 32 weft threads) and solidified at 550 °C witlun S
seconds.
O.Z. 5696-WO
Example 2 Production of a proton-conducting membrane ml of anhydrous trihydroxysilylpropylsulfonic acid, 30 ml of ethanol and 5 ml of water are mixed by stirring. 40 ml of TEOS (tetraethyl orthosilicate) are slowly added dropwise to this mixture with stirring. In order to bring about a certain degree of condensation this sol is stirred 5 in a closed vessel for 24 hours. The composite material from Example 1 is immersed in this sol for 15 minutes. Thereafter the sol in the saturated membrane is gelled in air for 60 minutes and dried.
The gel-filled membrane is dried at a temperature of 200 °C for 60 minutes, so that the gel solidifies and is made water-insoluble. In this way an impervious membrane is obtained which to has a proton conductivity at room temperature and normal ambient air of about 2~ 10'3 S/cm.
Example 3: Production of a proton-conducting membrane 25 g of tungstophosphoric acid are dissolved in 50 ml of the sol from Example 2. The composite material from Example 1 is immersed in this sol for 15 minutes. The subsequent is procedure is then as in Example 2.
Example 4: Production of a proton-conducting membrane 100 ml of titanium isopropoxide are added dropwise with vigorous stirring to 1 200 ml of water. The resulting precipitate is aged for 1 hour, then 8.5 ml of concentrated HN03 are 2o added and the precipitate is peptized at boiling for 24 hours. 50 g of tungstophosphoric acid are dissolved in 25 ml of the sol. A further 25 ml of trihydroxysilylpropylsulfonic acid are added to this solution, which is stirred at room temperature for 1 hour more.
The composite material from Example 1 is immersed in this sol for 15 minutes. The subsequent procedure is as in Example 2.
Example 5: Production of a proton-conducting membrane Trihydroxysilylmethylphosphonic acid dissolved in a little water is diluted with ethanol. The same amount of TEOS is added to the solution, and stirring is continued briefly. The composite material from Example 1 is immersed in this sol for 15 minutes. The subsequent 3o procedure is as in Example 2.
Claims (33)
1. A cation/proton-conducting membrane comprising as cation- and/or proton-conducting materials at least one immobilized hydroxysilyl acid and/or salt thereof
2. A membrane as claimed in claim 1, which is ceramic or vitreous.
3. A membrane as claimed in claim 1 or 2, comprising a composite material based on a perforate and pervious support comprising on and inside said support at least one inorganic component essentially comprising at least one compound of a metal, semimetal, mixed metal or phosphorus with at least one element from main groups 3 to 7.
4. A membrane as claimed in claim 3, wherein the support comprises a woven or nonwoven made of fibers of one or more materials selected from the group consisting of glasses, ceramics, natural substances, plastics, and minerals.
5. A membrane as claimed in any of claims 1 to 4, which conducts cations and/or protons at a temperature of from -40 °C to 300 °C.
6. A membrane as claimed in any of claims 1 to 5, wherein use is made as hydroxysilyl acid or precursor thereof of an organosilicon compound of the general formula [(RO)y-(R2)z Si-{R1-SO3-}a]x M x+ (I) or [(RO)y(R2)z Si-{R1-O b-P(O c R3)O2-}a]x M x+ (II) where R1 is a linear or branched alkyl or alkylene group having from 1 to 12 carbon atoms, a cycloalkyl group having from 5 to 8 carbon atoms or a unit of the general formula where n and m are each a number from 0 to 6, M is an H+, an NH4+ or a metal cation having a valence x of from 1 to 4, y is from 1 to 3, z is from 0 to 2, and a is from 1 to 3, with the proviso that y + z = 4 - a, b and c are 0 or 1, R and R2 are identical or different and are methyl, ethyl, propyl or butyl radicals or H, and R3 is the same as M or is a methyl, ethyl, propyl or butyl radical.
7. A membrane as claimed in claim 6, wherein use is made as hydroxysilyl acid of trihydroxysilylpropylsulfonic acid, trihydroxysilylpropylmethylphosphonic acid or dihydroxysilylpropyldisulfonic acid or salts thereof.
8. A membrane as claimed in any of claims 1 to 7, wherein the hydroxysilyl acid is immobilized with a hydrolyzed compound of phosphorus or with a hydrolyzed compound from the group of the nitrates, oxynitrates, chlorides, oxychlorides, carbonates, alkoxides, acetates, and acetylacetonates of the metals or semimetals.
9. A membrane as claimed in claim 8, wherein the hydroxysilyl acid is immobilized with a hydrolyzed compound obtained from titanium propoxide or ethoxide, tetramethyl or tetraethyl orthosilicate (TMOS, TEOS), zirconium nitrate, oxynitrate, propoxide, acetate or acetylacetonate, or methyl phosphate.
10. A membrane as claimed in any of claims 1 to 9, comprising at least one further ion-conducting compound selected from the group consisting of nanoscale Al2O3, ZrO2, TiO2 and SiO2 powders, iso- and heteropolyacids, zeolites, mordenites, aluminosilicates, .beta.-aluminas, zirconium, titanium, and cerium phosphates, phosphonates, and sulfoarylphosphonates, antimony acids, phosphorus oxides, sulfuric acid, and perchloric acid or salts thereof.
11. A membrane as claimed in any of claims 1 to 10, which is flexible.
12. A membrane as claimed in any of claims 1 to 11, which can be bent down to a smallest radius of 25 mm.
13. A membrane as claimed in any of claims 1 to 12, which has a thickness of less than 200 µm.
14. A process for producing a cation/proton-conducting membrane, which comprises infiltrating said membrane with a hydroxysilyl acid, salt thereof or precursor(s) thereof and immobilizing said acid, salt or precursor(s) on and in said membrane.
15. A process as claimed in claim 14, wherein the membrane is ceramic or vitreous.
16. A process as claimed in claim 14 or 15, wherein the membrane comprises a composite material based on a perforate and pervious support comprising on and inside said support at least one inorganic component essentially comprising at least one compound of a metal, semimetal, mixed metal or phosphorus with at least one element from main groups 3 to 7.
17. A process as claimed in claim 16, wherein the support comprises a woven or nonwoven made of fibers of one or more materials selected from the group consisting of glasses, ceramics, natural substances, plastics, and minerals.
18. A process as claimed in any of claims 14 to 17, wherein the membrane conducts cations and/or protons at a temperature of from -40 °C to 300 °C.
19. A process as claimed in any of claims 14 to 18, wherein use is made as hydroxysilyl acid or precursor thereof of an organosilicon compound of the general formula [(RO)y(R2)z Si-{R1-SO3-}a]x M x+ (I) or [RO)y(R2)z Si-{R1-O b-P(O c R3)O2-}a]x M x+ (II) where R1 is a linear or branched alkyl or alkylene group having from 1 to 12 carbon atoms, a cycloalkyl group having from 5 to 8 carbon atoms or a unit of the general formula where n and m are each a number from 0 to 6, M is an H+, an NH4+ or a metal cation having a valence x of from 1 to 4, y is from 1 to 3, z is from 0 to 2, and a is from 1 to 3, with the proviso that y + z = 4 - a, b and c are 0 or 1, R and R2 are identical or different and are methyl, ethyl, propyl or butyl radicals or H, and R3 is the same as M or is a methyl, ethyl, propyl or butyl radical.
20. A process as claimed in claim 19, wherein use is made as hydroxysilyl acid of trihydroxysilylpropylsulfonic acid, trihydroxysilylpropylmethylphosphonic acid or dihydroxysilylpropyldisulfonic acid or salts thereof.
21. A process as claimed in any of claims 14 to 20, wherein the hydroxysilyl acid is immobilized with a hydrolyzed compound of phosphorus or with a hydrolyzed compound from the group of the nitrates, oxynitrates, chlorides, oxychlorides, carbonates, alkoxides, acetates, and acetylacetonates of the metals or semimetals.
22. A process as claimed in claim 21, wherein the hydroxysilyl acid is immobilized with a hydrolyzed compound obtained from titanium propoxide or ethoxide, tetramethyl or tetraethyl orthosilicate (TMOS, TEOS), zirconium nitrate, oxynitrate, propoxide, acetate or acetylacetonate, or methyl phosphate.
23. A process as claimed in any of claims 14 to 22, wherein the membrane is infiltrated with a solution, sol or suspension which in addition to the hydroxysilyl acid, its salts or precursors further comprises at least one further material based on a hydrolyzed or hydrolyzable compound of a metal or semimetal, which contributes to immobilizing the hydroxysilyl acid.
24. A process as claimed in any of claims 14 to 23, where the membrane is infiltrated with a solution or suspension which in addition to the hydroxysilyl acid, its salts or precursors further comprises at least one further proton- or cation-conducting material.
25. A process as claimed in any of claims 14 to 24, wherein the membrane in addition to the immobilized hydroxylsilyl acid comprises least one further ion-conducting compound selected from the group consisting of nanoscale Al2O3, ZrO2, TiO2 and SiO2 powders, iso- and heteropolyacids, zeolites, mordenites, aluminosilicates, .beta.-aluminas, zirconium, titanium, and cerium phosphates, phosphonates, and sulfoarylphosphonates, antimony acids, phosphorus oxides, sulfuric acid, and perchloric acid or salts thereof.
26. A process as claimed in any of claims 14 to 25, wherein the membrane is flexible.
27. A process as claimed in any of claims 14 to 26, wherein the membrane can be bent down to a smallest radius of 25 mm.
28. A process as claimed in any of claims 14 to 27, wherein the membrane has a thickness of less than 200 µm..
29. A process as claimed in at least one of claims 15 to 28, wherein the membrane infiltrated with hydroxysilyl acid is first treated at a temperature of from 0 to 50 °C and then the hydroxysilyl acid is immobilized at a temperature of from 20 to 250 °C.
30. The use of a membrane as claimed in at least one of claims 1 to 13 as a catalyst for acid-or base-catalyzed reactions.
31. The use of a membrane as claimed in at least one of claims 1 to 13 as a membrane in fuel cells.
32. The use of a membrane as claimed in at least one of claims 1 to 13 as a membrane in electrodialysis, membrane electrolysis or other electrolysis.
33. A fuel cell comprising as electrolyte membrane a cation/proton-conducting membrane as claimed in any of claims 1 to 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10061920.7 | 2000-12-13 | ||
| DE10061920A DE10061920A1 (en) | 2000-12-13 | 2000-12-13 | Cation- / proton-conducting ceramic membrane based on a hydroxysilyl acid, process for its production and the use of the membrane |
| PCT/EP2001/012466 WO2002047801A1 (en) | 2000-12-13 | 2001-10-27 | Cation-conducting or proton-conducting ceramic membrane based on a hydroxysilylic acid, method for the production thereof and use of the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2431055A1 true CA2431055A1 (en) | 2002-06-20 |
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|---|---|---|---|
| CA002431055A Abandoned CA2431055A1 (en) | 2000-12-13 | 2001-10-27 | Cation/proton-conducting ceramic membrane based on a hydroxysilyl acid, its production and use |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20040028913A1 (en) |
| EP (1) | EP1345674A1 (en) |
| JP (1) | JP2004515896A (en) |
| AU (1) | AU2002221771A1 (en) |
| CA (1) | CA2431055A1 (en) |
| DE (1) | DE10061920A1 (en) |
| NO (1) | NO20032719D0 (en) |
| PL (1) | PL361860A1 (en) |
| WO (1) | WO2002047801A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1585183A1 (en) * | 2004-03-26 | 2005-10-12 | Fuji Photo Film Co. Ltd. | Compound for use as a solid electrolyte or proton conductor in a membrane electrode assembly in fuel cells |
| US7442459B2 (en) | 2005-05-13 | 2008-10-28 | Fujifilm Corporation | Solid electrolyte, membrane and electrode assembly, and fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10118346A1 (en) | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Self-cleaning, water-repellent textiles, used e.g. for tents, sports clothing and carpets, made by impregnating textile material with a suspension of hydrophobic particles and then removing the solvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1017476B1 (en) * | 1998-06-03 | 2006-10-18 | Degussa AG | Ion-conducting composite which is permeable to matter, method for producing said composite, and use of the same |
| US6468684B1 (en) * | 1999-01-22 | 2002-10-22 | California Institute Of Technology | Proton conducting membrane using a solid acid |
-
2000
- 2000-12-13 DE DE10061920A patent/DE10061920A1/en not_active Withdrawn
-
2001
- 2001-10-27 EP EP01270377A patent/EP1345674A1/en not_active Withdrawn
- 2001-10-27 JP JP2002549366A patent/JP2004515896A/en active Pending
- 2001-10-27 PL PL36186001A patent/PL361860A1/en unknown
- 2001-10-27 AU AU2002221771A patent/AU2002221771A1/en not_active Abandoned
- 2001-10-27 US US10/450,247 patent/US20040028913A1/en not_active Abandoned
- 2001-10-27 CA CA002431055A patent/CA2431055A1/en not_active Abandoned
- 2001-10-27 WO PCT/EP2001/012466 patent/WO2002047801A1/en not_active Application Discontinuation
-
2003
- 2003-06-13 NO NO20032719A patent/NO20032719D0/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1585183A1 (en) * | 2004-03-26 | 2005-10-12 | Fuji Photo Film Co. Ltd. | Compound for use as a solid electrolyte or proton conductor in a membrane electrode assembly in fuel cells |
| US7442459B2 (en) | 2005-05-13 | 2008-10-28 | Fujifilm Corporation | Solid electrolyte, membrane and electrode assembly, and fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| PL361860A1 (en) | 2004-10-04 |
| US20040028913A1 (en) | 2004-02-12 |
| NO20032719L (en) | 2003-06-13 |
| DE10061920A1 (en) | 2002-06-20 |
| NO20032719D0 (en) | 2003-06-13 |
| JP2004515896A (en) | 2004-05-27 |
| WO2002047801A1 (en) | 2002-06-20 |
| AU2002221771A1 (en) | 2002-06-24 |
| EP1345674A1 (en) | 2003-09-24 |
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