US20070128491A1 - Advanced solid acid electrolyte composites - Google Patents
Advanced solid acid electrolyte composites Download PDFInfo
- Publication number
- US20070128491A1 US20070128491A1 US11/485,715 US48571506A US2007128491A1 US 20070128491 A1 US20070128491 A1 US 20070128491A1 US 48571506 A US48571506 A US 48571506A US 2007128491 A1 US2007128491 A1 US 2007128491A1
- Authority
- US
- United States
- Prior art keywords
- solid acid
- membrane
- proton conducting
- secondary component
- conducting membrane
- 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
- 239000011973 solid acid Substances 0.000 title claims abstract description 295
- 239000002131 composite material Substances 0.000 title claims abstract description 151
- 239000003792 electrolyte Substances 0.000 title abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 204
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 138
- 239000001257 hydrogen Substances 0.000 claims abstract description 138
- 150000001875 compounds Chemical class 0.000 claims abstract description 78
- 239000000446 fuel Substances 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 45
- -1 poly(trimesic acid) Polymers 0.000 claims description 85
- 229910052751 metal Inorganic materials 0.000 claims description 80
- 239000002184 metal Substances 0.000 claims description 79
- 150000001768 cations Chemical class 0.000 claims description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 60
- 229920000642 polymer Polymers 0.000 claims description 58
- 239000011230 binding agent Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 230000003993 interaction Effects 0.000 claims description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 33
- 229910001477 LaPO4 Inorganic materials 0.000 claims description 27
- 239000000919 ceramic Substances 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 229920000557 Nafion® Polymers 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 229920002480 polybenzimidazole Polymers 0.000 claims description 21
- 229910052785 arsenic Inorganic materials 0.000 claims description 20
- 239000002086 nanomaterial Substances 0.000 claims description 20
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- 229920001721 polyimide Polymers 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000004642 Polyimide Substances 0.000 claims description 16
- 229910010272 inorganic material Inorganic materials 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 229910052732 germanium Inorganic materials 0.000 claims description 15
- 150000002484 inorganic compounds Chemical class 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 13
- 239000004020 conductor Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 230000007246 mechanism Effects 0.000 claims description 6
- 239000002322 conducting polymer Substances 0.000 claims description 5
- 229920001940 conductive polymer Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 239000011163 secondary particle Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 25
- 229930000044 secondary metabolite Natural products 0.000 abstract description 19
- 150000002431 hydrogen Chemical class 0.000 abstract description 18
- 238000000926 separation method Methods 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 121
- 210000004027 cell Anatomy 0.000 description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 229910009112 xH2O Inorganic materials 0.000 description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 239000012071 phase Substances 0.000 description 19
- 239000004693 Polybenzimidazole Substances 0.000 description 18
- 230000007704 transition Effects 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 15
- 241000894007 species Species 0.000 description 15
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical group OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 14
- 239000000370 acceptor Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 13
- 229910010271 silicon carbide Inorganic materials 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 11
- 229910052909 inorganic silicate Inorganic materials 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- MEAHOQPOZNHISZ-UHFFFAOYSA-M cesium;hydrogen sulfate Chemical compound [Cs+].OS([O-])(=O)=O MEAHOQPOZNHISZ-UHFFFAOYSA-M 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 8
- 230000036961 partial effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000087 stabilizing effect Effects 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229920005575 poly(amic acid) Polymers 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052747 lanthanoid Inorganic materials 0.000 description 6
- 150000002602 lanthanoids Chemical class 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000010128 melt processing Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000002071 nanotube Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910001848 post-transition metal Inorganic materials 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 230000000670 limiting effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 229910052706 scandium Inorganic materials 0.000 description 5
- 239000011669 selenium Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910017251 AsO4 Inorganic materials 0.000 description 4
- 229910020197 CePO4 Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910005833 GeO4 Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 229910003472 fullerene Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910018819 PO3F Inorganic materials 0.000 description 3
- 229910018830 PO3H Inorganic materials 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- 229910018143 SeO3 Inorganic materials 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004404 heteroalkyl group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 2
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- 229910015667 MoO4 Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910004074 SiF6 Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- FHESUNXRPBHDQM-UHFFFAOYSA-N diphenyl benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OC=2C=CC=CC=2)=CC=1C(=O)OC1=CC=CC=C1 FHESUNXRPBHDQM-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000006716 (C1-C6) heteroalkyl group Chemical group 0.000 description 1
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 1
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical group FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910002761 BaCeO3 Inorganic materials 0.000 description 1
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 229910003599 H2SeO4 Inorganic materials 0.000 description 1
- 229910003893 H2WO4 Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004954 Polyphthalamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920006355 Tefzel Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910008159 Zr(SO4)2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012078 proton-conducting electrolyte Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical class OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- NWUWMQRSDSSETA-UHFFFAOYSA-N thallane Chemical compound [TlH3] NWUWMQRSDSSETA-UHFFFAOYSA-N 0.000 description 1
- 229910000089 thallane Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-O trimethylammonium Chemical compound C[NH+](C)C GETQZCLCWQTVFV-UHFFFAOYSA-O 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
-
- 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
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- Electrochemical devices depend on the flow of protons, or the flow of both protons and electrons, though a proton conducting material, such as a membrane. Accordingly, materials which conduct protons, or both protons and electrons, have applications as electrolytes or electrodes in a number of electrochemical devices including fuel cells, hydrogen pumps, supercapacitors, sensors, hydrogen separation membranes and membrane reactors.
- Fuel cells are attractive alternatives to combustion engines for power generation, because of their higher efficiency and the lower level of pollutants produced from their operation.
- a fuel cell generates electricity from the electrochemical reaction of a fuel, e.g. methane, methanol, gasoline, or hydrogen, with oxygen normally obtained from air.
- fuel cells There are three common types of fuel cells i.e., 1) direct hydrogen/air fuel cells, in which hydrogen is stored and then delivered to the fuel cell as needed; 2) indirect hydrogen/air fuel cells, in which hydrogen is generated on site from a hydrocarbon fuel, cleaned of carbon monoxide, and subsequently fed to the fuel cell; and 3) direct alcohol fuel cells, such as methanol (“DMFC”), ethanol, isopropanol and the like, in which an alcohol/water solution is directly supplied to the fuel cell.
- DMFC methanol
- ethanol isopropanol and the like
- the operating efficiency of the device is partly limited by the efficiency of the electrolyte at transporting protons.
- perfluorinated sulphonic acid polymers, polyhydrocarbon sulfonic polymers, and composites thereof are used as electrolyte membrane materials for fuel cells.
- these conventional materials utilize hydronium ions (H 3 O + ) to facilitate proton conduction. Accordingly, these materials must be hydrated, and a loss of water immediately results in degradation of the conductivity of the electrolyte and therefore the efficiency of the fuel cell. Moreover, this degradation is irreversible, i.e., a simple reintroduction of water to the system does not restore the conductivity of the electrolyte.
- peripheral systems to ensure water recirculation and temperature control to keep the water from evaporating.
- These peripheral systems increase the complexity and cost of these fuel cells, from the use of expensive noble catalysts (Pt) to temperature requirements that cannot exceed much above 100° C.
- Pt noble catalysts
- the fuel cell catalysts and other systems cannot be operated to maximum efficiency. Higher temperatures can also reduce carbon monoxide poisoning of the fuel cell catalyst.
- CsHSO 4 solid acids such as CsHSO 4 can be used as the electrolyte in fuel cells operated at temperatures of 140-160° C.
- Use of this material greatly simplifies fuel cell design relative to polymer electrolyte fuel cells because hydration of the electrolyte is not necessary and, because of the elevated temperature of operation, residual CO in the fuel stream can be better tolerated.
- the high conductivity of CsHSO 4 and analogous materials results from a structural phase transition (referred to as a superprotonic phase transition) that occurs at 141° C.
- CsH 2 PO 4 has as superprotonic transition and is stable under fuel cell conditions (Boysen, D. A., et al. Science 2004, 303, 68-70).
- the compound meets the necessary conditions of long term chemical stability for operation as a fuel cell electrolyte, the compound is water soluble and only becomes useful as an electrolyte above its superprotonic phase transition (Baranov, A. I., et al. Ferroelectrics 1989, 100, 135-141). Therefore, a need exists for solid acid electrolyte materials with high proton conductivity over a large range of temperatures that are stable under fuel cell conditions.
- the present invention is directed to a proton conducting membrane comprising a stable electrolyte composite material having high protonic conductivity, improved mechanical properties and capability of extended operation at a wide range of temperatures; methods of preparing such a proton conducting membrane; devices incorporating such a membrane; and uses of such a membrane in applications, such as fuel cells, hydrogen separations, membrane reactors and sensors.
- the proton conducting membrane comprises a stable electrolyte composite material comprising a solid acid component, a surface-hydrogen-containing secondary component and an interface formed between the solid acid component and the secondary component.
- the composite material has improved mechanical property.
- the secondary component can improve the mechanical stability of solid acid electrolyte membrane with respect to thermal creep by reducing the propensity of solid acids to plastically deform both at ambient and elevated temperatures.
- the interactions between the solid acid surface and the surface of the secondary compound can also stabilize the surface of the solid acid with respect to dehydration, thus allowing operation of the electrochemical device using the composite electrolyte to higher temperatures with respect to the same device using a solid acid compound alone as its electrolyte.
- the composite material can have one or more features or advantages, such as, for example, high conductivity from near ambient to elevated temperature; mechanically stabilizing with respect to thermal creep; kinetically stabilizing with respect to dehydration; and increased conductivity in its superprotonic phases.
- the present invention provides a proton conducting membrane.
- the membrane includes a solid acid component capable of conducting protons in a solid state through a superprotonic mechanism, a secondary component having surface hydrogen, and a plurality of interfaces formed by the solid acid component and the secondary component.
- the interfaces are formed by hydrogen bonding interactions between the solid acid component and the secondary component.
- the proton conducting membrane further includes a structural binder selected from, for example, carbon materials, graphite, a polymer, a ceramic, glass, a metal, a nanostructure or a mixture thereof.
- the proton conducting membrane further includes a separate electrically conducting material.
- the present invention provides a proton conducting membrane having a plurality of solid acid particles capable of conducting protons in a solid state through a superprotonic mechanism, a plurality of secondary component particles having surface hydrogen, and a plurality of interfaces formed by the solid acid particles and the secondary component particles.
- the interfaces are formed by hydrogen bonding interactions between the solid acid particles and the secondary component particles.
- the proton conducting membrane includes a structural binder selected from, for example, carbon materials, graphite, a polymer, a ceramic, glass, a metal, a nanostructure or a mixture thereof.
- the present invention provides a proton conducting membrane made by contacting a solid acid component and a secondary component having a plurality of surface hydrogen under conditions sufficient to generate a composite, wherein the solid acid interact with the secondary component to form a plurality of interfaces.
- the proton conducting membrane of the present invention comprises a solid acid having the formula: M a H b (XO t ) c ; a secondary component having surface hydrogen and selected from the group consisting of a polymer and ceramic; and a plurality of interfaces formed between the solid acid and the secondary component, wherein M is a cation having a charge from +1 to +7, preferably from +1 to +4, and more preferably from +1 to +3; X is selected from the group consisting of S, Se, P, As, Si, Ge, V, Cr and Mn; and a, b, t and c are each independently a non-negative real number, preferably from 1 to 15, more preferably from 1 to 9, and even more preferably from 1 to 4.
- the proton conducting membrane of the present invention comprises an eulytite solid acid, a secondary component having surface hydrogen a plurality of interfaces formed between the solid acid and the secondary component.
- the proton conducting membrane of the present invention comprises a solid acid; a secondary component having the formula: M′ d (X′O y ) e *nH 2 O(H f X′′O z ) g ; and a plurality of interfaces formed between the solid acid and the secondary component, wherein M′ is a cation having a charge from +1 to +7, preferably from +1 to +4, and more preferably from +1 to +3; X′ and X′′ are each independently selected from the group consisting of S, Se, P, As, Si, Ge; n and g are non-negative real numbers; and d, e, f, y and z are each independently a non-negative real number, preferably from 1 to 15, more preferably from 1 to 9, and even more preferably from 1 to 4.
- the present invention provides a method for preparing a proton conducting membrane.
- the method includes contacting a solid acid component with a secondary component having a plurality of surface hydrogen to generate a composite, wherein the solid acid interacts with the secondary component to form a plurality of interfaces.
- the present invention provides a method of rehydrating a solid acid composite.
- the method includes contacting the solid acid composite with a water molecule under conditions sufficient for rehydrating.
- the present invention provides a method of melt-processing.
- the method includes contacting a solid acid with a preformed membrane, of the secondary component, in a melting state.
- the present invention provides a fuel system comprising a proton conducting membrane.
- the membrane includes a solid acid component, a secondary component and a plurality of interfaces formed by the solid acid and the secondary component.
- the fuel cell system provides electrical power to an external device.
- the present invention provides a use of the proton conducting membrane for hydrogen separation and in a device selected from the group consisting of a fuel cell, a membrane reactor and a sensor.
- FIG. 1 illustrates a comparison of conductivity of pure CsH 2 PO 4 versus a CsH 2 PO 4 /LaPO 4 *nH 2 O(H 3 PO 4 ) g composite, where n and g are non-negative real numbers.
- the composite has higher or equal conductivity to that of pure CsH 2 PO 4 at all measured temperatures. Measurements were taken upon cooling at 1° C./min, under flowing air atmospheres with a partial pressure ⁇ 0.7 atm.
- FIG. 2 illustrates the ability of the CsH 2 PO 4 /LaPO 4 *nH 2 O(H 3 PO 4 ) g composite to rehydrate below ⁇ 300° C.
- the conductivity of the composite can be measured up to 400° C. All measurements were taken with heating/cooling rates of 1° C./min, under flowing air atmospheres with a partial pressure ⁇ 0.7 atm.
- FIG. 3 illustrates the ability of the CsH 2 PO 4 /LaPO 4 *nH 2 O(H 3 PO 4 ) g composite to rehydrate at 156° C. after having been dehydrated at 400° C. for 6 hrs. Measurements were taken under flowing air atmospheres with a partial pressure ⁇ 0.7 atm.
- FIG. 4 illustrates a composite membrane prepared from CsH 2 PO 4 and SiC by mechanical mixing, followed by mechanical or thermal densification.
- FIG. 4A shows a top view of SC(0001) down the hexagonal axis.
- FIG. 4B shows a side view of the structure schematically absorbed species (represented by small spheres) on both Si and C surfaces (represented by large and medium spheres), respectively.
- FIG. 5 illustrates an ionomer structure of a sulfonated terafluorethylene.
- FIG. 6 illustrate scanning electron micrographs of the 3DOM polyimide membrane prepared by using a 550 nm silica template: (a) surface view; and (b) cross-sectional view.
- metal cation includes to elements of the periodic table that are metallic or semi-metallic and positively charged as a result of having fewer electrons in the valence shell than are present for the neutral metallic element.
- Metals that are useful in the present invention include, but are not limited to, the alkali metals, alkaline earth metals, transition metals, the lanthanides, and post-transition metals.
- proton conducting membrane includes to a matrix of material that is capable of conducting protons through the matrix.
- the proton conducting membrane can also conduct electrons.
- Proton conducting membranes of the present invention comprise solid acid composites and, optionally, a material that binds the composite together.
- solid acid includes to compounds, in particular, inorganic compounds, which have properties that are intermediate between those of a normal acid, such as, H 2 SO 4 , and a normal salt, such as Cs 2 SO 4 .
- a normal acid such as, H 2 SO 4
- a normal salt such as Cs 2 SO 4
- the chemical formula of the solid acids of the type used according to the present invention can be written as a combination of the salt and the acid, such as, M a H b (XO t ) c , where M is metal, XO t is oxyanion, subscripts a, b and c are non-negative real numbers.
- An example of a solid acid is CsH 2 PO 4 .
- the solid acid used in the present invention have structural hydrogen, which are superprotonic.
- a further example of the solid acid is a compound having eulytite structure, for example, with a space group I 4 3d.
- Solid acids have properties that are intermediate between those of a normal acid, such as, H 2 SO 4 , and a normal salt, such as, Cs 2 SO 4 .
- Solid acids generally comprise oxyanions, such as, SO 4 2 ⁇ , SO 3 2 ⁇ , SeO 4 2 ⁇ , SeO 3 2 ⁇ , PO 4 3 ⁇ , PO 3 F 2 ⁇ , PO 3 H 2 ⁇ , AsO 4 3 ⁇ , SiF 6 2 ⁇ or AlF 6 3 ⁇ , SiO 4 4 ⁇ , GeO 4 4 ⁇ , SeO 4 4 ⁇ , CrO 4 2 ⁇ , VO 4 3 ⁇ , MnO 4 2 ⁇ , MnO 4 ⁇ , WO 4 2 ⁇ , MoO 4 2 ⁇ , BF 4 ⁇ , PF 6 ⁇ and SbF 6 ⁇ , and the like, which are linked together via O—H—O hydrogen bonds.
- oxyanions such as, SO 4 2 ⁇ , SO 3 2 ⁇ , SeO 4 2 ⁇ , SeO 3 2 ⁇ , PO 4 3 ⁇ , PO 3 F 2 ⁇ , PO 3 H 2 ⁇ , AsO 4 3 ⁇ , SiF 6 2 ⁇ or AlF 6 3 ⁇
- the structure can contain more than one type of oxyanion XO 4 , XO 3 , XO 3 A, XF 4 or XF 6 group, and can also contain more than one type of cation M species.
- the term “superprotonic” includes to a phase transition from an ordered structure to a disordered structure accompanying by a significant increase in proton conductivity.
- CsHSO 4 undergoes superprotonic transition at 141° C. with an increase in proton conductivity by 3 to 4 orders of magnitude from 10 ⁇ 6 ⁇ ⁇ 1 cm ⁇ 1 to 10 ⁇ 3 - 10 ⁇ 2 ⁇ ⁇ 1 cm ⁇ 1 .
- structural binder includes to a matrix material that enhances the mechanical integrity and/or chemical stability of the proton conducting membrane.
- Structural binders useful in the present invention include, but are not limited to, carbon, graphite, a polymer, ceramic, glass, silicon dioxide (e.g., quartz), a semiconductor, a nanostructure, a metal and a mixture thereof.
- the structural binder can be electrically conducting or insulating. When the structural binder is electrically conducting it can conduct protons, electrons or both, such that the proton conducting membrane can conduct either protons across the membrane, or both protons and electrons across the membrane.
- the structural binder can be ionically conducting.
- non-negative real number includes to any number (e.g., whole or fractions) that is either a positive number or zero.
- the non-negative real numbers are selected such that the inorganic solid acids or the secondary component inorganic compounds are charge neutral.
- the present invention is directed to a proton conducting membrane comprising a stable electrolyte composite material.
- the composite material comprises a solid acid component, a secondary component and a plurality of interfaces formed by the solid acid and the secondary component.
- the solid acid and the secondary component can exist as particles of micrometer or nanometer dimensions with enhanced interactions between the solid acid and the secondary component.
- the interfaces are formed by hydrogen bonding interactions between the solid acid and the secondary component.
- the membrane further comprises a structural binder.
- the solid acid composite or the proton conducting membrane can be made by contacting a solid acid component with a secondary component having a plurality of surface hydrogen under conditions sufficient to generate a composite, wherein said solid acid component interacts with said secondary component to form a plurality of interfaces.
- the solid acid composites have one or more features or advantages, for example, high protonic conductivity; mechanically stabilizing with respect to thermal creep; kinetically stabilizing with respect to dehydration; and increased conductivity in their superprotonic phases.
- the current invention is directed to solid acid composites that have high efficiency and do not suffer reduction in the presence of catalytic materials, such as Ru, Pt and other transition metals, are stable in a liquid water environment, and have high proton conductivity over a large range of temperatures.
- catalytic materials such as Ru, Pt and other transition metals
- some solid acids composites are likely to express superprotonic conductivity from or even below ambient temperatures to elevated temperatures i.e., up to the dehydration point of the particular compound.
- These advantageous properties are attributed to the stabilizing effect of the secondary component and the formation of extended hydrogen bonding network interfaces.
- certain oxyanions, such as PO 4 and SiO 4 have shown better stabilities to reduction in the presence of catalytic materials than other oxyanions.
- the solid acid component can be organometllic compounds, inorganic compounds or mixtures thereof.
- the solid acids are compounds that are stable at an elevated temperature and can undergo superprotonic transitions. More preferably, the solid acids are inorganic compounds that can undergo superprotonic phase transitions.
- the superprotonic transition can take place at an ambient temperature, for example, about 20° C. or less, or at an elevated temperature, for example, greater than 130° C., such as in the range of 140° C. to 450° C.
- An exemplary example of such solid acid is CsH 2 PO 4 .
- the solid acids used herein are inorganic compounds containing one or more cations and one or more anions whose properties are intermediate between those of a normal acid, such as H 2 SO 4 and a normal salt, such as Cs 2 SO 4 .
- a normal acid such as H 2 SO 4
- a normal salt such as Cs 2 SO 4 .
- An example of a solid acid is CsHSO 4 .
- the chemical formula of the solid acids can be written as a combination of the salt and acid.
- the cation can be a metal cation or non-metal cation, such as NH 4 + .
- the solid acids are comprised of oxyanions, which are linked together via O—H—O hydrogen bonds, dipolar interactions, van der Waals interactions, ionic interactions or combinations of the foregoing interactions. preferably, the solid acids are linked via O—H—O hydrogen bonds.
- the structure can have more than one type of oxyanion.
- Metals that are useful in the present invention include alkali metals, alkaline earth metals, transition metals, the lanthanides, and post-transition metals.
- Alkali metals include, for example, Li, Na, K, Rb and Cs.
- Alkaline earth metals include, but are not limited to, Be, Mg, Ca, Sr and Ba.
- Transition metals include, but are not limited to, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg and Ac.
- the lanthanides include, for example, La, Ce, Pr, Nd, Pm, Sm, Eu, Dg, Tb, Dy, Ho, Er, Tm, Yb and Lu.
- Post-transition metals include, for example, B, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, and Po. Additional metals include the semi-metals.
- One of skill in the art will appreciate that many of the metals described above can each adopt several different oxidation states, all of which are useful in the present invention. In some instances, the most stable oxidation state is formed, but other oxidation states are also useful in the present invention.
- Metal cations useful in the present invention include, but are not limited to, metal cations having a 1+ charge, a 2+ charge, a 3+ charge, a 4+ charge, a 5+ charge, a 6+ charge and a 7+ charge. Metal cations having other charges are also useful in the present invention.
- the compounds of the present invention can include more than one type of metal.
- Useful elements for the oxyanions of the compounds of the present invention include, but are not limited to, B, P, Si, As, Ge, S, Se, Sb, W, Cr, Mn and V. Some of the useful cations of these elements include, but are not limited to, B 3+ , P 4+ , P 5+ , Si 4+ , As 5+ , Ge 4+ , S 4+ , S 5+ , S 6+ , Se 4+ , Se 6+ , Sb 6+ , W 3+ , W 4+ , W 5+ , W 6+ , Cr 6+ , V 4+ , V 5+ , Mn 2+ , Mn 4+ , Mn 6+ and Mn 7+ .
- B B, P, Si, As, Ge, S, Se, Sb, W, Cr, Mn and V.
- Oxyanions useful in the present invention include, but are not limited to, SO 4 2 ⁇ , SO 3 2 ⁇ , SeO 4 2 ⁇ , SeO 3 2 ⁇ , PO 4 3 ⁇ , PO 3 F 2 ⁇ , PO 3 H 2 ⁇ , AsO 4 3 ⁇ , SiF 6 2 ⁇ or AlF 6 3 ⁇ , SiO 4 4 ⁇ , GeO 4 4 ⁇ , SeO 4 4 ⁇ , CrO 4 2 ⁇ , VO 4 3 ⁇ , MnO 4 2 ⁇ , MnO 4 ⁇ , WO 4 2 ⁇ , MoO 4 2 ⁇ , BF 4 ⁇ , PF 6 ⁇ and SbF 6 ⁇ .
- the oxyanions are linked together via O—H—O hydrogen bonds.
- the oxyanions can be linked together via O—H—O hydrogen bonds, dipolar interactions, van der Waals interactions, ionic interactions or combinations of interactions.
- the compounds of the present invention can contain more than one type of oxyanions.
- One of skill in the art will appreciate that other oxyanions are also useful in the present invention.
- the solid acid component is a compound having formnula I: M a H b (XO t ) c , where M is a cation having a charge from +1 to +7, preferably, from +1 to +4, more preferably from +1 to +3, most preferably from +1 to +2;
- X is an element that can form oxyanions; and
- a, b, t and c are each independently a non-negative real number, preferably from 1 to 15, such as more preferably from 1 to 9, and even more preferably from 1 to 4, such as, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0.
- M can be a metal cation, including, but not limiting to, alkali and alkaline metals, such as Li + , Be 2+ , Na + , Mg 2+ , K + , Ca 2+ , Rb + , Sr 2+ , Cs + , Ba 2+ ; transition metals, such as, Sc 3+ , V 3+ , V 5+ , Cr 3+ , Cr 5+ , Mn 2+ , Mn 3+ , Mn 6+ , Mn 7+ , Fe 2+ , Fe 3+ , Co + , Co 2+ , Ni 2+ , Cu + , Cu 2+ , Zn 2+ , Y 3+ , Nb 3+ , Mo 3+ , Mo 6+ , Ta 3+ , Ta 5+ , W 3+ , W 6+ , Ru 2+ , Rh 2+ , Rh 3+ , Pd 2+ , Pd 4+ , Ag + , Cd 2
- M is a metal cation selecting from the group consisting of Li + , Be 2+ , Na + , Mg 2+ , K + , Ca 2+ , Rb + , Sr 2+ , Cs + , Ba 2+ , Mn 2+ , Fe 2+ , Co + , Co 2+ , Ni 2+ , Cu + , Cu 2+ , Zn 2+ , Ru 2+ , Rh 2+ , Pd 2+ , Ag + , Cd 2+ , Pt 2+ , Au + , Hg + , Hg 2+ , In + , Tl + , Ge 2+ , Sn 2+ , Pb 2+ and mixtures thereof.
- M is a non-metal cation, including, but not limiting to, for example, NH 4 + .
- X is an element selected from the group consisting of S, Se, P, As, Si, Ge, V, Cr, W and Mn.
- the solid acid component can also be a mixture of different kinds of solid acid.
- the solid acid component is a compound having the formula Cs 2 (HSO 4 )(H 2 PO 4 ), which is a mixture of CsHSO 4 and CsH 2 PO 4 .
- the solid acid component can be a compound having different types of cations and/or oxyanions.
- the solid acid component is a compound having the formula Ia: (M A ) a′ (M B ) a′′ H b (XO t ) c , where M A and M B are each independently a cation having +1 to +7 charge; preferably, from +1 to +4; and more preferably, from +1 to +3.
- Suitable cations include, but are not limited to, alkali and alkaline metals, such as Li + , Be 2+ , Na + , Mg 2+ , K + , Ca 2+ , Rb + , Sr 2+ , Cs + , Ba 2+ ; transition metals, such as, Sc 3+ , V 3+ , V 5+ , Cr 3+ , Cr 5+ , Mn 2+ , Mn 3+ , Mn 6+ , Mn 7+ , Fe 2+ , Fe 3+ , Co + , Co 2+ , Ni 2+ , Cu + , Cu 2+ , Zn 2+ , Y 3+ , Nb 3+ , Mo 3+ , Mo 6+ , Ta 3+ , Ta 5+ , W 3+ , W 6+ , Ru 2+ , Rh 2+ , Rh 3+ , Pd 2+ , Pd 4+ , Ag + , Cd 2+ , Cd 3+ ,
- X is an element that can form oxyanions and selected from the group consisting of S, Se, P, As, Si, Ge, V, Cr, W and Mn.
- Each of the subscripts a′, a′′, b, t, and c is independently a non-negative real number, preferably from 1 to 15, more preferably from 1 to 9, and ven more preferably from 1 to 4, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0.
- Preferred cations for M A and M B include, but are not limited to, Li + , Be 2+ , Na + , Mg 2+ , K + , Ca 2+ , Rb + , Sr 2+ , Cs + , Ba 2+ , Mn 2+ , Fe 2+ , Co + , Co 2+ , Ni 2+ , Cu + , Cu 2+ , Zn 2+ , Ru 2+ , Rh 2+ , Pd 2+ , Ag + , Cd 2+ , Pt 2+ , Au + , Hg + , Hg 2+ , In + , Tl + , Ge 2+ , Sn 2+ , Pb 2+ , NH 4 + and mixtures thereof.
- M A and M B are cations include, but are not limited to, one or more species selected from the group consisting of Li + , Be 2+ , Na + , Mg 2+ , K + , Ca 2+ , Rb + , Sr 2+ , Cs + , Ba 2+ and NH 4 + .
- An exemplary of the solid acid of this type is CsKHPO 4 .
- the solid acid is a compound having the formula Ib: (M A ) a′ (M B ) a′′ (M C ) a′′′ H b (XO t ) c , where M A , M B and M C are each independently a cation having a charge from +1 to +7; preferably from +1 to +4; and more preferably from +1 to +3. M A , M B and M C are each independent cations and are selected from the group as defined above. X is the same as defined above.
- Each of the subscripts a′, a′′, a′′′, b, t, and c is independently a non-negative real number, preferably from 1 to 15, more preferably from 1 to 9, and even more preferably from 1 to 4, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0.
- solid acids include, but are not limited to, CsH 2 PO 4 , Cs 2 HPO 4 , Cs 5 (HSO 4 ) 3 (H 2 PO 4 ) 2 , Cs 2 (HSO 4 )(H 2 PO 4 ), Cs 3 (HSO 4 ) 2 (H 2 PO 4 ), Cs 3 (HSO 4 ) 2 (H 1.5 (S 0.5 P 0.5 )O 4 ), Cs 3 H 3 (SO 4 ) 3 .xH 2 O, TlHSO 4 , CsHSeO 4 , Cs 2 (HSeO 4 )(H 2 PO 4 ), Cs 3 H(SeO 4 ) 2 (NH 4 ) 3 H(SO 4 ) 2 , (NH 4 ) 2 (HSO 4 )(H 2 PO 4 ), Rb 3 H(SO 4 ) 2 , Rb 3 H(SeO 4 ) 2 , Cs 1.5 Li 1.5 H(SO 4 ) 2 , Cs 2 Na(HSO 4 ) 3
- the solid acids of the formulas I, Ia and Ib can undergo superprotonic transition at an elevated temperature, for example, CsHSO 4 and CsH 2 PO 4 can undergo superprotonic transition at about 140° C. and 230° C., respectively.
- the structural hydrogens of the solid acids of the formulas I, Ia and Ib are capable of forming hydrogen bonding network with the secondary component, which has hydrogen bonding donors and acceptors.
- the solid acids have an eulytite structure with structural hydrogen, are superprotonic and have a space group of I 4 3d, a body-centered cubic crystal structure having rotoinversion symmetry for every 90° of rotation about the face axis, a three-fold axis of symmetry down the body diagonal, and a diagonal glide with steps of one quarter unit cell edge in each direction.
- the solid acids are represented by formula II: M 4i H j (XO k ) 3i , wherein M is at least one metal and each independently a metal cation.
- X is at least one member and each independently selected from the group consisting of P, Si, As, Ge, S, Se, W, Cr and V.
- each of subscripts i, j and k is independently a non-negative real number.
- the solid acids are compounds having the formula IIa: M 1+ i M 2+ j M 3+ k M 4+ l M 5+ m H(3n+4o+2p ⁇ i ⁇ 2j ⁇ 3k ⁇ 4l ⁇ 5m)(X +5 O 4 ) n (X +4 O 4 ) o (X +6 O 4 ) p , wherein each M is a metal cation of the labeled charge state, and each X is an element selected from the group consisting of P, Si, As, Ge, S, Se, W, Cr and V, having the labeled charge state.
- each of subscripts i, j, k, l, m, n, o and p is a non-negative real number.
- the solid acids are compounds of the formula III: M 2+ 4 H(XO 4 ) 3 , wherein M 2+ is a metal cation having a +2 charge.
- M 2+ is a metal cation having a +2 charge.
- compound Ba 4 H(PO 4 ) 3 can be thought of as an intermediate to Ba 3 La(PO 4 ) 3 , and Ba 4 (PO 4 ) 2 (SO 4 ). With the incorporation of hydrogen and the inherent rotation of the PO 4 groups, this compound is a preferred solid acid of the present invention.
- the solid acids are compounds of the formula IIIa: M 2+ 4 H (1+i+j) (X +5 O 4 ) (3 ⁇ i ⁇ j) (X +4 O 4 ) i (X +6 O 4 ) j , wherein M 2+ is a metal cation having a +2 charge, and each X is an element selected from the group consisting of P, Si, As, Ge, S, Se, W, Cr and V, having the labeled charge state.
- each of subscripts i and j is a non-negative real number.
- the solid acids are compounds of the formula IV: M 2+ 3 M 3+ H j (XO 4 ) 3 ⁇ j (X′O 4 ) j , wherein M 2+ is a metal cation having a +2 charge; M 3+ is a metal cation having a +3 charge; X is a member selected from the group consisting of P, V and As; and X′ is a member selected from the group consisting of Si and Ge.
- the compound Ba 3 BiH(PO 4 ) 2 (SiO 4 ) is an intermediate compound between Ba 3 Bi(PO 4 ) 2 (SiO 4 ) and Bi 4 (SiO 4 ) 3 .
- the reduced charge of the SiO 4 group (formally, +4 for Si) compared to a PO 4 group (formally, +5 for P) requires the incorporation of a proton for charge balance.
- the present invention provides compounds of the formula V: M 1+ j M 2+ 3 ⁇ j M 3+ H j (XO 4 ) 3 , wherein M 1+ is a metal cation having a +1 charge; M 2+ is a metal cation having a +2 charge; and M 3+ is a metal cation having a +3 charge.
- the compound KBa 2 BiH(PO 4 ) 3 is an intermediate compound between KBaBi 2 (PO 4 ) 3 , and Ba 3 Bi(PO 4 ) 3 .
- Superprotonic conductivity arises due to the presence of protons attached to the rotationally disordered tetrahedral of the compound.
- the present invention provides compounds of the formula Va: M 1+ i M 2+ (4 ⁇ i ⁇ j) M 3+ j H (1+i+j+k ⁇ l) (X 5+ O 4 ) (3 ⁇ k ⁇ l) (X +4 O 4 ) k (X +6 O 4 ) l , wherein each M is a metal cation of the labeled charge state, and each X is an element selected from the group consisting of P, Si, As, Ge, S, Se, W, Cr and V, having the labeled charge state.
- each of subscript i, j, k and l are independently a non-negative real number.
- the present invention provides compounds of the formula VI: M 1+ j M 2+ (4n ⁇ l ⁇ j) M (2+n) H j (XO 4 ) 3n , wherein M 1+ is a metal cation having a +1 charge; M 2+ is a metal cation having a +2 charge; M (2+n) is a metal cation having a +3, +4 or +5 charge; and subscript n is a non-negative real number.
- the compound KBa 6 ZrH(PO 4 ) 6 because of the incorporation of hydrogen into the eulytite structure (with its inherent rotations of the PO 4 groups) is another preferred compound for expressing superprotonic conductivity.
- the present invention provides compounds of Formula VIa: M 1+ j M 2+ (4n ⁇ l ⁇ j) M (2+n) H (j+k*n ⁇ l*n) (X +5 O 4 ) (3 ⁇ k ⁇ l)*n (X +4 O 4 ) k*n (X +6 O 4 ) l*n , wherein each M is a metal cation of the labeled charge state, and each X is an element selected from the group consisting of P, Si, As, Ge, S, Se, W, Cr and V, having the labeled charge state.
- each of subscripts j, k, l and n are independently a non-negative real number.
- the present invention provides compounds of formula VII: M 2+ (4n ⁇ l) M (2+n ⁇ j) H j (XO 4 ) 3n , wherein M 2+ is a metal cation having a +2 charge; M (2+n ⁇ j) is a metal cation having a +3, +4 or +5 charge; and subscript n is a non-negative real number.
- M 2+ is a metal cation having a +2 charge
- M (2+n ⁇ j) is a metal cation having a +3, +4 or +5 charge
- subscript n is a non-negative real number.
- the known compound Ba 7 Sn +4 (PO 4 ) 6 can have the Sn +4 atoms reduced, in the presence of a hydrogen containing atmosphere, to Sn +2 atoms.
- Hydrogen is then simultaneously incorporated in to the eulytite structure (creating Ba 7 Sn +2 H 2 (PO 4 ) 6 ) for charge balance.
- the combination of the inherent rotations of the PO 4 groups in this eulytite structure and the presence of acid protons effectuate superprotonic conductivity.
- the present invention provides compounds of Formula VIIa: M 2+ (4n ⁇ l) M (2+n+j) H (j+k*n ⁇ l*n) (X +5 O 4 ) (3 ⁇ k ⁇ l)*n (X +4 O 4 ) k*n (X +6 O 4 ) l*n , wherein each M is a metal cation of the labeled charge state, and each X is an element selected from the group consisting of P, Si, As, Ge, S, Se, W, Cr and V, having the labeled charge state.
- each of subscripts j, k, l and n are independently a non-negative real number.
- the solid acid is selected from the group consisting of M 2+ 4 H(XO 4 ) 3 , M 2+ 3 M 3+ H j (XO 4 ) 3 ⁇ j (X′O 4 ) j , M 1+ j M 2+ 3 ⁇ j M 3+ H j (XO 4 ) 3 , M 1+ j M 2+ (4n ⁇ l ⁇ j) M (2+n) H j (XO 4 ) 3n and M 2+ (4n ⁇ l) M (2+n ⁇ j) H j (XO 4 ) 3n , wherein M 1+ is a metal cation having a +1 charge; M 2+ is a metal cation having a +2 charge; M 3+ is a metal cation having a +3 charge; M (2+n) is a metal cation having a +3, +4 or +5 charge; M (2+n ⁇ j) is a metal cation having a +3, +4 or +5 charge; and subscripts j
- any combination of the above examples have superprotonic conductivity over a large temperature range and are stable in a liquid water environment.
- a 4:3 of cation to anion ratio (corresponding to M 4 (XO 4 ) 3 , i.e., the general formula) is maintained, while the hydrogen atoms are incorporated into the structure for charge neutrality.
- the incorporation of the appropriate amount of protons into the structure is possible.
- the most general formula for superprotonic solid acid eulytites simply maintains an overall ratio of 4:3 for the number of metal cations to number of anions in the structure, regardless of the exact stoichiometry, with some amount of stoichiometric hydrogen incorporated into the crystal structure.
- This generalization also applies to non-homogenous tetrahedral anions such as PO 3 F, PO 3 H, AsO 3 F, SiO 3 F, and the like, as well as non-tetrahedral anions that might be in the eulytite structure (such as I ⁇ 1 in the compound Pb 8 (PO 4 ) 5 I).
- the cations need not to be individual atoms such as K, Ba, or Bi, but can equally be NH 4 + , or other small molecules. As long as the eulytite structure is maintained (with the inherent rotations of the oxyanions) and protons are incorporated into the crystalline structure, all such compounds exhibit superprotonic conductivity.
- Some solid acids can be prepared by contacting a metal, a carbonate salt, a metal oxide or a metal hydoxide with a predetermined amount of an acid in an aqueous solution, then evaporating the solvent.
- CsH 2 PO 4 can be prepared by reacting one equiv. of Cs 2 CO 3 with one equiv. of H 3 PO 4 .
- CsHSO 4 can be prepared by reacting one equiv. of Cs 2 CO 3 with one equiv. of H 2 SO 4 .
- Synthesis routes to superprotonic solid acids include, but are not limited to: hydrothermal methods, melt processing, high pressure/temperature methods, single crystal growth from phosphate and silicate gels, ion exchange procedures, and solid state synthesis followed by reduction/incorporation of hydrogen.
- Various methods for preparing solid acids are described in the U.S. Pat. No. 6,468,684 and US Patent Application No. 2006/0020070 incorporated herein by reference.
- the secondary component in the solid acid composite can be an organic compound, an organometallic compound, an inorganic compound, a ceramic, a nanostructure, a metal or a polymer.
- the secondary component has a plurality of surface hydrogens and is capable of forming hydrogen bonds with the solid acids.
- suitable secondary component includes, but is not limited to, an inorganic compound, a ceramic material, a nanostructure and a polymer, each of the compounds, material structures or polymers having hydrogen bond donors and/or acceptors on the respective surfaces.
- the surface hydrogen of the secondary compounds can interact with solid acids through hydrogen bonding, dipolar interactions, van der Waals interactions or combinations of interactions.
- the surface hydrogen of the secondary component interact with the surface of the solid acid compounds, for example, through hydrogen bonding, to form a plurality of interfaces that are favorable with respect to high protonic conductivities and stabilities.
- the secondary component can interact with the solid acid to form a hydrogen bonded network at the interfaces leading to increased resistance for mechanical creep and high conductivity for solid acid.
- the secondary component is an inorganic compound.
- inorganic compounds have hydrogen atoms on their surfaces. In general, these compounds can be classified into four groups: 1) crystallographic hydrates, where the water is incorporated into the crystal structure (e.g., Na 2 H 2 SiO 4 *3H 2 O, Sr 3 (PO 4 )*4H 2 O, BaHAsO 4 *H 2 O, Ca 8 (HPO 4 ) 2 (PO 4 ) 4 *5H 2 O, etc. see, Schmid, R. L. et al. Acta Cryst. 1985 , C 41, 638-641; Collin, R. L. J. Chem. and Eng. Data 1964, 9(2), 165-66; Nabar, M. A.
- the secondary component is an inorganic compound of the formula VIII: M′ d (X′O y ) e *nH 2 O(H f X′′O z ) g , where M′ is a cation having a charge from +1 to +7; preferably from +1 to +4; more preferably, from +1 to +3.
- X′ and X′′ are each independently an element that can form oxyanions.
- Subscripts d, e, f, y and z are each independently a non-negative real number, preferably from 1 to 15, more preferably from 1 to 9, and even more preferably from 1 to 4, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0.
- M′ can be a metal cation selected from the group consisting of alkali and alkaline metals, such as Li + , Be 2+ , Na + , Mg 2+ , K + , Ca 2+ , Rb + , Sr 2+ , Cs + , Ba 2+ ; transition metals, such as, Sc 3+ , V 3+ , V 5+ , Cr 3+ , Cr 5+ , Mn 2+ , Mn 3+ , Mn 6+ , Mn 7+ , Fe 2+ , Fe 3+ , Co + , Co 2+ , Ni 2+ , Cu + , Cu 2+ , Zn 2+ , Y 3+ , Nb 3+ , Mo 3+ , Mo 6+ , Ta 3+ , Ta 5+ , W 3+ , W 6+ , Ru 2+ , Rh 2+ , Rh 3+ , Pd 2+ , Pd 4+ , Ag + , Cd 2+
- M′ is a metal cation selected from the group consisting of Li + , Be 2+ , Na + , Mg 2+ , K 30 , Ca 2+ , Rb + , Sr 2+ , Cs + , Ba 2+ , Mn 2+ , Fe 2+ , Co + , Co 2+ , Ni 2+ , Cu + , Cu 2+ , Zn 2+ , Ru 2+ , Rh 2+ , Pd 2+ , Ag + , Cd 2+ , Pt 2+ , Au + , Hg + , Hg 2+ , In + , Tl + , Ge 2+ , Sn 2+ , Pb 2+ and mixtures thereof.
- M′ is a metal cation including, but not limiting to, Li + , Be 2+ , Na + , Mg 2+ , K + , Ca 2+ , Rb + , Sr 2+ , Cs + , Ba 2+ and mixtures thereof.
- M′ is a non-metal cation, including, but not limiting to, NH 4 + , pyridinium ion, pyrrolium ion, imidazolium ion, (R 1 )NH 3 + , (R 1 )(R 2 )NH 2 + and (R 1 )(R 2 )(R 3 )NH + , where R 1 , R 2 and R 3 are each independently alkyl, C 3-12 cycloalkyl, arylalkyl, heteroalkyl, aryl and heteroaryl.
- Alkyl groups include linear alkyl or branched alkyl, preferably C 1-6 alkyl.
- Cycloalkyl groups include monocyclic, bicyclic, tricyclic and spiro alkyls.
- Aryl groups include C 6-12 aryl and fused aromatic compounds.
- Heteroalkyl groups refer to alkyl groups containing at least one heteroatom selected from O, N and S. Preferred heteroalkyls are C 1-6 heteroalkyls.
- Heteroaryl groups refer to aryl groups that contain from one to five heteroatoms selected from N, O, and S.
- ammonium ions include, but are not limited to, (C 2 H 5 ) 2 NH 2 + , CH 3 NH 3 + , (CH 3 ) 2 NH 2 + , (CH 3 ) 3 NH + , C 5 H 6 N + (pyridinium ion), C 4 H 5 N + (pyrrolium ion), C 3 H 5 N 2 + (imidazolium ion) and C 3 H 4 ON + (oxazolium ion).
- X′ and X′′ are each independently an element selected from the group consisting of S, Se, P, As, Si, Ge, V, Cr, W and Mn.
- Exemplary secondary component inorganic compounds include SiO 2 *xH 2 O, LaPO 4 *xH 2 O, LaPO 4 *xH 2 O(H 3 PO 4 ) n , CePO 4 *xH 2 O(H 3 PO 4 ) n , PrPO 4 *xH 2 O(H 3 PO 4 ) n , NdPO 4 *xH 2 O(H 3 PO 4 ) n , PmPO 4 *xH 2 O(H 3 PO 4 ) n , SmPO 4 *xH 2 O(H 3 PO 4 ) n , EuPO 4 *xH 2 O(H 3 PO 4 ) n , GdPO 4 *xH 2 O(H 3 PO 4 ) n , TbPO 4 *xH 2 O(H 3 PO 4 ) n , DyPO 4 *xH 2 O(H 3 PO 4 ) n , HoPO 4 *xH 2 O(H 3 PO 4 ) n , ErPO 4 *xH 2 O(H 3 PO 4
- the secondary component of the formula VIII has surface hydrogens resulting from the bonded H 2 O and/or acid, H f X′′O z .
- the compound is capable of forming a hydrogen bond network with the solid acid component resulting in a solid acid composite with increased thermal stability, improved mechanical properties, and high proton conductivity.
- the secondary component can be an inorganic eulytite compound.
- M Na, K, Rb, Ag, Ba, Sr, Ca, La, Ce, Pr, Bi, Pb, and the like
- X Si, Ge, P, As, V, S, Se, Cr
- Table 1 A list of some known eulytite compounds can be found in Table 1. In addition to the types of compounds listed in Table 1, there is evidence of significant solubilities of the different compounds with each other and hence, a large number of intermediate compounds can be synthesized (Perret, R. et al.
- the secondary inorganic compounds can be prepared by contacting a metal, a metal oxide, a metal hydroxide or a metal carbonate with a predetermined amount of acid in an aqueous solution; a protic organic solvent, such as an alcohol; a polar aprotic organic solvent, such as an amide or a sufoxide; or a mixed aqueous-organic solution.
- a protic organic solvent such as an alcohol
- a polar aprotic organic solvent such as an amide or a sufoxide
- a mixed aqueous-organic solution Preferably, the reaction is conducted in an aqueous environment.
- La(PO 4 ) can be prepared by reacting of La 2 O 3 with a stoichiometric amount of H 3 PO 4 in water.
- the secondary component can be an eulytite compound having a formula selected from the group consisting of M +3 4 (XO 4 ) 3 *nH 2 O(H f X′O z ) g , M +2 3 M +3 (XO 4 ) 3 *nH 2 O(H f X′O z ) g , M +1 j M +2 3 ⁇ j M +3 1+j (XO 4 ) 3 *nH 2 O(H f X′O z ) g , M +2 4 (XO 4 ) 2 (X′O 4 ) *nH 2 O(H f X′′O z ) g and M +2 4n ⁇ l M +(2+n) (XO 4 ) 3n *nH 2 O(H f X′O z ) g , where M is a metal as defined above and having the stated charge; X and X′ are each independently an element selected from the group consisting of
- Subscripts j, f, z, g and n are as defined above.
- the secondary component itself can be a composite material, such as ceramics having hydrogen bond donors and/or hydrogen bond acceptors molecules attached to the surfaces to provide hydrogen bonding active surface hydrogens.
- a composite material such as ceramics having hydrogen bond donors and/or hydrogen bond acceptors molecules attached to the surfaces to provide hydrogen bonding active surface hydrogens.
- Such composite materials include, but are not limited to ceramics, metals and glass.
- Preferred ceramic material includes, for example, silicon carbide (SiC), Si 3 N 4 , LaPO 4 , YPO 4 , AlPO 4 , CePO 4 , ZrO 2 , TiO 2 , BaZrO 3 , BaTiO 3 or Y 2 O 3 .
- Preferred metals include gold, silver, platinum, cobalt, nickel and palladium.
- the surface of SiC can contain a functional group, such as —OH, —NH 2 , NH 2 C(O)—, —COOH, —Si—H; or a molecule, such as NH 3 or H 2 O.
- the SiC can contain silanol groups, eg., Si—OH, absorbed hydrogen atoms (Si/C—H), water molecules (Si/C—OH 2 ) or ammonia (Si/C—NH 3 ).
- the surface of the ceramic materials can be modified through physical or chemical absorption by contacting the surface with the appropriate chemicals, including H 2 O, NH 3 , alcohols, amide, thiols, hydroxides or acids at ambient to elevated temperatures.
- the absorption reaction is carried out in solution, such as an aqueous solution.
- the acids used for absorption on the surface can be inorganic acids, such as HNO 3 , H 2 SO 4 , H 3 PO 4 , hydrogen halide, H 3 BO 3 , H 2 SeO 4 and H 2 WO 4 ; and organic acids, such as carboxylic acids.
- inorganic acids such as HNO 3 , H 2 SO 4 , H 3 PO 4 , hydrogen halide, H 3 BO 3 , H 2 SeO 4 and H 2 WO 4
- organic acids such as carboxylic acids.
- the chemicals used to modify the surface structure can be in either gas, liquid or solution phase.
- the absorbed species can remain stable on the surface at high temperatures (e.g. ⁇ 300° C.) for an extended period of time as a result of the formation of dative bonds between the donor molecules and the surface. Examples of stabilizing interactions of the absorbed species, such as NH 3 , water and hydroxyl ion on the SiC surface are shown below.
- the secondary component can be hompolymers, copolymers or polymer blends having hydrogen bond donor and/or acceptors attached to the polymers, preferably having a plurality of surface hydrogen suitable for hydrogen bonding.
- Suitable polymers can contain acid and/or base functionalities.
- polymers include, but are not limited to, polyimides; polyimidazoles, such as polybenzimidazoles, poly(2-hydroxybenzimidazole), poly(benzimidazole-5-carboxylic acid) and poly(2-nonyl benimidazole); poly(trimesic acid)s; polyamic acids; polyamic acids/polyimides; polyamines, polyamides, such as polyphthalamide; poly(monododecylphosphate); poly(dihexadadecyl phosphate), poly(phenyl phosphoric acid); polyaniline; a phosphated tetrafluroethylene coplolymer; and Nafion®, a sulfonated tetrafluorethylene copolymer manufactured by Dupont de Nemours chemical company.
- polyimides such as polybenzimidazoles, poly(2-hydroxybenzimidazole), poly(benzimidazole-5-carboxylic acid) and poly(2-nony
- the polymers have a cross-linked structure with surface hydrogens.
- the cross-linked polymers can be synthesized by homopolymerizing a multifunctional monomer or copolymerizing at least two multifunctional monomers.
- the monomers used for preparing cross-linked polymers typically have at least two reactive functional groups.
- An example of such a monomer is trimesic acid having the formula: C 6 H 3 (COOH) 3 with three carboxylic acid groups at 1, 3 and 5 positions of the benzene ring.
- the compound is a crystalline powder and has a melting temperature about ⁇ 375° C., and is used as a plasticizer to engineer the mechanical properties, epoxy resins and synthetic fibers.
- a composite membrane of a solid acid and trimesic acid can be formed by grinding the two compounds together and then mechanically compressing the mixture into the desired membrane shape.
- the trimesic acid can then be cross-linked to itself by heating at 250° C., forming a polymer support structure in the composite membrane.
- the hydrogens on the carboxylic groups can then interact with the non-bonded oxygens of the solid acid, while the hydrogens of the solid acid can form bonds with the double bonded carbonyl oxygens of the carboxylic groups and the residues of the hydroxyl groups of the carboxylic acids.
- the interaction of the solid acids and the polymer particles result in hydrogen bonds of medium strength being formed between the solid acid and polymer particles. These bonds are formed at random, greatly enhancing the protonic conductivity at the solid acid/polymer interface. At the same time, the medium strength bonds mechanically strengthen the interaction between the solid acid and polymer, thus transferring the mechanical properties of the polymer to the solid acid.
- the secondary component is a polyimidazole, such as polybenzimidazole (PBI), which can be mixed and made into a proton conducting electrolyte membrane with properties well suited for applications such as fuel cells, hydrogen separation membranes, electrolyzers, electrochromic displays, supercapacitors, and gas sensors (H 2 , CO, etc.).
- PBI polybenzimidazole
- solid acid/PBI proton conducting composite membranes have many advantages. First, solid acids have vapor pressures, which are several orders of magnitude lower than phosphoric acid, so that expensive graphitization of application parts is not necessary.
- solid acid electrolytes do not solubilize noble metal catalysts, allowing the use of much smaller catalyst particles (i.e., high catalyst surface area) and hence, lower catalyst loadings and MEA cost.
- the mechanical, chemical and thermal stabilities of PBI are a nearly ideal match for use with solid acid membranes operating in the range 200-300° C.
- the material maintains its polymer-like properties (e.g., compressive/tensile strengths and Poisson's ratio) up to ⁇ 540° C. and is highly resistant to both oxidation and reduction even at temperatures above 400° C.
- PBI can be synthesized by polymerization of 3,3′-diaminobenzidine and diphenyl isophthalate (see, Buckley, A. et al.
- the secondary component can be an ionomer, for example, a sufonated tetrafluorethylene copolymer, such as Nafion® (tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer) having the formula:
- Nafion® tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer
- These unique polymers have ionic properties as a result of incorporating perfluorovinyl ether groups terminated with sulfonate groups onto a polytetrafluoroethylene (e.g., Teflon) backbone.
- Nafion has excellent thermal (>300° C.) and mechanical stability, and resistance to chemical attack.
- Nafion can be cast into thin films by heating in aqueous alcohol at 250° C.
- Nafion derivatives are first synthesized by the copolymerization of tetrafluoroethylene and a derivative of a perfluoro(alkyl vinyl ether) with sulfonyl acid fluoride.
- the latter reagent can be prepared by the pyrolysis of its respective oxide or carboxylic acid to the olefinated.
- the resulting product is an —SO 2 F thermoplastic that is extruded into films of required thickness.
- This form of Nafion is chemically activated by hydrolysis by soaking the film in aqueous acid solution; this process gives the superacid —SO 3 H form (see, Mauritz, K. A. et al. “State of Understanding of Nafion” Chem. Rev. 2004, 104: 4535-4585; and U.S. Pat. No. 3,282,875 incorporated herein by reference).
- copolymer such as a phosphated tetrafluorethylene copolymer can be prepared using the similar methods.
- the secondary component can be polyimide, polyamic acid or a mixture of polyamic acid and polyimide.
- Polyimide can be synthesized by dehydration of polyamic acid as shown below:
- Polyamic acid has both hydrogen bond donors and acceptors, which can interact with solid acid, such as CsH 2 PO 4 to form composite materials having disordered hydrogen bonded network at the interface leading to high proton conductivity.
- Polyimide has oxygen and nitrogen atoms, which can interact with the hydrogen, such as surface hydrogen of the solid acid to form hydrogen bonds interfaces, which can also lead to high proton conductivity.
- the secondary component can be a nanostructure.
- Suitable nanostructures include, but are not limited to, finctionalized carbon nanotubes and functionalized fullerenes. Both single-wall and multi-wall nanotubes can be used. A person of skill in the art will appreciate that other functionalized nano materials can also be used.
- the nanostructure are functionalized with functional groups that can form hydrogen bonds with the solid acids. Suitable functional groups include, but are not limited to, OH, —NH 2 , NH 2 C(O)—, —COOH and —SH.
- Functionalized carbon nanostructures can be prepared according to the process known in the art (see, Smalley, R. E. et al.
- Carbon Nanotubes Synthesis, Structure, Properties and Applications , Springer; 1st Ed, 2001; Ajayan, Z. P. et al. “Making Functional Materials with Nanotubes” Material Res. Soc. Sym. Proc. 2002, V. 706; Geckeler, K. E. Functional Nanomaterials ; American Scientific Publishers, 2006).
- the solid acid composite materials also have interfaces with increased structural disorder compared to bulk solid acids, such that increased resistance to mechanical creep, improved thermal stability and enhanced proton conductivity are observed.
- the interfaces are formed by interactions between the solid acid component and the secondary component.
- the interfaces can be formed through hydrogen bonding, dipolar interaction, van der Waals interactions or combinations of forces.
- the interfaces are formed through hydrogen bonding interactions.
- Hydrogen bond donors are surface hydrogens and hydrogen bond acceptors are molecules or structures with atoms having lone-pair electrons. Examples of atoms suitable for hydrogen bonding include, but are not limited to, N, O, S or halogens, for example, F, Cl, and Br.
- the solid acids can be both hydrogen bonding donors and acceptors.
- the secondary component can be hydrogen bond donors and/or acceptors.
- the interfaces are formed by hydrogen bonding interactions between the hydrogen bond donors, such as surface hydrogens and acceptors of the solid acids and the hydrogen bond donor and acceptors of the secondary component.
- the hydrogen bond donors of the secondary component are surface hydrogens.
- the interfaces are formed by hydrogen bonding interactions between the hydrogen bond donors and acceptors of the solid acids and the surface hydrogens of the secondary component. The interfaces are formed such that they can provide high protonic conductivity, mechanically stabilizing solid acid electrolyte membranes with respect to thermal creep, and kinetically stabilizing the surfaces of solid acids with respect to, dehydration.
- the dimension of the interfaces can be controlled by using different solid acids, different secondary components or by alteration of the size of the solid acid particles and/or secondary component particles.
- the interfaces formed have a dimension ranging from about 5 nm to about 5 ⁇ m. The dimension of the interfaces is determined from the average distance of the particles in the composite.
- the interfaces can be formed by a solid acid and a secondary component selected from the group consisting of an inorganic compound, a polymer, a nanostructure, a metal, glass and ceramic material.
- the solid acid can be a compound with the formulas I, Ia, Ib, II, IIa, III, IIIa, IV, V, VI, VIa, VII, VIIa or combinations of the foregoing.
- the interfaces are formed between the solid acids and inorganic compounds, such as a compound having the formula VIII: M′ d (X′O y ) e *nH 2 O(H f X′′O z ) g as described above.
- the interfaces are formed by solid acids and an eulytite compound having the formula: M +3 4 (XO 4 ) 3 *nH 2 O(H f X′O z ) g , where the M is a metal selected from the group consisting of Na, K, Rb, Ag, Ba, Sr, Ca, La, Ce, Pr, Nd, Pm, Sm, Eu, Dg, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi, Pb; X and X and X′ are each independently an element selected from the group consisting of Si, Ge, P, As, V, S, Se, Cr, Mn and W; and subscripts d, y, e, n, f, g, z are non-negative real numbers.
- the interfaces are comprised of hydrogen bond network formed through hydrogen bonding interactions between the solid acids and the secondary compounds.
- interfaces are formed by solid acids and ceramics with modified surface structure, which are suitable for hydrogen bonding.
- ceramics include, for example SiC with hydrogen bonding donor molecules attached to the surface.
- interfaces are formed by solid acids and polymers having surface hydrogens, which are suitable for hydrogen bonding.
- Polymers with surface hydrogens include, but are not limited to, PBI, poly(trimesic acid), polyimide, polyamide, polyamine and Nafion.
- interfaces are formed by solid acids and functionalized nanostructures. Exemplary finctionalized nanostructures include, but are not limited to, hydroxyl or amino functionalized carbon nanotubes.
- the solid acid composite material can be prepared by mixing solid acids, such as solid acid particles with a secondary component, such as secondary component particles.
- the solid acid and the secondary component are interconnected through interfaces formed by hydrogen bonding interactions, dipolar interactions, van der Waals interactions or combinations of different interactions.
- the composite materials can be either crystalline, amorphous or have a mixed morphology.
- the dimension of the solid acid particles and secondary component particles can be in the ranges of about 1 mn to about 25 ⁇ m.
- Exemplary particle dimensions of the composite material are from about 1 nm to about 200 nm, 100 nm to about 500 nm, from about 300 nm to about 1 ⁇ m, from about 800 nm to about 5 ⁇ m, from about 900 nm to about 8 ⁇ m, from about 300 nm to about 5 ⁇ m, from about 500 nm to about 10 ⁇ m, from about 5 ⁇ m to about 20 ⁇ m and from about 15 ⁇ m to about 25 ⁇ m.
- the dimension of the solid acid composite particles can be in the range from nanometers to micrometers, for example, from about 5 nm to about 50 ⁇ m.
- the particles can adopt various symmetrical, unsymmetrical or irregular shapes. Examples of regular particle shapes include, but are not limited to, spherical, oval, cubical, cylindrical, polyhedral or combinations thereof.
- the solid acid composite particles can have a regular arrangement or a random distribution depending on the solid acid and the secondary component used, which have allowed the fine tuning of the structure and properties of the interfaces formed.
- the composite material can be prepared by mechanically grinding the two components together in a predetermined ratio to achieve intimate mixture.
- CsH 2 PO 4 /LaPO 4 *nH 2 O(HPO 4 ) g can be prepared by mechanically grinding solid acid CsH 2 PO 4 with secondary compound LaPO 4 *nH 2 O(HPO 4 ) g .
- the solid acid composite can be prepared by mixing a 1:1 molar ratio of CsH 2 PO 4 and LaPO 4 *nH 2 O(HPO 4 ) g at temperatures from about 23° C. to about 300° C. in ambient pressure.
- the solid acid composite material can be prepared by co-precipitation from a solution.
- a composite of CsH 2 PO 4 and Nafion can be formed by co-precipitation from an aqueous solution at about 60° C.
- a thin film composite useful as a fuel cell membrane is prepared by casting a thin layer of the material in an aqueous solution over a flat surface, such as glass dish.
- the composite can be prepared by melt-processing.
- the solid acid can be melt-processed onto a preformed membrane containing a secondary component.
- the composite material has surprising and unexpected advantages over bulk solid acid materials.
- the composite material exhibits a superprotonic-like conductivity far below the phase transition temperatures of the pure solid acid ( FIG. 1 ).
- solid acid composite CsH 2 PO 4 /LaPO 4 *nH 2 O(H 3 PO 4 ) shows superprotonic-like conductivity far below the superprotonic phase transition temperatures of CsH 2 PO 4 .
- the composite material was capable of being dehydrated above 350° C. and then rehydrated below 350° C., a property not possible with a pure solid acid sample ( FIGS. 2 and 3 ).
- the secondary compound interacts with the solid acid and thermodynamically stabilizes the surface of the solid acid (e.g., with respect to dehydration) by either increasing the effective partial pressure of water at the solid acid's surface or through the formation of a highly stable surface layer phase.
- secondary compound LaPO 4 *nH 2 O(H 3 PO 4 ) interacts with CsH 2 PO 4 , then thermodynamically stabilizes the surface of CsH 2 PO 4 .
- the mechanical properties of the solid acid composites are more favorable with respect to plastic deformation as the solid acid composites reduce express the “superplasicity” of the solid acids in the superprotonic phase and the plastic deformation by twinning found in solid acids at lower temperatures.
- the proton conducting membranes of the present invention include a solid acid composite.
- the solid acid composite comprises a solid acid component, wherein the solid acid component is capable of conducting protons in a solid state through a superprotonic mechanism; a secondary component having a plurality of surface hydrogen; and a plurality of interfaces formed by the solid acid component and the secondary component.
- the composite is formed through the interaction of solid acid and the secondary compound.
- the interactions are hydrogen bonding interactions between the solid acid and the secondary compound. More preferably, the hydrogen bonds are formed between the solid acid and the surface hydrogens of the secondary component.
- the present invention provides a proton conducting membrane prepared by contacting a solid acid component with a secondary component having a plurality of surface hydrogen under conditions sufficient to generate a composite, wherein said solid acid component interacts with said secondary component to form a plurality of interfaces.
- Solid acid composite membrane can be prepared combining the solid acid and the secondary component in a volume ratio from about 9:1 to about 1:1 at ambient temperature or elevated temperatures. For example, a volume ratio of 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1.
- the proton conducting membrane comprises a solid acid composite comprising a solid acid of the formula I: M a H b (XO t ) c , a secondary component being a compound of the formula VIII: M′ d (X′O y ) e *nH 2 O(H f X′′O z ) g , and interfaces formed by the solid acid and the secondary component, where M and M′ are each independently a metal cation as defined above; X, X′ and X′′ are each independently an element that is capable of forming oxyanions and are as defined above; subscripts a, b, t, c, d, y, e, f and z are each independently a non-negative real number, preferably from 1 to 15, more preferably from 1 to 9, and even more preferably from 1 to 4, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3,
- the proton conducting membrane comprises a solid acid of the formulas Ia, Ib, II, Ia, III, IIIa, IV, V, VI, VIa, VII or VIIa; a secondary compound selected from the group consisting of formula VIII, SiO 2 *xH 2 O, LaPO 4 *xH 2 O, LaPO 4 xH 2 O(H 3 PO 4 ) n , CePO 4 *xH 2 O(H 3 PO 4 ) n ; and interfaces formed by the solid acid and the secondary compound.
- the proton conducting membrane comprises a solid acid of the formulas I, Ia, Ib, II, IIa, III, IIIa, IV, V, VI, VIa, VII or VIIa; a secondary component selected from the group consisting of a polymer, a metal, ceramics and a nanostructure, such as functionalized carbon nanotubes or fullerenes; and aplurality of interfaces formed by the solid acid and the secondary component.
- the membrane can be prepared by mechanically grinding the two components together in a predetermined ratio and mechanically compressing to form a membrane with a desired shape.
- CsH 2 PO 4 /LaPO 4 *nH 2 O(HPO 4 ) g can be prepared by mechanically grinding solid acid CsH 2 PO 4 with secondary compound LaPO 4 *nH 2 O(HPO 4 ) g .
- the proton conducting membrane can also be prepared by co-precipitation from a solution followed by mechanical comprssing.
- a proton conducting membrane of CsH 2 PO 4 and Nafion can be prepared by co-precipitation from an aqueous solution at about 60° C.
- the proton conducting membrane can be prepared by melt-processing.
- a solid acid/poly(imide) composite is prepared by melt-processing of the solid acid onto a preformed membrane containing polyimide.
- the proton conducting membrane of the present invention has several unexpected characteristics.
- the solid acid composite proton conducting membrane has a proton conductivity from about 10 ⁇ 3 ⁇ ⁇ 1 cm ⁇ 1 to about 0.2 ⁇ ⁇ 1 cm ⁇ 1 in the temperature ranging from about 130° C. to about 330° C.
- the composite material or the proton conducting membrane containing the composite material is also capable of being dehydrated above certain temperatures and then rehydrated below certain temperatures, a property not possible with the pure solid acid.
- solid acid composite CsH 2 PO 4 /LaPO 4 *nH 2 O(HPO 4 ) g can be dehydrated above 350° C. and then rehydrated below 350° C. ( FIGS. 2 and 3 ).
- the present invention also provides a method of rehydrating a solid acid composite or a proton conducting membrane containing the solid acid composite.
- the method includes contacting the solid acid composite with a water molecule under conditions sufficient for rehydrating.
- the water can be either in the liquid phase or vapor phase, preferably, the composite is in contact with water vapor between about 100° C. to about 500° C.
- Solid acids have certain characteristics that can be advantageous when used as a proton conducting membrane.
- the proton transport process does not rely on the motion of hydronium ions, thus solid acids need not be humidified and their conductivity is substantially independent of humidity.
- Another advantage is that solid acids are generally stable against thermal decomposition at elevated temperatures.
- the thermal decomposition temperature for some of the solid acids described in this specification can be as high as 350° C.
- solid acid based membranes can be operated at elevated temperatures, e.g. temperatures above 100° C.
- the conductivity of solid acids can be purely protonic, or both electronic and protonic depending on the choice of the cation in the oxyanion. That is, by using a given amount of a variable valence element such as V, Cr, Co, Mn or a combination of the variable valence elements, the solid acid can be made to conduct electrons as well as protons.
- a variable valence element such as V, Cr, Co, Mn or a combination of the variable valence elements
- solid acids are dense, inorganic materials, they are impermeable to gases and other fluids that can be present in the electrochemical environment, e.g., gases and hydrocarbon liquids.
- Solid acids exhibit another advantageous property for applications in proton conducting membranes. Under certain conditions of temperature and pressure, the crystal structure of a solid acid can become disordered. Concomitant with this disorder is a high conductivity, as high as 10 ⁇ 3 to 10 ⁇ 2 ⁇ ⁇ 1 cm ⁇ 1 . Because of the high proton conductivity of the structurally disordered state, it is known as a superprotonic phase. The proton transport is facilitated by rapid reorientations of oxyanions, which occur because of the disorder.
- solid acids enter a superprotonic state at a temperature between about 50 and about 250° C. at ambient pressures.
- the transition into the superprotonic phase can be either sharp or gradual.
- the superprotonic phase is marked by an increase in conductivity, often by several orders of magnitude.
- the solid acid is superprotonic and retains its high proton conductivity until the decomposition or melting temperature is reached.
- the solid acids of the present invention can also be operated at a temperature above the superprotonic transition temperature, and below the decomposition or melt temperature.
- the present invention provides a material comprised of a solid acid composite embedded in a preexisting structure, such as a polymer, a ceramic, glass, a metal or a nanostructure.
- a preexisting structure such as a polymer, a ceramic, glass, a metal or a nanostructure.
- the solid acid composite provides the desired electrochemical activity, whereas the preexisting structure provides mechanical support and increases chemical stability.
- the present invention further comprises a structural binder.
- Structural binders useful in the present invention include, but are not limited to, carbon materials, such as graphite, graphite black, acetylene black, carbon black, Vulcan®XC72, and Vulcan®XC72R; a polymer; a ceramic; glass; silicon dioxide; a semiconductor; a nanostructure; and a metal.
- the structural binder is electrically conducting.
- the structural binder can be a conducting polymer, conducting ceramic, semiconductor or a metal.
- the structural binder is a ceramic, semiconductor or metal, it can be mixed with a polymer.
- the structural binder is silicon dioxide.
- the structural binder is quartz.
- the structural binder is fumed silica or colloidal silica.
- the structural binder when the structural binder is carbon, the structural binder can be graphite, carbon black, a nanostructure, such as carbon nanotubes, and the like.
- a structural binder of the present invention i.e., carbon black and carbon nanotubes or graphite and carbon nanotubes, for example.
- carbon black and carbon nanotubes or graphite and carbon nanotubes are useful as a structural binder of the present invention.
- other carbon forms are useful in the present invention.
- the structural binder is silicon dioxide
- the structural binder can be quartz, fumed silica, colloidal silica, and the like.
- silicon dioxide structural binders are useful in the present invention.
- the structural binder can be electrically conducting or insulating.
- Electrically conducting polymers include, but are not limited to, poly(vinylpyridine), poly(pyrrole), poly(phenylenevinylene), poly(thiophene), poly(acetylene) poly(aniline), poly(phenylene) and the like.
- Additional polymers useful in the present invention include high melt temperature thermoplastic or thermoset fluoropolymers (Teflon, TFE, PFA, FEP, Tefzel, Kalrez, and Viton), or high melt temperature polymers (PBI, PES, PMR-15 polyimide matrix resin, EVA, and “nylons” such as PA-6 and PA-6,6).
- the structural binder can comprise either an electrically conducting polymer, an insulating polymer, or some combination of both.
- One of skill in the art will appreciate that other types of electrically conducting and insulating polymers are useful in the present invention.
- the structural binder when the structural binder is a metal, the structural binder can be any suitable metal, metal oxide, metal salt, or metal complex using a metal such as those described above.
- the structural binder can include more than one metal element, and can also incorporate non-metal species in the structural binder.
- the structural binder when the structural binder is a ceramic, can be any ceramic stable under fuel cell conditions such as, zirconia (ZrO 2 ), alumina (Al 2 O 3 ), titanium dioxide (TiO 2 ), or ceria (CeO 2 ).
- the structural binder can include more than one ceramic material, as well as non-ceramic species.
- ZrO 2 zirconia
- Al 2 O 3 alumina
- TiO 2 titanium dioxide
- CeO 2 ceria
- the structural binder can include more than one ceramic material, as well as non-ceramic species.
- non-ceramic species One of skill in the art will appreciate that other ceramics are useful in the present invention.
- the structural binder when the structural binder is a semiconductor, the structural binder can be any semiconductor stable under fuel cell conditions such as, but not limited to, silicon (Si), silicon carbide (SiC), germanium (Ge), carbon (C, in diamond form), zinc-selenide (ZnSe), gallium-arsenide (GaAs), gallium-nitride (GaN), and indium-phosphide (InP) and the like.
- the structural binder can include more than one semiconductor material, as well as non-semiconductor species. One of skill in the art will appreciate that other semiconductors are useful in the present invention.
- the present invention provides a proton conducting membrane further comprising a separate conducting material.
- Separate conducting materials useful in the present invention include, but are not limited to, carbon materials, polymers, ceramics and metals, as described above.
- the separate conducting material is ionically conducting.
- Separate conducting materials useful in the current invention include ionically conductive materials such as, scandium doped ceria (SDC, oxygen ion conductor), yttrium stabilized zirconium (YSZ, oxygen ion conductor), and perovskites (e.g., BaZr 1 ⁇ x Y x O 3 and BaCeO 3 , proton and oxygen ion conductors, respectively). More than one separate conducting material can be used in the structural binders of the present invention. One of skill in the art will appreciate that other conducting materials are also useful in the present invention.
- the present invention provides a proton conducting membrane comprising a solid acid composite that includes at least one variable valence element.
- the present invention provides a proton conducting membrane being thermally stable at temperatures above about 100° C.
- the proton conducting membrane has a proton conductivity of about 10 ⁇ 5 ⁇ ⁇ 1 cm ⁇ 1 or higher at the temperature of use.
- the proton conducting membrane can conduct both protons and electrons.
- the present invention provides a proton conducting membrane comprising additional types of solid acids.
- the present invention provides a composite material comprising a solid acid composite embedded in a supporting matrix and operated at a slightly elevated temperature.
- the solid acid composite is in its superprotonic phase, exhibits high conductivity, and provides the desired electrochemical functions;
- the support matrix can provide mechanical support, and it can also serve to protect the solid acid from water in the environment.
- a high temperature of operation can render the solid acid composite into its superprotonic state.
- a high temperature of operation can also ensure that any water present in the electrochemical device will be present in the form of steam rather than liquid water, making the H 2 O less likely to attack the solid acid.
- the compounds and proton conducting membranes of the present invention are useful in hydrogen/air fuel cells, hydrogen/oxygen fuel cells direct alcohol fuel cells, hydrogen separation membranes, membrane reactors, supercapacators, electrochromic displays, hydrogen sensors and other membrane based electrochemical devices.
- the present invention provides a fuel cell system comprising a proton membrane.
- the proton membrane includes a solid acid component, a secondary component and hydrogen bonding network interfaces formed by the solid acid and the secondary component.
- the fuel system provides electrical power to an external device.
- the present invention also provides a use of the solid acid composite proton conducting membrane for hydrogen separation and in a device selected from the group consisting of a fuel cell, a membrane reactor and a sensor.
- Other useful applications of the compounds and proton conducting membranes of the present invention will be apparent to one of skill in the art.
- a hydrogen/air fuel cell is one in which the proton conducting membrane is a solid acid composite/matrix composite of the type described herein. Because the membrane need not be humidified, the fuel cell system can be simpler than one which uses a hydrated polymer membrane. The humidification system normally required for fuel cell utilizing a Nafion or related polymer membrane can be eliminated. Hence, less rigid temperature monitoring and control can be used in the solid acid based system as compared with Nafion based fuel cell systems. These differences allow a more efficient cell system.
- the proton conducting membranes of the present invention have a partial pressure of water of less than 1 atm. In other embodiments, the proton conducting membranes of the present invention have water on the surface of the membrane, but not in the interior of the membrane.
- the hydrogen/air fuel cell can be operated at temperatures above 100° C.
- the tolerance of the Pt/Ru catalysts to carbon monoxide CO poisoning increases with increasing temperature.
- a fuel cell of the instant invention operated at a temperature above 100° C. can withstand higher concentrations of CO in the hydrogen fuel than a Nafion based fuel cell which is typically operated at a temperature lower than 100° C.
- the high temperature of operation also enhances the kinetics of the electrochemical reactions, and can thereby result in a fuel cell with higher overall efficiency.
- a direct alcohol fuel cell is constructed using a proton conducting membrane comprising a solid acid composite/matrix support of the type described herein.
- Useful alcohols include methanol, ethanol, isopropanol, and the like. Because the membrane needs not to be humidified, the fuel cell system is much simpler and thus less costly than state of the art direct alcohol fuel cell systems.
- the humidification system normally required for fuel cell utilizing a Nafion or related polymer membrane is eliminated.
- temperature monitoring and control in the solid acid based system does not need to be as tight as in Nafion based fuel cell systems. Because the solid acid composite based membrane needs not to be humidified, the fuel cell can be operated at elevated temperatures. High temperatures can enhance the kinetics of the electrochemical reactions. This results in a fuel cell with very high efficiency.
- Another significant advantage of the fuel cell of the instant invention results from the decreased permeability of the membrane to alcohol.
- Direct alcohol fuel cells in which Nafion or another hydrated polymer serves as the membrane, alcohol crossover through the polymeric membrane lowers fuel cell efficiencies.
- the impermeability of a solid acid composite membrane can improve this efficiency.
- the present invention provides a use of the solid acid composite proton conducting membrane for hydrogen separation.
- the metal catalyst such as Ru/Pt catalyst in a hydrogen/air fuel cell is sensitive to CO poisoning, particularly at temperatures close to ambient. Therefore, in an indirect hydrogen/air fuel cell, the hydrogen produced by the reformer is often cleaned, of e.g. CO to below 50 ppm, before it enters the fuel cell for electrochemical reaction.
- the hydrogen separation membrane contemplated by the instant invention can be made of a mixed proton and electron conducting membrane, as described herein. Hydrogen gas, mixed with other undesirable gases, is introduced onto one side of the membrane. Clean hydrogen gas is extracted from the other side of the membrane.
- H + and e ⁇ On the inlet side of the membrane, hydrogen gas is dissociated into H + and e ⁇ .
- both of these species can migrate through the membrane.
- the membrane is substantially impermeable to other gases and fluids. Hence, CO and other undesirable gases or fluids cannot so migrate.
- the H + and e ⁇ On the outlet side of the membrane, the H + and e ⁇ recombine to form hydrogen gas.
- the overall process is driven by the hydrogen chemical potential gradient, which is high on the inlet side of the membrane and low on the outlet side of the membrane.
- Another type of hydrogen separation membrane uses a membrane made of a proton conducting composite of the type described herein, and is connected to a current source. Hydrogen gas, mixed with other undesirable gases, is introduced onto one side of the membrane and clean hydrogen gas is extracted from the other side of the membrane. Application of a current causes the hydrogen gas to dissociate into H + and e ⁇ . As the membrane conducts only protons, these protons are the only species which can migrate through the membrane. The electrons migrate through the current source to the outlet side of the membrane, where the H + and e ⁇ recombine to form hydrogen gas.
- the membrane is substantially impervious to other gases and fluids. Hence, CO and other undesirable gases or fluids cannot migrate through the proton conducting membrane. The overall process is driven by electric current applied via the current source.
- Additional devices incorporating the proton conducting membranes of the present invention include membrane reactors, in which a mixed proton and electron conducting membrane of the type described herein is utilized.
- the general reaction is that reactants A+B react to form products C+D, where D is hydrogen gas.
- Use of a mixed proton and electron conducting membrane in this reactor can enhance the reaction to give yields that exceed thermodynamic equilibrium values.
- the reactants form products C+H 2 .
- the hydrogen concentration builds up and the forward reaction is slowed.
- the hydrogen is immediately extracted from the reaction region via transport through the membrane, and the forward reaction is enhanced.
- Examples of reactions in which the yield can be enhanced by using such a membrane reactor include (1) the steam reformation of methane (natural gas) to produce syngas: CH 4 +H 2 O ⁇ CO+3H 2 ; (2) the steam reformation of CO to produce CO 2 and H 2 : CO+H 2 O ⁇ CO 2 +H 2 ; (3) the decomposition of H 2 S to H 2 and S, (4) the decomposition of NH 3 to H 2 and N 2 ; (5) the dehydrogenation of propane to polypropylene; and (6) the dehydrogenation of alkanes and aromatic compounds to various products.
- a second type of membrane reaction is one utilizing a mixed proton and electron conducting membrane of the type described herein.
- the general reaction is that the reactants A+B form the products C+D, where B is hydrogen.
- the hydrogen enters the reaction region via transport through the mixed conducting membrane, whereas the reactant A is introduced at the inlet to the membrane reactor, and is mixed with other species.
- the manner in which the hydrogen is introduced into the reactant stream (through the membrane) ensures that only the reactant A, and none of the other species reacts with hydrogen. This effect is termed selective hydrogenation.
- a third type of membrane reaction is one utilizing only a proton conducting membrane of the type described herein.
- the general reaction is that the reactants A+B form the product C, where B is hydrogen.
- the hydrogen enters from the “anode” side of the membrane reactor and is conducted to the reaction region via transport through the proton conducting membrane, whereas the reactant A is introduced on the “cathode” side of the membrane reactor, and is “hydrogenated” at the cathode surface to form the reactant, C.
- the reactant A may be mixed with other species.
- the manner in which the hydrogen is introduced into the reactant stream (through the membrane) ensures that only the reactant A, and none of the other species, reacts with hydrogen. This effect is termed selective hydrogenation.
- ethylene can be hydrogenated to ethane by such a process using such a membrane: C 2 H 4 ⁇ C 2 H 6 .
- the mixed proton and electron conducting membranes described herein provide an advantage over state-of-the-art membranes in that the conductivity is high at temperatures as low as 100° C., and the membranes are relatively inexpensive. Selective hydrogenation at temperatures close to ambient can have particular application in synthesis of pharmaceutically important compounds which cannot withstand high temperatures.
- the present invention provides a method for preparing a proton conducting membrane.
- the method includes contacting a solid acid component with a secondary component having a plurality of surface hydrogen to generate a composite.
- the method further includes contacting with a structural binder.
- the solid acid component and secondary component exist as particles having various shapes, sizes and dimensions.
- the formation of the solid acid composite can be realized by mechanically mixing of the solid acid and the secondary compound in the presence or absence of a structural binder.
- the composite can be formed through co-precipitation.
- the proton conducting membranes of the present invention can be prepared by a variety of means.
- One method involves mechanically pressing an evenly dispersed layer of solid acid composite into a highly dense layer supported on the anode and/or cathode layers.
- the solid acid composite layer can be compressed at temperatures ranging from ambient to above the melt temperature of the solid acid.
- Another method involves mixing the solid acid and the secondary compound with a supporting structure that is electrochemically unreactive, to form a composite.
- a first embodiment uses a solid acid/secondary compound mixed with a melt-processable polymer as the supporting matrix structure.
- Composite membranes of the solid acid/secondary compound and poly(vinylidene fluoride) can be prepared by simple melt-processing methods. The three components can be lightly ground together then hot-pressed at 180° C. and 10 kpsi for 15 minutes.
- additional melt-processable polymers are useful in the present invention, such as those described herein as polymer binders.
- thermoset polymer in monomer or prepolymer form in with the solid acid/secondary compound composite, and then starting the polymerization in situ.
- composite membranes of the solid acid compound and the polyester resin marketed under the name Castoglas by Buehler, Inc. can be synthesized by lightly grinding the solid acid and pre-polymer together and then adding the crosslinking agent to start the polymerization.
- Composite membrane of solid acid composite and poly(trimesic acid) can be prepared by grinding and then heating the mixture to 250° C. to start the polymerization.
- thermoset polymers can be used.
- the solid acid/secondary compound composite is ground and then mixed with the monomer dicyclopentadiene.
- the polymerization catalyst is introduced into the mixture, which is then poured onto a Teflon plate and pressed into a thin film. The film is cured at 100° C. for approximately 2 hours.
- additional thermoset polymers are useful in the present invention.
- Another method for preparing solid acid-polymer composites or solid acid-secondary compound-polymer composites is suspension coating.
- the solid acid/secondary component composite is dissolved in a water-ethanol solution, and the polymer PTFE is dispersed into this solution.
- a composite membrane is formed by casting the suspension, allowing the solvents to evaporate, and then mechanically pressing at either ambient or elevated temperatures.
- the solid acid or solid acid-secondary compound composite can be synthesized from aqueous solution and the matrix material is synthesized separately. The two components are then mixed and ground together. The mixture is then pressed at either ambient or elevated temperatures, preferably at an elevated temperature which causes the solid acid and/or polymer to melt and flow, to yield a dense composite membrane.
- Electrically conductive composite membranes are prepared by combining at least one solid acid or solid acid-secondary compound composite and an electrically conductive structural binder.
- the electrically conductive structural binder can be an electronically conducting polymer, such as poly(aniline) or poly(imidazole), or a typical metal, such as aluminum or copper, as well as a conductive carbon material.
- the electronically conducting component is a metal, it can be advantageous to introduce a chemically and electrically inert polymer into the composite simply to serve as a binder and provide the membrane with good mechanical properties.
- the processing methods described above can be used to prepare such composite membranes.
- Electrically conductive composites can also be prepared by performing direct chemical substitutions with variable valence ions. Substitution in the oxyanion or metal cation component with a variable valence element can provide the desired electronic conductivity. Large ions with variable valence, such as thallium, indium, lead and tin can be used for these substitutions.
- the solid acid or solid acid-secondary compound composite so modified can be used in an electrochemical device directly, or can be combined with a supporting matrix material as described above.
- FIG. 1 shows a comparison of the conductivity of pure CsH 2 PO 4 versus a CsH 2 PO 4 /LaPO 4 *H 2 O(H 3 PO 4 ) g composite material.
- the composite has higher or equal conductivity to that of pure CsH 2 PO 4 at all measured temperatures. Measurements were taken upon heating and cooling at 1° C./min, under flowing air atmospheres with a water partial pressure ⁇ 0.4 atm.
- FIGS. 2 and 3 illustrate the stability of solid acid composite and the rehydrating of the solid acid composite.
- the conductivity of the solid acid composite CsH 2 PO 4 /LaPO 4 *H 2 O(H 3 PO 4 ) g can be measured up to 400° C., whereas a sample of pure solid acid CsH 2 PO 4 would melt at ⁇ 330° C., resulting in a short circuit in the experimental setup used. All measurements were taken with heating/cooling rates of 1° C./min, under flowing air atmospheres with a water partial pressure ⁇ 0.4 atm.
- the solid acid composite CsH 2 PO 4 /LaPO 4 *H 2 O(H 3 PO 4 ) g also has the ability to rehydrate at 156° C. after having been dehydrated at 400° C. for 6 hrs, a property not seen in CsH 2 PO 4 .
- Solid acid CsH 2 PO 4 is prepared as described above.
- SiC is purchased from ElectroAbrasives Company.
- a solid acid composite membrane of CsH 2 PO 4 -silicon carbide is prepared by mechanical mixing a 9:1 volume ratio of CsH 2 PO 4 and SiC in methanol using a mortar and a pestle at about 23° C. under ambient pressure followed by mechanical or thermal densification.
- the hydrogen bond donor and/or acceptor molecules are absorbed on the surface of the SiC to provide a surface with active hydrogen bond donors and/or acceptors.
- the SiC surface containing H 2 O, NH 3 or alcohol has been prepared ( FIGS. 4 a and 4 b ).
- Solid acid CsH 2 PO 4 is prepared as described above. Trimesic acid is purchased from Aldrich Chemical Company. A composite membrane of CsH 2 PO 4 and trimesic acid of the formula: C 6 H 3 (COOH) 3 is prepared by grinding a 95:5 volume ratio of CsH 2 PO 4 and trimesic acid together using a mortar and a pestle and oven, at about 23° C. under an ambient pressure and then mechanically compressing the mixture into the desired membrane shape. The trimesic acid are then cross-linked to itself by heating at 250° C., to form a polymer support structure in the composite membrane.
- Trimesic acid is purchased from Aldrich Chemical Company.
- a composite membrane of CsH 2 PO 4 and trimesic acid of the formula: C 6 H 3 (COOH) 3 is prepared by grinding a 95:5 volume ratio of CsH 2 PO 4 and trimesic acid together using a mortar and a pestle and oven, at about 23° C. under an ambient pressure and then mechanically compressing the mixture into the
- the hydrogens on the carboxylic groups can then interact with the non-bonded oxygens of CsH 2 PO 4 , while the hydrogens of CsH 2 PO 4 can form bonds with the double bonded oxygens of the carboxylic groups. Both cases result in hydrogen bonds of medium strength being formed between the solid acid and polymer particles. These bonds are formed at random, greatly enhancing the protonic conductivity at the solid acid/polymer interface. At the same time, the medium strength bonds mechanically strengthen the interaction between solid acid and polymer, thus transferring the mechanical properties of the polymer to the solid acid.
- Solid acid CsH 2 PO 4 is prepared as described above.
- Nafion® is purchased from Aldrich Chemical Company.
- a solid acid composite of CsH 2 PO 4 and Nafion is prepared by co-precipitation from an aqueous solution at 60° C.
- a thin film composite useful as a fuel cell membrane is prepared by casting a thin layer of the material in an aqueous solution over a flat oven glass dish surface. The film is then formed by co-precipition of Nafion and CsH 2 PO 4 as water is evolved at 60° C. in an oven.
- the CsH 2 PO 4 is precipitated in the hydrophilic channels of the Nafion polymer matrix ( FIG. 5 ).
- Solid acid CsH 2 PO 4 is prepared as described above.
- Polybenzimidazole is synthesized by polymerization of 3,3′-diaminobenzidine and diphenyl isophthalate according to reported procedures.
- a solid acid composite membrane of CsH 2 PO 4 and polybenzimidazole (PBI) is prepared by either precipitation of CsH 2 PO 4 from aqueous solution into the pores of a PBI membrane, followed by mild mechanical compression, or by simply melting the CsH 2 PO 4 into the porous PBI membrane at temperatures above 330° C. and pH 2 O ⁇ 1 atm.
- the volume ratio of CsH 2 PO 4 and PBI is 85:15.
- the processes are carried out at temperatures from about 23° C. to about 300° C. under ambient pressure.
- Solid acid CsH 2 PO 4 is prepared as described above.
- Polyimide, Kapton® is purchased from Dupont Chemical Company.
- a solid acid composite membrane of CsH 2 PO 4 and polyimide is prepared by first creating a polyimide film from polyamic acid in a solvent (Munakata, et al. Chem. Commun., 2005, 3986-3988).
- the solid acid, CsH 2 PO 4 is then deposited in the polymer by precipitation from aqueous solution at 60° C.
- the CsH 2 PO 4 is then taken above its melt temperature at 330° C., under at water partial pressure of 0.7 atm, and the composite film is densified by mild compression at 50 psi.
- Solid acid CsH 2 PO 4 is prepared as described above. Muti-walled Fullerene, nanotubes, 20-50 nm OD, 5-20 micron long are purchased from Alfa Aesar Company. The nanotubes are functionalized with carboxylic acid group according to a reported method (Smalley, R. E. et al. Carbon Nanotubes: Synthesis, Structure, Properties and Applications , Springer; 1st Ed, 2001; Ajayan, Z. P. et al. “Making Functional Materials with Nanotubes” Material Res. Soc. Sym. Proc. 2002, V. 706).
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/485,715 US20070128491A1 (en) | 2005-07-13 | 2006-07-12 | Advanced solid acid electrolyte composites |
PCT/US2006/027340 WO2007009059A2 (fr) | 2005-07-13 | 2006-07-13 | Composites electrolytiques acides solides ameliores |
US12/268,202 US7932299B2 (en) | 2005-07-13 | 2008-11-10 | Advanced solid acid electrolyte composites |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US69901805P | 2005-07-13 | 2005-07-13 | |
US11/485,715 US20070128491A1 (en) | 2005-07-13 | 2006-07-12 | Advanced solid acid electrolyte composites |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/268,202 Continuation US7932299B2 (en) | 2005-07-13 | 2008-11-10 | Advanced solid acid electrolyte composites |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070128491A1 true US20070128491A1 (en) | 2007-06-07 |
Family
ID=37637977
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/485,715 Abandoned US20070128491A1 (en) | 2005-07-13 | 2006-07-12 | Advanced solid acid electrolyte composites |
US12/268,202 Active US7932299B2 (en) | 2005-07-13 | 2008-11-10 | Advanced solid acid electrolyte composites |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/268,202 Active US7932299B2 (en) | 2005-07-13 | 2008-11-10 | Advanced solid acid electrolyte composites |
Country Status (2)
Country | Link |
---|---|
US (2) | US20070128491A1 (fr) |
WO (1) | WO2007009059A2 (fr) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090169954A1 (en) * | 2005-11-30 | 2009-07-02 | Nippon Sheet Glass Company , Limited | Electrolyte Membrane and Fuel Cell Using the Same |
US20090220846A1 (en) * | 2008-02-29 | 2009-09-03 | Toyota Jidosha Kabushiki Kaisha | Proton conductor, and fuel cell and fuel cell system including proton conductor |
WO2010028323A1 (fr) * | 2008-09-06 | 2010-03-11 | Cyvolt Energy Systems, Inc. | Pile à combustible utilisant directement des mélanges polyhydriques comme combustible |
US20100294662A1 (en) * | 2009-05-19 | 2010-11-25 | Honeywell International Inc. | Fast response electrochemical organophosphate sensor |
US20120031774A1 (en) * | 2010-08-04 | 2012-02-09 | Chang Gung University | Electrode for an electrochemical device and method for detecting hydrogen peroxide using the electrode |
US20130177835A1 (en) * | 2010-07-23 | 2013-07-11 | National University Corporation Toyohashi University Of Technology | Proton conductor and method of producing proton conductor |
WO2015006010A3 (fr) * | 2013-06-21 | 2015-05-07 | Dong-Kyun Seo | Oxydes métalliques obtenus à partir de solutions acides |
US9233863B2 (en) | 2011-04-13 | 2016-01-12 | Molycorp Minerals, Llc | Rare earth removal of hydrated and hydroxyl species |
US9242900B2 (en) | 2009-12-01 | 2016-01-26 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Porous geopolymer materials |
US9296654B2 (en) | 2011-09-21 | 2016-03-29 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Geopolymer resin materials, geopolymer materials, and materials produced thereby |
US9308511B2 (en) | 2009-10-14 | 2016-04-12 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Fabricating porous materials using thixotropic gels |
US9365691B2 (en) | 2010-08-06 | 2016-06-14 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Fabricating porous materials using intrepenetrating inorganic-organic composite gels |
US9975787B2 (en) | 2014-03-07 | 2018-05-22 | Secure Natural Resources Llc | Removal of arsenic from aqueous streams with cerium (IV) oxide compositions |
US10829382B2 (en) | 2017-01-20 | 2020-11-10 | Skysong Innovations | Aluminosilicate nanorods |
US10926241B2 (en) | 2014-06-12 | 2021-02-23 | Arizona Board Of Regents On Behalf Of Arizona State University | Carbon dioxide adsorbents |
CN113839074A (zh) * | 2021-09-24 | 2021-12-24 | 上海交通大学 | 一种固体酸质子传导膜的制备方法 |
CN118472335A (zh) * | 2024-07-12 | 2024-08-09 | 大连海事大学 | 一种高温浸渍固体酸的NiO/YSZ复合电解质膜及其制备方法以及固体酸燃料电池的制备方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9059444B2 (en) * | 2008-01-31 | 2015-06-16 | Massachusetts Institute Of Technology | Highly conducting solid state ionics for electrochemical systems and methods of fabricating them using layer-by layer technology |
EP2253038B1 (fr) | 2008-02-12 | 2014-12-03 | Council of Scientific & Industrial Research | Composition à conductivité protonique améliorée |
EP2450983B1 (fr) * | 2008-10-29 | 2013-12-11 | Samsung Electronics Co., Ltd. | Composition d'électrolyte et de l'encre catalyseur et la membrane d'électrolyte solide formée en utilisant les mêmes |
US8273486B2 (en) | 2009-01-30 | 2012-09-25 | Honeywell International, Inc. | Protecting a PEM fuel cell catalyst against carbon monoxide poisoning |
KR101093703B1 (ko) * | 2009-06-25 | 2011-12-15 | 삼성에스디아이 주식회사 | 연료전지용 고분자 전해질막 및 그 제조방법 |
DE102021207392A1 (de) | 2021-07-13 | 2023-01-19 | Robert Bosch Gesellschaft mit beschränkter Haftung | Brennstoffzelle sowie Brennstoffzellenstapel |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5576115A (en) * | 1992-01-17 | 1996-11-19 | Ente Per Le Nuove Tecnologie, L'energia E L'ambiente (Enea) | Composite polymeric electrolyte |
US6059943A (en) * | 1997-07-30 | 2000-05-09 | Lynntech, Inc. | Composite membrane suitable for use in electrochemical devices |
US6468684B1 (en) * | 1999-01-22 | 2002-10-22 | California Institute Of Technology | Proton conducting membrane using a solid acid |
US6716548B1 (en) * | 1998-12-18 | 2004-04-06 | Universite Laval | Composite electrolyte membranes for fuel cells and methods of making same |
US7255962B2 (en) * | 2004-07-01 | 2007-08-14 | California Institute Of Technology | Eulytite solid acid electrolytes for electrochemical devices |
-
2006
- 2006-07-12 US US11/485,715 patent/US20070128491A1/en not_active Abandoned
- 2006-07-13 WO PCT/US2006/027340 patent/WO2007009059A2/fr active Application Filing
-
2008
- 2008-11-10 US US12/268,202 patent/US7932299B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5576115A (en) * | 1992-01-17 | 1996-11-19 | Ente Per Le Nuove Tecnologie, L'energia E L'ambiente (Enea) | Composite polymeric electrolyte |
US6059943A (en) * | 1997-07-30 | 2000-05-09 | Lynntech, Inc. | Composite membrane suitable for use in electrochemical devices |
US6716548B1 (en) * | 1998-12-18 | 2004-04-06 | Universite Laval | Composite electrolyte membranes for fuel cells and methods of making same |
US6468684B1 (en) * | 1999-01-22 | 2002-10-22 | California Institute Of Technology | Proton conducting membrane using a solid acid |
US20030008190A1 (en) * | 1999-01-22 | 2003-01-09 | California Institute Of Technology | Proton conducting membrane using a solid acid |
US7125621B2 (en) * | 1999-01-22 | 2006-10-24 | California Institute Of Technology | Proton conducting membrane using a solid acid |
US7255962B2 (en) * | 2004-07-01 | 2007-08-14 | California Institute Of Technology | Eulytite solid acid electrolytes for electrochemical devices |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090169954A1 (en) * | 2005-11-30 | 2009-07-02 | Nippon Sheet Glass Company , Limited | Electrolyte Membrane and Fuel Cell Using the Same |
US20090220846A1 (en) * | 2008-02-29 | 2009-09-03 | Toyota Jidosha Kabushiki Kaisha | Proton conductor, and fuel cell and fuel cell system including proton conductor |
US7833675B2 (en) * | 2008-02-29 | 2010-11-16 | Toyota Jidosha Kabushiki Kaisha | Proton conductor, and fuel cell and fuel cell system including proton conductor |
WO2010028323A1 (fr) * | 2008-09-06 | 2010-03-11 | Cyvolt Energy Systems, Inc. | Pile à combustible utilisant directement des mélanges polyhydriques comme combustible |
US20100294662A1 (en) * | 2009-05-19 | 2010-11-25 | Honeywell International Inc. | Fast response electrochemical organophosphate sensor |
US9308511B2 (en) | 2009-10-14 | 2016-04-12 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Fabricating porous materials using thixotropic gels |
US9242900B2 (en) | 2009-12-01 | 2016-01-26 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Porous geopolymer materials |
US20130177835A1 (en) * | 2010-07-23 | 2013-07-11 | National University Corporation Toyohashi University Of Technology | Proton conductor and method of producing proton conductor |
US20120031774A1 (en) * | 2010-08-04 | 2012-02-09 | Chang Gung University | Electrode for an electrochemical device and method for detecting hydrogen peroxide using the electrode |
US8702924B2 (en) * | 2010-08-04 | 2014-04-22 | Chang Gung University | Electrode for an electrochemical device and method for detecting hydrogen peroxide using the electrode |
US9365691B2 (en) | 2010-08-06 | 2016-06-14 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Fabricating porous materials using intrepenetrating inorganic-organic composite gels |
US9233863B2 (en) | 2011-04-13 | 2016-01-12 | Molycorp Minerals, Llc | Rare earth removal of hydrated and hydroxyl species |
US9296654B2 (en) | 2011-09-21 | 2016-03-29 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Geopolymer resin materials, geopolymer materials, and materials produced thereby |
US9862644B2 (en) | 2011-09-21 | 2018-01-09 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Geopolymer resin materials, geopolymer materials, and materials produced thereby |
US10170759B2 (en) | 2013-06-21 | 2019-01-01 | Arizona Board Of Regents On Behalf Of Arizona State University | Metal oxides from acidic solutions |
WO2015006010A3 (fr) * | 2013-06-21 | 2015-05-07 | Dong-Kyun Seo | Oxydes métalliques obtenus à partir de solutions acides |
US9975787B2 (en) | 2014-03-07 | 2018-05-22 | Secure Natural Resources Llc | Removal of arsenic from aqueous streams with cerium (IV) oxide compositions |
US10577259B2 (en) | 2014-03-07 | 2020-03-03 | Secure Natural Resources Llc | Removal of arsenic from aqueous streams with cerium (IV) oxide compositions |
US10926241B2 (en) | 2014-06-12 | 2021-02-23 | Arizona Board Of Regents On Behalf Of Arizona State University | Carbon dioxide adsorbents |
US11745163B2 (en) | 2014-06-12 | 2023-09-05 | Arizona Board Of Regents On Behalf Of Arizona State University | Carbon dioxide adsorbents |
US10829382B2 (en) | 2017-01-20 | 2020-11-10 | Skysong Innovations | Aluminosilicate nanorods |
CN113839074A (zh) * | 2021-09-24 | 2021-12-24 | 上海交通大学 | 一种固体酸质子传导膜的制备方法 |
CN118472335A (zh) * | 2024-07-12 | 2024-08-09 | 大连海事大学 | 一种高温浸渍固体酸的NiO/YSZ复合电解质膜及其制备方法以及固体酸燃料电池的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US20100330455A1 (en) | 2010-12-30 |
US7932299B2 (en) | 2011-04-26 |
WO2007009059A2 (fr) | 2007-01-18 |
WO2007009059A3 (fr) | 2009-05-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7932299B2 (en) | Advanced solid acid electrolyte composites | |
US7125621B2 (en) | Proton conducting membrane using a solid acid | |
Goñi-Urtiaga et al. | Solid acids as electrolyte materials for proton exchange membrane (PEM) electrolysis | |
He et al. | High-performance proton-conducting fuel cell with b-site-deficient perovskites for all cell components | |
Javed et al. | A critical review of electrolytes for advanced low-and high-temperature polymer electrolyte membrane fuel cells | |
Shah et al. | Electrochemical properties of a co-doped SrSnO3− δ-based semiconductor as an electrolyte for solid oxide fuel cells | |
Wang et al. | Enhanced proton conduction with low oxygen vacancy concentration and favorable hydration for protonic ceramic fuel cells cathode | |
CN100405648C (zh) | 聚合物膜、燃料电池用的薄膜电极组件及含其的燃料电池系统 | |
CN101297377A (zh) | 质子导电性杂化材料和使用其的用于燃料电池的催化剂层 | |
Rao et al. | α-ZrP nanoreinforcement overcomes the trade-off between phosphoric acid dopability and thermomechanical properties: nanocomposite HTPEM with stable fuel cell performance | |
US7255962B2 (en) | Eulytite solid acid electrolytes for electrochemical devices | |
Muthumeenal et al. | Recent research trends in polymer nanocomposite proton exchange membranes for electrochemical energy conversion and storage devices | |
Shao et al. | Fuel cells: Materials needs and advances | |
WO2022157757A1 (fr) | Ensembles membranes et couches de séparation pour piles à combustible et électrolyseurs | |
JP2006179448A (ja) | 電解質膜及びこれを用いた膜−電極接合体並びにこれを用いた燃料電池 | |
Vignesh et al. | Proton Conductors: Physics and Technological Advancements for PC-SOFC | |
Pandey | Recent progresses in membranes for proton exchange membrane fuel cell (PEMFC) for clean and environmentally friendly applications | |
KR20090032564A (ko) | 연료 전지용 고분자 전해질막, 이를 포함하는 연료 전지용막-전극 어셈블리 및 연료 전지 시스템 | |
Mosa et al. | Sol–Gel Materials for Batteries and Fuel Cells | |
CN113839074B (zh) | 一种固体酸质子传导膜的制备方法 | |
Xie et al. | Designing Proton Conducting Electrolytes for Low-Temperature Ceramic Fuel Cells | |
Mohanapriya et al. | 12 Electrolyte Membrane | |
Chisholm et al. | Proton conducting membrane using a solid acid | |
Mohanapriya et al. | Electrolyte Membrane for 2D Nanomaterials | |
Park et al. | Breakthrough oxygen electrode reaction kinetics using BaCe0. 7Zr0. 1Y0. 1Yb0. 1O3− δ based composite air electrodes for reversible solid oxide cells |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CALIFORNIA INSTITUTE OF TECHNOLOGY, CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHISHOLM, CALUM;HAILE, SOSSINA M.;REEL/FRAME:018347/0223;SIGNING DATES FROM 20060915 TO 20061002 |
|
AS | Assignment |
Owner name: TRIPLEPOINT CAPITAL LLC, CALIFORNIA Free format text: SECURITY AGREEMENT;ASSIGNOR:SUPERPROTONIC, INC.;REEL/FRAME:021328/0833 Effective date: 20080211 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |