WO2005004262A2 - Fuel cells comprising laminar flow induced dynamic conducting interfaces, electronic devices comprising such cells, and methods employing same - Google Patents
Fuel cells comprising laminar flow induced dynamic conducting interfaces, electronic devices comprising such cells, and methods employing same Download PDFInfo
- Publication number
- WO2005004262A2 WO2005004262A2 PCT/US2004/020597 US2004020597W WO2005004262A2 WO 2005004262 A2 WO2005004262 A2 WO 2005004262A2 US 2004020597 W US2004020597 W US 2004020597W WO 2005004262 A2 WO2005004262 A2 WO 2005004262A2
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- WO
- WIPO (PCT)
- Prior art keywords
- electrode
- fuel cell
- liquid
- fuel
- channel
- Prior art date
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 133
- 239000007800 oxidant agent Substances 0.000 claims description 41
- 230000001590 oxidative effect Effects 0.000 claims description 33
- 239000012528 membrane Substances 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 125000006850 spacer group Chemical group 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 230000036647 reaction Effects 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 1
- 210000004027 cell Anatomy 0.000 description 142
- 239000012530 fluid Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 238000013461 design Methods 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000005518 polymer electrolyte Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012286 potassium permanganate Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002047 photoemission electron microscopy Methods 0.000 description 3
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 3
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 235000012545 Vaccinium macrocarpon Nutrition 0.000 description 2
- 235000002118 Vaccinium oxycoccus Nutrition 0.000 description 2
- 244000291414 Vaccinium oxycoccus Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 235000004634 cranberry Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 238000005459 micromachining Methods 0.000 description 2
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- 239000004417 polycarbonate Substances 0.000 description 2
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- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 241001502883 Marcia Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008365 aqueous carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000001053 micromoulding Methods 0.000 description 1
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- 150000002926 oxygen Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229950011087 perflunafene Drugs 0.000 description 1
- UWEYRJFJVCLAGH-UHFFFAOYSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C21F UWEYRJFJVCLAGH-UHFFFAOYSA-N 0.000 description 1
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- UPIXZLGONUBZLK-UHFFFAOYSA-N platinum Chemical compound [Pt].[Pt] UPIXZLGONUBZLK-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
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- 238000011002 quantification Methods 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
-
- 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
- H01M8/08—Fuel cells with aqueous electrolytes
-
- 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
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- 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
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
-
- 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
- This invention relates to the field of induced dynamic conducting interfaces. More particularly, this invention relates to laminar flow induced dynamic conducting interfaces for use in micro-fluidic batteries, fuel cells, and photoelectric cells.
- a key component in many electrochemical cells is a semi-permeable membrane or salt bridge.
- One of the primary functions of these components is to physically isolate solutions or solids having different chemical potentials.
- fuel cells generally contain a semi-permeable membrane (e.g., a polymer electrolyte membrane or PEM) that physically isolates the anode " and cathode regions while allowing ions (e.g., hydrogen ions) to pass through the membrane.
- a semi-permeable membrane e.g., a polymer electrolyte membrane or PEM
- FIG. 1 shows a cross-sectional schematic illustration of a polymer electrolyte fuel cell 2.
- PEFC 2 includes a high surface area anode 4 that acts as a conductor, an anode catalyst 6 (typically platinum alloy), a high surface area cathode 8 that acts as a conductor, a cathode catalyst 10 (typically platinum), and a polymer electrolyte membrane (PEM) 12 that serves as a solid electrolyte for the cell.
- the PEM 12 physically separates anode 4 and cathode 8.
- Fuel in the gas and/or liquid phase (typically hydrogen or an alcohol) is brought over the anode catalyst 6 where it is oxidized to produce protons and electrons in the case of hydrogen fuel, and protons, electrons, and carbon dioxide in the case of an alcohol fuel.
- the electrons flow through an external circuit 16 to the cathode 8 where air, oxygen, or an aqueous oxidant (e.g., peroxide) is being constantly fed.
- Protons produced at the anode 4 selectively diffuse through PEM 12 to cathode 8, where oxygen is reduced in the presence of protons and electrons at cathode catalyst 10 to produce water.
- the PEM used in conventional PEFCs is typically composed of a perfluorinated polymer with sulphonic acid pendant groups, such as the material sold under the tradename NAFION by DuPont (Fayetteville, NC) (see: Fuel Cell Handbook, Fifth Edition by J. Hirschenhofer, D. Stauffer, R. Engleman, and M. Klett, 2000, Department of Energy— FETL, Morgantown,
- the PEM serves as catalyst support material, proton conductive layer, and physical barrier to limit mixing between the fuel and oxidant streams. Mixing of the two feeds would result in direct electron transfer and loss of efficiency since a mixed potential and/or thermal energy is generated as opposed to the desired electrical energy. Operating the cells at low temperature does not always prove advantageous. For example, carbon monoxide (CO), which may be present as an impurity in the fuel or as the incomplete oxidation product of an alcohol, binds strongly to and "poisons" the platinum catalyst at temperatures below about 150 °C.
- CO carbon monoxide
- DMFC direct methanol fuel cell
- the cell utilizes methanol fuel directly, and does not require a preliminary reformation step.
- DMFCs are of increasing interest for producing electrical energy in mobile power (low energy) applications.
- the semi- permeable membrane used to separate the fuel feed (i.e., methanol) from the oxidant feed (i.e., oxygen) is typically a polymer electrolyte membrane (PEM) of the type developed for use with gaseous hydrogen fuel feeds.
- PEMs polymer electrolyte membrane
- methanol crossover an undesirable occurrence known as "methanol crossover” takes place, whereby methanol travels from the anode to the cathode through the membrane.
- methanol crossover also causes depolarization losses (mixed potential) at the cathode and, in general, leads to decreased cell performance. Therefore, in order to fully realize the promising potential of DMFCs as commercially viable portable power sources, the problem of methanol crossover must be addressed.
- other improvements are also needed including: increased cell efficiency, reduced manufacturing costs, increased cell lifetime, and reduced cell size/weight. In spite of massive research efforts, these problems persist and continue to inhibit the commercialization and development of DMFC technology.
- the present invention provides a fuel cell that includes (a) a first electrode; (b) a second electrode; and (c) a channel contiguous with at least a portion of the first and the second electrodes; such that when a first liquid is contacted with the first electrode, a second liquid is contacted with the second electrode, and the first and the second liquids flow through the channel, a multistream laminar flow is established between the first and the second liquids, and a current density of at least 0.1 mA/cm 2 is produced.
- the present invention provides a device that includes a fuel cell as described above.
- the present invention provides a portable electronic device that includes a fuel cell as described above.
- the present invention provides a method of generating an electric current that includes operating a fuel cell as described above.
- the present invention provides a method of generating water that includes operating a fuel cell as described above.
- the present invention provides a method of generating electricity that includes flowing a first liquid and a second liquid through a channel in multistream laminar flow, wherein the first liquid is in contact with a first electrode and the second liquid is in contact with a second electrode, wherein complementary half cell reactions take place at the first and the second electrodes, respectively, and wherein a current density of at least 0.1 mA/cm 2 is produced.
- the present invention provides a fuel cell that includes a first electrode and a second electrode, wherein ions travel from the first electrode to the second electrode without traversing a membrane, and wherein a current density of at least 0.1 mA/cm 2 is produced.
- the present invention provides the improvement comprising replacing the membrane separating a first and a second electrode of a fuel cell with a multistream laminar flow of a first liquid containing a fuel in contact with the first electrode, and a second liquid containing an oxidant in contact with the second electrode, and providing each of the first liquid and the second liquid with a common electrolyte.
- the present invention provides a fuel cell that includes (a) a support having a surface; (b) a first electrode connected to the surface of the support; (c) a second electrode connected to the surface of the support and electrically coupled to the first electrode; (d) a spacer connected to the surface of the support, which spacer forms a partial enclosure around at least a portion of the first and the second electrodes; and (e) a microchannel contiguous with at least a portion of the first and the second electrodes, the microchannel being defined by the surface of the support and the spacer.
- the presently preferred embodiments described herein may possess one or more advantages relative to other devices and methods, which can include but are but not limited to: reduced cost; increased cell lifetime; reduced internal resistance of the cell; reduction or elimination of methanol crossover or fouling of the cathode; ability to recycle left-over methanol that crosses over into the oxidant stream back into the fuel stream; ability to increase reaction kinetics proportionally with temperature and/or pressure without compromising the integrity of a membrane; and ability to fabricate a highly efficient, inexpensive, and lightweight cell.
- FIG. 1 shows a cross-sectional schematic illustration of a polymer electrolyte fuel cell.
- FIG. 2 shows a cross-sectional schematic illustration of a direct methanol fuel cell.
- FIG. 3 shows a schematic illustration of modes of fluid flow.
- FIG. 4 shows a schematic illustration of the relationship between input stream geometry and mode of fluid flow.
- FIG. 5 shows a schematic illustration of the relationship between microfluidic flow channel geometry and mode of fluid flow.
- FIG. 6 shows a schematic illustration of a diffusion-based micro- extractor.
- FIG. 7 shows a schematic illustration of a direct methanol fuel cell containing a laminar flow induced dynamic interface.
- FIG. 8A shows a schematic illustration of side-by-side microfluidic channel configuration and 8B shows a face-to-face microfluidic channel configuration.
- FIG. 9 shows a perspective view of a laminar flow fuel cell in accordance with the present invention.
- FIG. 10 shows an exploded perspective view of the fuel cell shown in FIG. 9.
- FIG. 11 shows a plot of current vs. voltage for a copper-zinc laminar flow fuel cell.
- FIG. 12 shows a plot of current vs. voltage for a platinum-platinum laminar flow fuel cell.
- FIG. 13A shows the top view of a laminar flow cell with face-to-face electrodes, and 13B its cross-section.
- FIG. 14 shows a plot of potential vs.
- FIG. 15 shows a power density to potential plot for a laminar fuel cell with a ferrous sulfate and potassium permanganate fuel-oxidant combination.
- FIG. 16 shows a plot of potential vs. current density plot for a laminar fuel cell with a formic acid and oxygen saturated aqueous sulfuric acid fuel- oxidant combination.
- Fig. 17 shows a power density to potential plot for a laminar fuel cell with a formic acid and oxygen saturated aqueous sulfuric acid fuel-oxidant combination.
- FIG. 18 shows a plot of potential vs.
- FIG. 19 shows a power density to potential plot for a laminar fuel cell with a formic acid and potassium permanganate fuel-oxidant combination.
- FIG. 20 shows a plot of potential vs. current density plot for a laminar fuel cell with a methanol and oxygen saturated aqueous sulfuric acid fuel- oxidant combination.
- Fig. 21 shows a power density to potential plot for a laminar fuel cell with a methanol and oxygen saturated aqueous sulfuric acid fuel-oxidant combination.
- An electrochemical cell in accordance with the present invention does not require a membrane, and is therefore not constrained by the limitations inherent in conventional membranes. Instead, a mechanism has been developed by which ions can travel from one electrode to another without traversing a membrane, and which allows proton conduction while preventing mixing of the fuel and oxidant streams. This mechanism, described more fully herein below, involves establishing laminar flow induced dynamic conducting interfaces.
- electrochemical cell is to be understood in the very general sense of any seat of electromotive force (as defined in Fundamentals of Physics, Extended Third Edition by David Halliday and Robert Resnick, John Wiley & Sons, New
- electrochemical cell refers to both galvanic (i.e., voltaic) cells and electrolytic cells, and subsumes the definitions of batteries, fuel cells, photocells (photovoltaic cells), thermopiles, electric generators, electrostatic generators, solar cells, and the like.
- galvanic i.e., voltaic
- electrolytic cells subsumes the definitions of batteries, fuel cells, photocells (photovoltaic cells), thermopiles, electric generators, electrostatic generators, solar cells, and the like.
- the structural components of a DMFC will have the following characteristics.
- the membrane should (1) be resistant to harsh oxidizing/reducing environments; (2) possess mechanical toughness; (3) be resistant to high temperatures and pressures (e.g., 0-160 °C and 1-10 atm); (4) be impermeable to methanol under all operating conditions; (5) conduct protons with minimal ohmic resistance and mass transport losses; and (6) be composed of lightweight and inexpensive materials.
- Both the anode and cathode preferably, should (1) exhibit high catalytic activity; (2) possess a large surface area; (3) require minimal amounts of precious metals; and (4) be easily to fabricated.
- the anode should preferably show tolerance to carbon monoxide
- the cathode should preferably show tolerance to methanol if so needed.
- the integrated fuel cell assembly itself should preferably (1 ) have few moving parts; (2) require no external cooling system; (3) require no fuel reformer or purifier; (4) be composed of durable and inexpensive components; (5) be easily fabricated; (6) be easily integrated into fuel cell stacks; and (7) provide highly efficient energy conversion (i.e., at least 50%).
- fluid flow can be categorized into two regimes: laminar flow and turbulent flow.
- laminar flow In steady or laminar flow (FIG. 3), the velocity of the fluid at a given point does not change with time (i.e., there are well- defined stream lines).
- turbulent flow In turbulent flow the velocity of the fluid at a given point does change with time. While both laminar and turbulent flow occur in natural systems (e.g., in the circulatory system), turbulent flow generally predominates on the macroscale. In contrast, laminar flow is generally the norm on the microfluidic scale.
- Re Reynolds number
- Td diffusion time scale
- An electrochemical cell embodying features of the present invention includes (a) a first electrode; (b) a second electrode; and (c) a channel contiguous with at least a portion of the first and the second electrodes.
- a first liquid is contacted with the first electrode
- a second liquid is contacted with the second electrode
- the first and the second liquids flow through the channel
- a multistream laminar flow is established between the first and the second liquids, and a current density of at least 0.1 mA cm 2 is produced.
- Flow cell designs embodying features of the present invention introduce a new paradigm for electrochemical cells.
- a fuel cell 20 embodying features of the present invention that does not require a PEM nor is subject to several of the limitations imposed by conventional PEMs is shown in FIG. 7.
- both the fuel input 22 e.g. an aqueous solution containing MeOH and a proton source
- the oxidant input 24 e.g., a solution containing dissolved oxygen or hydrogen peroxide and a proton source
- multistream laminar flow induces a dynamic proton-conducting interface 28 that is maintained during fluid flow.
- the IDCI is established between anode 30 and cathode 32.
- a proton gradient is created between the two streams and rapid proton diffusion completes the circuit of the cell as protons are produced at anode 30 and consumed at cathode 32.
- the IDCI prevents the two solutions from mixing and allows rapid proton conduction by diffusion to complete the circuit.
- the liquid containing the fuel and the liquid containing the oxidant each contains a common electrolyte, which is preferably a source of protons (e.g., a Br ⁇ nsted acid).
- an electrochemical cell embodying features of the present invention produces current densities of at least 0.1 mA/cm 2 , more preferably of at least 1 mA/cm 2 , still more preferably of at least 2 mA/cm 2 .
- a current density of 27 mA cm 2 has been produced in accordance with presently preferred embodiments.
- the current density produced by a cell be substantially matched to the requirements for a particular application.
- an electrochemical cell embodying features of the present invention is to be utilized in a cellular phone requiring a current density of about 10 mA/cm 2 , it is preferred that the electrochemical cell produce a current density that is at least sufficient to match this demand.
- the methanol is completely consumed before it diffuses into the oxidant stream.
- concentration of methanol is controlled by a methanol sensor coupled to a fuel injector or to a flow rate monitor.
- a water immiscible oxidant fluid stream having a very low affinity for methanol and a high affinity for oxygen and carbon dioxide can be used in conjunction with the laminar flow-type cell shown in FIG. 7.
- At least one such family of fluids viz., perfluorinated fluids such as perfluorodecalin available from F2 Chemicals Ltd., Preston, UK
- perfluorinated fluids such as perfluorodecalin available from F2 Chemicals Ltd., Preston, UK
- FIG.8 shows two alternative cell designs.
- the anode and cathode are positioned side-by-side, analogous to the placement shown in FIG. 7.
- FIG. 8B the anode and cathode are positioned face-to-face.
- the optimization of cell dimensions can be achieved via computer modeling (e.g., using fluid flow modeling programs, Microsoft EXCEL software, etc.) to correlate optimum laminar flow conditions (i.e., minimum mixing) with easily fabricated channel dimensions and geometries.
- Critical values for the Reynolds number can be calculated for an array of cell designs with respect to channel width, depth, length, flow rate, and interfacial surface area. In this manner, a channel design that provides the greatest power output and highest fuel conversion can be determined.
- the electrodes are then patterned onto a support (e.g., a soda lime or Pyrex glass slide).
- the electrodes may be sacrificial electrodes (i.e., consumed during the operation of the electrochemical cell) or non-sacrificial electrodes (i.e., not consumed by the operation of the electrochemical cell). In preferred embodiments, the electrodes are non-sacrificial. In any event, the type of electrode used in accordance with the present invention is not limited. Any conductor with bound catalysts that either oxidize or reduce methanol or oxygen is preferred. Suitable electrodes include but are not limited to carbon electrodes, platinum electrodes, palladium electrodes, gold electrodes, conducting polymers, metals, ceramics, and the like.
- the electrode patterns can be produced by spray coating a glass slide and mask combination with dispersions of metallic (preferably platinum) particles in an organic or aqueous carrier.
- a preferred dispersion of platinum particles in an organic carrier is the inexpensive paint product sold under the trade name LIQUID BRIGHT PLATINUM by Wale Apparatus (Hellertown, PA).
- the patterned slide is then baked in a high temperature oven in the presence of oxygen or air to produce a thin conductive layer of pure platinum.
- This technique enables production of thin, high surface area, mechanically robust, low resistance platinum electrodes on glass slides.
- they can be decorated with ruthenium using chemical vapor deposition, sputtering, or a technique known as spontaneous electroless deposition (see: A. Wieckowski et al. J. Catalysis,
- the microchannel can be constructed readily from flat, inexpensive, precision starting materials as shown in FIGS. 9-10 using techniques such as those described by B. Zhao, J. S. Moore, and D. J. Beebe in Science, 2001, 291,
- MicroChannel 34 can be constructed from commercially available glass slides 36 and cover slips 38.
- the microchannel 34 can be sealed with an ultraviolet-based chemically resistant adhesive.
- a preferred ultraviolet- based chemically resistant adhesive is that sold by Norland Products, Inc. (Cranberry, NJ), which is chemically resistant to most water-miscible solvents.
- the cell thus produced will have chemical resistance and can be employed as a single channel laminar flow DMFC.
- optimization experiments can be performed in which the efficiency of the cell is evaluated with respect to concentration of methanol, concentration of proton, oxidant composition, flow rate, and temperature. Evaluation of cell performance is determined based on cell potential, current density, peak power, and power output.
- the single channel laminar flow DMFC is reusable, and multiple experiments can be performed with the same cell.
- the fuel and oxidant are introduced into the flow channel with the aid of one or more pumps, preferably with the aid of one or more high-pressure liquid chromatography (HPLC) fluid pumps.
- HPLC high-pressure liquid chromatography
- the flow rate of the fuel and oxidant streams can be controlled with two HPLC pumps to enable precise variation of the flow rate from 0.01 to 10 mL/ in.
- This approach allows for the use of large reservoirs of fuel and oxidant that can be heated to constant temperatures and maintained under inert atmosphere, air, or oxygen, as needed.
- the effluent streams can be monitored for the presence of methanol to quantify chemical conversion, cell efficiency, and methanol crossover, by sampling the effluent stream and subjecting it to gas chromatographic analysis. In this manner, the optimized operating conditions for a single channel laminar flow DMFC can be determined. It is noted that the fabrication technique described above can be readily extended to the construction of multi-channel laminar flow DMFC stacks for use in devices having increased power requirements.
- a single channel laminar flow DMFC can be constructed using materials with sufficient structural integrity to withstand high temperatures and/or pressures.
- Graphite composite materials similar to those used in
- DMFCs from Manhattan Scientific or ceramic materials (similar to those used in DMFCs from Los Alamos National Laboratory) can be used in view of their light weight, mechanical integrity, high temperature stability, corrosion resistance, and low cost.
- a variety of fabrication techniques can be used to produce the microchannel including micro-milling, micro-molding, and utilizing an Electric Discharge Machine (EDM) such as is used in the fabrication of injection molds.
- EDM Electric Discharge Machine
- the electrodes can be deposited as described above, and a chemically inert gasket used to seal the cell.
- the gasket can be made, for example, from a fluoropolymer such as polytetrafluoroethylene sold under the trade name TEFLON by DuPont (Wilmington, DE).
- aqueous solutions of 2M copper sulphate and zinc sulphate were prepared.
- the zinc sulphate solution was brought into the channel first over the zinc electrode with the aid of a syringe pump (this filled the entire channel with liquid and care was take to remove all air bubbles).
- the copper sulphate solution was then introduced over the copper electrode.
- Laminar flow was established between the electrodes and a current to voltage plot was developed as shown in FIG. 11.
- the flow rates of the two solutions were held constant and equal to each other (e.g., at 0.1 mL/min) in order for the induced dynamic conducting interface to exist between the two electrodes. If the flow rates were different and the opposing stream touched the opposite electrode, the cell would short and produce no current.
- the flow rates of the two solutions be similar (i.e., differ by less than about 15 percent, more preferably by less than about 10 percent, and still more preferably by less than about 5 percent).
- a Laminar Flow Cell Using Non-Sacrificial Electrodes Two flat platinum electrodes (ca. 0.125 x 20 x 3 mm) were imbedded into a block of polycarbonate by micro-machining channels and adhering the electrodes into these channels, creating a flat substrate with exposed electrode surfaces. The electrodes were both of equivalent size and ran parallel to each other with a gap of approximately 5 mm. On top of this electrode assembly was assembled a flow channel composed of double stick tape and a microscope coverglass as shown in Figure 11. The cell was sealed and the input adapters were secured with commercially available epoxy (Loctite Quick Set Epoxy, Rocky Hill, CT).
- the fuel cell system 1301 has the anode and cathode electrodes in a face-to-face orientation similar to Figure 8B. Using a very similar fabrication scheme as described below, the side-by- side orientation of the cathode and anode electrodes as shown in Figure 8A may also be obtained.
- the fuel cell system 1301 includes multiple parts that are stacked in layers.
- FIG. 13 a schematic top view and a cross sectional view is given of such a stacked layer assembly, wherein the fuel stream 1302 and oxidant stream 1304 will convene at a Y-shaped junction and continue to flow laminarly in parallel in the common fluidic channel 1306 in which the catalyst covered electrodes 1308 cover part of the walls.
- the central support layer 1300 that carries the outline of the fluidic channel 1306 and supports the catalyst covered anode and cathode electrodes 1308 with their leads 1310 may be fabricated according to the following procedure. First, a negative of the channel shape, a master, is obtained in thick photoresist (SU-8 series, Microchem, Newton, MA) via standard photolithographic techniques using transparency films as the mask.
- This master is replicated into an elastomeric mold, typically a silicone rubber (poly(dimethylsiloxane) (PDMS) or SILGARDTM 184, Dow Corning, Midland, Ml), to obtain a positive relief structure of the fluidic channel 1306 (for a detailed description of this type of procedure see Duffy et al., Anal. Chem. (1998) 70, pp.4974-4984).
- a silicone rubber poly(dimethylsiloxane) (PDMS) or SILGARDTM 184, Dow Corning, Midland, Ml
- the mold is replicated to obtain the desired central support layer.
- a liquid UV-curable polyurethane adhesive Norland Optical Adhesive no.
- Shadow evaporation of metals is used to apply the anode and cathode electrodes 1308 in the appropriate shapes to the central support layer.
- chromium usually 2-50 nm
- gold usually 50-1500 nm
- the seed layer for consecutive electrodeposition of the catalyst, for example Platinum Black plated on gold on each electrode separately at 2.6 V with a current density of about 10 mA/cm 2 for 3 minutes.
- both the anode and cathode consist of electrodeposited Platinum Black. Similar procedures may be used to apply other metals or combinations thereof.
- the central support layer 1300 carrying the electrodes 1308 is clamped between two gasket layers 1314 (typically 1-10 mm in thickness) that form the top and the bottom wall of the fluidic channel 1306 embedded in the central support structure 1300. These two gasket layers 1314 are shaped for easy access to the leads 1310 that are connected to the electrodes 1308.
- slabs of a silicone elastomer for example PDMS
- Other materials including glass, PLEXIGLASTM, other gasket materials (for example, rubber) or a combination of any of such materials could be used as well.
- fluidic tubing is placed in the gaskets.
- the tubes may be kept in place by a pressure-fit mechanism.
- more rigid top and bottom capping layers 1322 may be applied, such as 2 mm-thick
- Saturated oxygen solutions were obtained by bubbling oxygen gas (99.99%, S.J. Smith Welding Supply) through an aqueous solution of 1-50% H 2 SO 4 at 298 K for at least 15 minutes.
- Oxygen solutions may also be prepared by bubbling oxygen or air in aqueous emulsions of fluorinated solvents as described in "Emulsions for Fuel Cells", filed June 27, 2003, inventors Larry J. Markoski et al., U.S. Patent Application Serial No. , Attorney Docket No. 09800240-0048, hereby incorporated by reference in its entirety.
- an oxygen solution may be obtained by bubbling oxygen gas or air in an emulsion made by emulsifying 10 mL of perfluorodecaline (PFD) in 20 mL of 0.5 M sulfuric acid with an amount of ZONYL ® FS-62 equivalent to 1 % of the total weight of the emulsion.
- PFD perfluorodecaline
- Other examples of oxidants are solutions of ozone, hydrogen peroxide, permanganate salts, manganese oxide, fluorine, chlorine, bromine, and iodine.
- Other examples of fuels are solutions of ethanol, propanol, formaldehyde, ferrous chloride, and sulfur.
- this technology will be especially useful in portable and mobile fuel cell systems, such as in cellular phones, laptop computers, DVD players, televisions, palm pilots, calculators, pagers, hand-held video games, remote controls, tape cassettes, CD players, AM and FM radios, audio recorders, video recorders, cameras, digital cameras, navigation systems, wristwatches, and the like. It is also contemplated that this technology will also be useful in automotive and aviation systems, including systems used in aerospace vehicles and the like.
Abstract
Description
Claims
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JP2006517709A JP2007526598A (en) | 2003-06-27 | 2004-06-25 | Fuel cell with laminar flow induced dynamic conductive interface, electronic device with the cell, and method of using the same |
CA002540396A CA2540396A1 (en) | 2003-06-27 | 2004-06-25 | Fuel cells comprising laminar flow induced dynamic conducting interfaces, electronic devices comprising such cells, and methods employing same |
EP04756200A EP1649532A2 (en) | 2003-06-27 | 2004-06-25 | Fuel cells comprising laminar flow induced dynamic conducting interfaces, electronic devices comprising such cells, and methods employing same |
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US10/609,017 | 2003-06-27 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006101967A2 (en) * | 2005-03-21 | 2006-09-28 | The Board Of Trustees Of The University Of Illinois | Membraneless electrochemical cell and microfluidic device without ph constraint |
EP2026399A1 (en) * | 2007-08-09 | 2009-02-18 | Korea Advanced Institute of Science and Technology | Membraneless micro fuel cell |
US7651797B2 (en) | 2002-01-14 | 2010-01-26 | The Board Of Trustees Of The University Of Illinois | Electrochemical cells comprising laminar flow induced dynamic conducting interfaces, electronic devices comprising such cells, and methods employing same |
CN112751053A (en) * | 2019-10-30 | 2021-05-04 | 武汉轻工大学 | Flexible microfluid photoelectric fuel cell |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US7435503B2 (en) * | 2004-06-10 | 2008-10-14 | Cornell Research Foundation, Inc. | Planar membraneless microchannel fuel cell |
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US20070026266A1 (en) * | 2005-07-19 | 2007-02-01 | Pelton Walter E | Distributed electrochemical cells integrated with microelectronic structures |
US7901817B2 (en) * | 2006-02-14 | 2011-03-08 | Ini Power Systems, Inc. | System for flexible in situ control of water in fuel cells |
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US20090035644A1 (en) * | 2007-07-31 | 2009-02-05 | Markoski Larry J | Microfluidic Fuel Cell Electrode System |
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US8163429B2 (en) * | 2009-02-05 | 2012-04-24 | Ini Power Systems, Inc. | High efficiency fuel cell system |
US8492052B2 (en) | 2009-10-08 | 2013-07-23 | Fluidic, Inc. | Electrochemical cell with spacers for flow management system |
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US20120070766A1 (en) | 2010-09-21 | 2012-03-22 | Massachusetts Institute Of Technology | Laminar flow fuel cell incorporating concentrated liquid oxidant |
US9105946B2 (en) | 2010-10-20 | 2015-08-11 | Fluidic, Inc. | Battery resetting process for scaffold fuel electrode |
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US8783304B2 (en) | 2010-12-03 | 2014-07-22 | Ini Power Systems, Inc. | Liquid containers and apparatus for use with power producing devices |
US9065095B2 (en) | 2011-01-05 | 2015-06-23 | Ini Power Systems, Inc. | Method and apparatus for enhancing power density of direct liquid fuel cells |
CN103339762B (en) | 2011-01-13 | 2016-03-30 | 伊莫基动力系统公司 | Flow cell stack |
US8906572B2 (en) | 2012-11-30 | 2014-12-09 | General Electric Company | Polymer-electrolyte membrane, electrochemical fuel cell, and related method |
FR3015776A1 (en) * | 2013-12-24 | 2015-06-26 | Rhodia Operations | ELECTROCHEMICAL CELL FOR A LIQUID FUEL CELL, ESPECIALLY FOR A BATTERY CALLED "REDOXFLOW" |
BR112019000713B1 (en) | 2016-07-22 | 2023-04-25 | Nantenergy, Inc | ELECTROCHEMICAL CELL AND METHOD OF CONSERVING MOISTURE INSIDE AN ELECTROCHEMICAL CELL |
DE102018002746A1 (en) | 2018-04-06 | 2019-10-10 | Analytconsult Gbr | Method and device for storing electrical energy in chemical redox compounds - Efficient redox flow battery |
WO2020231718A1 (en) | 2019-05-10 | 2020-11-19 | Nantenergy, Inc. | Nested annular metal-air cell and systems containing same |
FR3126998B1 (en) * | 2021-09-13 | 2024-04-05 | Fairbrics | Membraneless electrolysis cell and its use in electrolysis reactions |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5534120A (en) * | 1995-07-03 | 1996-07-09 | Toto Ltd. | Membraneless water electrolyzer |
WO2003061037A2 (en) * | 2002-01-14 | 2003-07-24 | Board Of Trustees Of University Of Illinois | Electrochemical cells comprising laminar flow induced dynamic conducting interfaces, electronic devices and methods using such cells |
US20040058217A1 (en) * | 2002-09-20 | 2004-03-25 | Ohlsen Leroy J. | Fuel cell systems having internal multistream laminar flow |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1522308A (en) * | 1967-02-24 | 1968-04-26 | Alsthom Cgee | Electrolytic cycle for semi-permeable diaphragm fuel cell |
FR2146142B1 (en) * | 1971-07-20 | 1974-03-15 | Alsthom Cgee | |
US3849275A (en) * | 1972-06-16 | 1974-11-19 | J Candor | Method and apparatus for removing and/or separating particles from fluid containing the same |
US4066526A (en) * | 1974-08-19 | 1978-01-03 | Yeh George C | Method and apparatus for electrostatic separating dispersed matter from a fluid medium |
US4311594A (en) * | 1975-12-01 | 1982-01-19 | Monsanto Company | Membrane separation of organics from aqueous solutions |
CA1222281A (en) * | 1983-06-17 | 1987-05-26 | Yasuo Ando | Secondary battery having the separator |
JPH041657Y2 (en) * | 1984-12-10 | 1992-01-21 | ||
JPH0815598B2 (en) | 1991-03-13 | 1996-02-21 | 光八 上村 | Ion water generator |
US5413881A (en) * | 1993-01-04 | 1995-05-09 | Clark University | Aluminum and sulfur electrochemical batteries and cells |
RU2174728C2 (en) * | 1994-10-12 | 2001-10-10 | Х Пауэр Корпорейшн | Fuel cell using integrated plate technology for liquid-distribution |
US5863671A (en) * | 1994-10-12 | 1999-01-26 | H Power Corporation | Plastic platelet fuel cells employing integrated fluid management |
DE4443939C1 (en) * | 1994-12-09 | 1996-08-29 | Fraunhofer Ges Forschung | PEM fuel cell with structured plates |
JPH10211447A (en) | 1997-01-28 | 1998-08-11 | Mitsubishi Heavy Ind Ltd | Method for separating and recovering cathode material and anode material of secondary battery |
DE19841302C2 (en) | 1998-09-10 | 2002-12-19 | Inst Mikrotechnik Mainz Gmbh | Reactor and process for carrying out electrochemical reactions |
DE19923738C2 (en) * | 1999-05-22 | 2001-08-09 | Daimler Chrysler Ag | Fuel cell system and method for operating a fuel cell system |
US6924058B2 (en) * | 1999-11-17 | 2005-08-02 | Leroy J. Ohlsen | Hydrodynamic transport and flow channel passageways associated with fuel cell electrode structures and fuel cell electrode stack assemblies |
US20020041991A1 (en) * | 1999-11-17 | 2002-04-11 | Chan Chung M. | Sol-gel derived fuel cell electrode structures and fuel cell electrode stack assemblies |
US6641948B1 (en) | 1999-11-17 | 2003-11-04 | Neah Power Systems Inc | Fuel cells having silicon substrates and/or sol-gel derived support structures |
US6312846B1 (en) * | 1999-11-24 | 2001-11-06 | Integrated Fuel Cell Technologies, Inc. | Fuel cell and power chip technology |
JP2001325983A (en) * | 2000-05-16 | 2001-11-22 | Sumitomo Electric Ind Ltd | Redox flow cell |
US20030003336A1 (en) * | 2001-06-28 | 2003-01-02 | Colbow Kevin Michael | Method and apparatus for adjusting the temperature of a fuel cell by facilitating methanol crossover and combustion |
-
2003
- 2003-06-27 US US10/609,017 patent/US7252898B2/en not_active Expired - Fee Related
-
2004
- 2004-06-25 KR KR1020057025089A patent/KR20060021916A/en not_active Application Discontinuation
- 2004-06-25 WO PCT/US2004/020597 patent/WO2005004262A2/en not_active Application Discontinuation
- 2004-06-25 EP EP04756200A patent/EP1649532A2/en not_active Withdrawn
- 2004-06-25 CA CA002540396A patent/CA2540396A1/en not_active Abandoned
- 2004-06-25 JP JP2006517709A patent/JP2007526598A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5534120A (en) * | 1995-07-03 | 1996-07-09 | Toto Ltd. | Membraneless water electrolyzer |
WO2003061037A2 (en) * | 2002-01-14 | 2003-07-24 | Board Of Trustees Of University Of Illinois | Electrochemical cells comprising laminar flow induced dynamic conducting interfaces, electronic devices and methods using such cells |
US20040058217A1 (en) * | 2002-09-20 | 2004-03-25 | Ohlsen Leroy J. | Fuel cell systems having internal multistream laminar flow |
Non-Patent Citations (4)
Title |
---|
CHOBAN E R ET AL: "Microfluidic fuel cell based on laminar flow" JOURNAL OF POWER SOURCES, ELSEVIER, AMSTERDAM, NL, vol. 128, no. 1, 29 March 2004 (2004-03-29), pages 54-60, XP004493639 ISSN: 0378-7753 * |
CHOBAN E R ET AL: "MICROFLUIDIC FUEL CELLS THAT LACK A PEM" PROCEEDINGS OF THE ANNUAL POWER SOURCES CONFERENCE, vol. 40, 2002, pages 317-320, XP009031634 * |
FERRIGNO R ET AL: "Membraneless Vanadium Redox Fuel Cell Using Laminar Flow" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 124, 15 October 2002 (2002-10-15), pages 12930-12931, XP002282850 ISSN: 0002-7863 * |
P.J. A. KENIS AND AL: "Fabrication inside microchannels using fluid flow" ACCOUNTS OF CHEMICAL RESEARCH, vol. 33, 2000, pages 841-847, XP002380095 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7651797B2 (en) | 2002-01-14 | 2010-01-26 | The Board Of Trustees Of The University Of Illinois | Electrochemical cells comprising laminar flow induced dynamic conducting interfaces, electronic devices comprising such cells, and methods employing same |
US8283090B2 (en) | 2002-01-14 | 2012-10-09 | The Board Of Trustees Of The University Of Illinois | Electrochemical cells comprising laminar flow induced dynamic conducting interfaces, electronic devices comprising such cells, and methods employing same |
WO2006101967A2 (en) * | 2005-03-21 | 2006-09-28 | The Board Of Trustees Of The University Of Illinois | Membraneless electrochemical cell and microfluidic device without ph constraint |
WO2006101967A3 (en) * | 2005-03-21 | 2007-05-31 | Univ Illinois | Membraneless electrochemical cell and microfluidic device without ph constraint |
US7635530B2 (en) | 2005-03-21 | 2009-12-22 | The Board Of Trustees Of The University Of Illinois | Membraneless electrochemical cell and microfluidic device without pH constraint |
EP2026399A1 (en) * | 2007-08-09 | 2009-02-18 | Korea Advanced Institute of Science and Technology | Membraneless micro fuel cell |
CN112751053A (en) * | 2019-10-30 | 2021-05-04 | 武汉轻工大学 | Flexible microfluid photoelectric fuel cell |
CN112751053B (en) * | 2019-10-30 | 2022-03-29 | 武汉轻工大学 | Flexible microfluid photoelectric fuel cell |
Also Published As
Publication number | Publication date |
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CA2540396A1 (en) | 2005-01-13 |
JP2007526598A (en) | 2007-09-13 |
WO2005004262A3 (en) | 2006-07-06 |
EP1649532A2 (en) | 2006-04-26 |
US20040072047A1 (en) | 2004-04-15 |
KR20060021916A (en) | 2006-03-08 |
US7252898B2 (en) | 2007-08-07 |
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