CA2362298A1 - Solid gel membrane - Google Patents
Solid gel membrane Download PDFInfo
- Publication number
- CA2362298A1 CA2362298A1 CA002362298A CA2362298A CA2362298A1 CA 2362298 A1 CA2362298 A1 CA 2362298A1 CA 002362298 A CA002362298 A CA 002362298A CA 2362298 A CA2362298 A CA 2362298A CA 2362298 A1 CA2362298 A1 CA 2362298A1
- Authority
- CA
- Canada
- Prior art keywords
- electrochemical cell
- rechargeable electrochemical
- anode
- hydroxide
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 113
- 239000007787 solid Substances 0.000 title claims abstract description 77
- 229920000642 polymer Polymers 0.000 claims abstract description 63
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 239000000446 fuel Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 11
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 47
- 239000011701 zinc Substances 0.000 claims description 46
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 44
- 229910052725 zinc Inorganic materials 0.000 claims description 44
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 40
- 241000894007 species Species 0.000 claims description 36
- 239000003792 electrolyte Substances 0.000 claims description 31
- -1 poly(sodium 4-styrenesulfonate) Polymers 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 22
- 230000001588 bifunctional effect Effects 0.000 claims description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000003505 polymerization initiator Substances 0.000 claims description 17
- 230000005855 radiation Effects 0.000 claims description 17
- 230000003014 reinforcing effect Effects 0.000 claims description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- 125000006850 spacer group Chemical group 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 10
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 10
- 235000011151 potassium sulphates Nutrition 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 9
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000002322 conducting polymer Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229920001464 poly(sodium 4-styrenesulfonate) Polymers 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 239000002759 woven fabric Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- BSSNZUFKXJJCBG-OWOJBTEDSA-N (e)-but-2-enediamide Chemical compound NC(=O)\C=C\C(N)=O BSSNZUFKXJJCBG-OWOJBTEDSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229920002261 Corn starch Polymers 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000008120 corn starch Substances 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 3
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000075 oxide glass Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical group [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910001923 silver oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- 229920006254 polymer film Polymers 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000007784 solid electrolyte Substances 0.000 abstract description 5
- 239000004984 smart glass Substances 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 66
- 239000010408 film Substances 0.000 description 16
- 239000008151 electrolyte solution Substances 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 210000001787 dendrite Anatomy 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 239000004693 Polybenzimidazole Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006262 metallic foam Substances 0.000 description 3
- 229920002480 polybenzimidazole Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 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
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IQIJRJNHZYUQSD-UHFFFAOYSA-N ethenyl(phenyl)diazene Chemical compound C=CN=NC1=CC=CC=C1 IQIJRJNHZYUQSD-UHFFFAOYSA-N 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/121—Charge-transfer complexes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/22—Immobilising of electrolyte
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/16—Swelling agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
- B01D2323/385—Graft polymerization involving radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/50—Membrane in gel form
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Abstract
A highly conductive polymer based solid gel membrane is disclosed. The membrane is especially well-suited for use in such electrochemical devices a s metal/air, Zn/MnO2, Ni/Cd and hydrogen fuel cells, as well as in electrochromic devices such as smart windows and flat paneldisplays. Furthermore, in rechargeable electrochemical cells, the solid gel membrane i s highlyeffective for use as a separator between the anode and charging electrode. In accordance with the principles of the invention, the highly conductive membrane comprises a support or substrate and a polymeric gel composition having an ionic species contained in a solution phase thereof. T he polymer-based gel is prepared by adding an ionic species to a monomer soluti on followed by polymerization. After polymerization, the ionic species is embedded in the polymer-based gel where it remains. The ionic species behave s like a liquid electrolyte, while at the same time, the polymer-based solid g el membrane provides a smooth impenetrable surface that allows for the exchange of ions. An advantage of the novel membrane is that its measured ionic conductivity is much higher than previously observed in prior art solid electrolytes or electrolyte-polymer films.
Description
SOLID GEL MEMBRANE
Field of the Invention This invention relates generally to solid gel membranes, and more particularly to an ionic-conducting polymer-based solid gel membrane.
Background of the Invention Electrochemical devices generally incorporate an electrolyte source to provide the anions or canons necessary to produce an electrochemical reaction.
A
zinc/air system, for example, requires the diffusion of hydroxide anions, and typically will incorporate an aqueous potassium hydroxide solution as the to electrolyte. The lifetime of this battery is however, limited for several reasons.
First, the naked zinc anode is corroded by both the aqueous electrolyte and air Second, the air channels of the air cathode gradually become blocked by water from the electrolyte solution and third, the electrolyte solution becomes contaminated with zinc oxidation product that diffuses from the anode.
Various methods have been used to address the many problems associated with the use of aqueous electrolytes in zinc anode based systems such as zinc/air fuel cells. Additives, for example, have been introduced into the electrolyte solution to extend its lifetime and to protect the anode from corrosion. United States Patent 4,118,551 discloses the use of inorganic additives such as mercury, indium, tin, lead, lead compounds, cadmium or thallium oxide to reduce corrosion of a zinc electrode. Many of these additives however, are expensive and more significantly, are very toxic. United States Patent 4,378,414 discloses the use of a mufti-layer separator between the positive and negative electrodes to reduce corrosion of the anode and contamination of the electrolyte by zinc oxidation products. In addition, hydrophobic materials have been introduced into zinc/air devices to prevent water permeation into the air channels of the cathode. Introduction of hydrophobic materials is however, a difficult process and may result in decreased performance of the cathode.
In addition to zinc/air systems, other metal/air systems, such as aluminum/air, lithium/air, cadmium/air, magnesium/air, and iron/air systems, also have the potential for many different applications due to their theoretically high ampere-hour capacity, voltage, and specific energy. In actual practice however, these very promising theoretical values are greatly reduced due to the corrosion of the metal anode in the electrolyte.
A solid state hydroxide conductive electrolyte polybenzimidazole ("PBI") 1o film is disclosed in United States Patent 5,688,613 and comprises a polymeric support structure having an electrolyte active species dispersed therein, wherein the polymer structure is in intimate contact with both the anode and the cathode.
This PBI film, however, does not absorb water and therefore, does not hold water within the membrane, causing it to dry out quickly.
United States Patent 3,871,918 discloses an electrochemical cell embodying an electrode of zinc powder granules suspended in a gel comprised of methylenebisacrylamide, acrylic acid and acrylamide. Potassium hydroxide serves as the electrolyte, and is contained within the gel.
With regard to devices that rely on the conduction of cations, while there 2o has been a significant amount of research in this area, most proton conducting membranes are very expensive to produce and typically do not function at room temperature. In the 1970's for example, a fully fluorinated polymer membrane, NAFION~ (DuPont, Wilmington, DE USA) was introduced and has served as the basis from which subsequent proton conducting membranes have evolved.
United States Patent 5,468,574 discloses a proton conductive membrane that is characterized as a highly sulfonated polymeric membrane composed of block copolymers of sulfonated polystyrene, ethylene and butylene blocks. In 1997, NASA's Jet Propulsion Laboratory disclosed the development of an improved proton conductive membrane composed of sulfonated poly(ether ether ketone), commonly known as H-SPEEK.
The separator in a cell or battery physically separates and electrically insulates electrodes of different polarity. While serving as a barrier to the transport of active materials of the different electrodes, a separator should also provide ionic conduction. Good ionic conductivity is necessary to ensure that an electrochemical cell/battery is capable of delivering usable amounts of power for a given application.
In a rechargeable electrochemical cell, a separator is also used to prevent short circuiting caused by metal dendrite penetration during recharging. For to example, in rechargeable zinc/air cells, zinc on the surface of the negative zinc electrode (anode) is dissolved as zincate ion into the electrolyte solution during discharge. Then, during the charge, when the charging current is typically below 20 mA/cm2, depending on the particular anode used, the zincate ion forms dendritic zinc, which is needle-like and grows from the negative electrode toward the charging electrode. Unfortunately, these needle-like structures can pierce through conventional separators causing an internal short circuit. The service life of the cell is consequently terminated. In addition to preventing dendrite penetration, the separator must allow for the exchange of electrolytic ions during both discharging and charging of the cell.
2o The most commonly used separators in rechargeable cells are porous insulator films of polyolefins, polyvinyl alcohol (PVA), nylon, or cellophane Acrylic compounds may also be radiation-grafted onto these separators to make them more wettable and permeable to the electrolyte. Although much work has been done to improve the performance of separators, dendrite penetration problems are frequently encountered with these and other conventional separators, as well as problems involving diffusion of reaction products such as the metal oxide to remaining parts of the cell.
With conventional separators, controlling the pore size of the separator is the only effective way to avoid dendrite penetration and prevent product diffusion.
By doing this, however, the ionic conductivity of the separator is also greatly reduced. This creates a bottleneck for high charging-discharging current density operations, important considerations for use in some applications, such as in electrical vehicles.
United States Patent 5,549,988 discloses an electrolyte system separator disposed between the cathode and anode of a rechargeable electrochemical battery.
The electrolyte system includes a polymer matrix prepared from polyacrylic acid or to derivatives thereof. An electrolyte species, such as KOH or HzS04, is then added to the polymer matrix to complete the system. However, as reported in the patent, the measured ionic conductivities of the disclosed electrolyte-polymer films are low, ranging from 0.012 S/cm to 0.066 S/cm. Although these conductivities are acceptable for some applications, they are inadequate for other high rate operations including electrical vehicles.
An electrochemical reaction is also involved in the function of electrochromic devices (ECD's). Electrochromism is broadly defined as a reversible optical absorption change induced in a material by an electrochemical redox process. Typically, an electrochromic device contains two different electrochromic materials (ECM's) having complementary properties; the first is generally reduced, undergoing a color (1)-to-color (2) transition during reduction, while the second material is oxidized, undergoing a similar transition upon the loss of electrons.
Basically, there are two types of electrochromic devices, depending upon the location of the electrochromic materials within the device. In a thin-film type device, the two ECM's are coated onto the two electrodes and remain there during the redox coloration process. In a solution-phase device, both ECM's are dissolved in an electrolyte solution and remain their during the coloration cycle. The solution-phase device is typically more reliable and has a longer lifetime, however, in order to maintain the colored state, an external power source must be continuously applied. As the thin-film type device does not need an external power source to maintain its colored state, power consumption is greatly reduced, making this an advantage for such energy-saving applications as smart windows. The drawback of the thin-film type device is that it has a short lifetime. After a certain number of cycles, ECM films can lose contact with the electrode, or they may no longer be capable of phase change and the device expires.
With regard to solution-phase devices, United States Patent 5,128,799, for to example, discloses a method of reducing the current required to maintain the colored state which involves the addition of gel into the device. While reducing energy consumption however, the addition of the gel into the device also greatly reduces the switching speed of the device. With regard to thin-film devices, attempts to extend the lifetime of the device have included changes to the crystal structure of the film. While such changes have increased the lifetime of thin-film devices to an extent, the typical lifetime of such devices is still not satisfactory.
The foregoing problems thus present major obstacles to the successful development and commercialization of fuel cell technology, a green energy source, and of electrochromic devices such as smart windows and flat panel displays, which 2o have several energy-saving, decorative, and information display applications. With respect to the problems associated with rechargeable electrochemical cells, it is clear that there is a great need for a separator that can provide improved ionic conductivity while providing an effective barrier against the penetration of metal dendrites and the diffusion of reaction products.
Summary of the Invention The present invention provides polymer-based solid gel membranes that contain ionic species within the gel's solution phase and that are highly conductive to anions or canons. In accordance with the principles of the invention, solid gel membranes may be produced for use in such power sources as, for example, metal/air (e.g. zinc/air, cadmium/air, lithium/air, magnesium/air, iron/air, and aluminum/air), Zn/Ni, Zn/IVInOz, Zn/AgO, Fe/Ni, lead-acid, Ni/Cd, and hydrogen fuel cells, as well as for use in electrochromic devices, such as smart windows and flat panel displays. Additionally, the instant polymeric solid gel membranes are useful in rechargeable electrochemical cells, wherein the solid gel membrane is employed as a separator between the charging electrode and the anode.
With respect to a zinc/air fuel cell battery, for example, conductive membranes of the present invention may be used to protect the anode, as well as the to cathode. In such a system, the ionic species is contained within the solution phase of the solid gel membrane, allowing it to behave as a liquid electrolyte without the disadvantages. The gel membrane protects the anode from corrosion (by the electrolyte as well as by air) and prevents zinc oxidation product from the anode from contaminating the electrolyte. With regard to the cathode, as the membrane is itself a solid, there is no water to block the air channels of the cathode. As a result, the system will have an extended lifetime.
As used herein, the term "anode" refers to and is interchangeable with the term "negative electrode". Likewise, "cathode" refers to and is interchangeable with the term "positive electrode".
2o The present invention also includes rechargeable electrochemical cells that use the solid gel membrane as a separator between the anode and charging electrode. Such a separator provides many advantages that conventional separators lack. For example, it provides a smooth impenetrable surface that allows the exchange of ions for both discharging and charging of the cell while preventing fast dendrite penetration and the diffusion of reaction products such as metal oxide to remaining parts of the cell. Furthermore, the measured ionic conductivities of the present solid gel membranes are much higher than those of prior art solid electrolytes or electrolyte-polymer films. For example, the observed conductivity values for the present separators are surprisingly about 0.10 S/cm or more.
Even more surprisingly, ionic conductivities as high as 0.36 S/cm have been measured, and it is possible that higher values still may be observed. Thus, these unique and unprecedented properties distinguish the separator of the present invention from previous designs that merely trap dendrite growth and slow penetration.
Accordingly, the principles of the present invention relate, in one aspect, to a rechargeable electrochemical cell comprising a separator, an anode, a cathode, and a charging electrode. Optionally, a liquid electrolyte, such as one of those mentioned herein and/or commonly known by those of skill in the art, may also be to included in the rechargeable cell. The liquid (aqueous) electrolyte contacts the separator, each electrode, and a porous spacer, if employed. The separator comprises an ion-conducting polymer-based solid gel membrane which includes a support onto which a polymer-based gel having an ionic species contained within a solution phase thereof is formed. The support may be a woven or nonwoven fabric or one of the electrodes.
The polymer-based gel comprises a polymerization product of one or more monomers selected from the group of water soluble ethylenically unsaturated amides and acids. The polymer-based gel also includes a water soluble or water swellable polymer, which acts as a reinforcing element. In addition, a chemical 2o polymerization initiator (listed below) may optionally be included. The ionic species is added to a solution containing the polymerization initiator (if used), the monomer(s), and the reinforcing element prior to polymerization, and it remains embedded in the polymer gel after the polymerization.
Polymerization is carried out at a temperature ranging from room temperature to about 130° C, but preferably at an elevated temperature ranging from about 75° to about 100° C. Higher heating temperatures, such as those ranging from about 95° to about 100° C, provide a stiffer polymer surface, which is a desirable property in rechargeable cell applications. Optionally, the polymerization may be carried out using radiation in conjunction with heating.
Alternatively, the polymerization may be performed using radiation alone without raising the temperature of the ingredients, depending on the strength of the radiation. Examples of radiation types useful in the polymerization reaction include, but are not limited to, ultraviolet light, y-rays or x-rays.
In the rechargeable cell, the cathode and charging electrode may be a single bifunctional electrode or may be individual and separate electrodes. The separator is positioned between the anode and charging electrode. In alkaline systems, the hydroxide ionic species typically comes from an aqueous alkaline solution of to potassium hydroxide, sodium hydroxide, lithium hydroxide, or combinations thereof. Preferably in a potassium hydroxide solution, for example, the base has a concentration ranging from about 0.1 wt. % to about 55 wt. %, and most preferably about 37.5 wt. %. In acidic systems, the proton comes from an aqueous acidic electrolyte solution, such as a solution of perchloric acid, sulfuric acid, hydrochloric acid, or combinations thereof. The concentration of perchloric acid, for example, preferably ranges from about 0.5 wt. % to about 70 wt. %, and most preferably about 13.4 wt. %. The membrane separator may also be used in neutral systems, wherein the ionic species comes from a saturated aqueous neutral solution of ammonium chloride and potassium sulfate; a saturated solution of ammonium 2o chloride, potassium sulfate, and sodium chloride; or a saturated neutral solution of potassium sulfate and ammonium chloride.
When the cathode and charging electrode are individual and separate electrodes, the charging electrode is positioned between the separator and cathode, and a porous spacer is optionally positioned between the charging electrode and cathode.
In another aspect, the invention is a rechargeable electrochemical cell comprising a separator, a metal anode (preferably zinc), an air cathode, and a charging electrode. In this system, the separator is a hydroxide conducting polymer-based solid gel membrane comprising a support onto which a polymer-based gel having a hydroxide species contained within a solution phase thereof is formed. The polymer-based gel comprises polysulfone as a reinforcing element and a polymerization product of a polymerization initiator, methylenebisacrylamide, acrylamide, and methacrylic acid. The hydroxide species comes from an aqueous alkaline solution (ranging from about 0.1 wt. % to about 55 wt. % potassium hydroxide, sodium hydroxide, lithium hydroxide, or a mixture thereof), which is added to the polymerization initiator, methylenebisacrylamide, acrylamide, methacrylic acid, and polysulfone prior to polymerization. The air cathode and to charging electrode may be a single bifunctional electrode or may be individual and separate electrodes. The separator is positioned between the metal anode and charging electrode. The ionic conductivity of the separator typically ranges from about 0.10 S/cm to about 0.36 S/cm, but may be higher.
In another aspect, the present invention is an electrochemical cell comprising first and second electrodes and one or more polymer based solid gel membranes disposed there between. In one embodiment, the electrochemical cell is a zinc/air cell having an anode protective solid gel membrane and a hydroxide conducting solid gel membrane disposed between the zinc anode and the air cathode. In another embodiment of a zinc/air system, both the anode and cathode are protected 2o by a solid gel membrane of the present invention, and an aqueous electrolyte is disposed between the two.
In a further embodiment of this aspect of the invention, the electrochemical cell is an aluminum/air cell, wherein a hydroxide conductive solid gel membrane is applied to the aluminum anode to protect it from corrosion.
In yet a further embodiment of this aspect of the invention, the electrochemical cell is an aluminum/air cell, wherein a hydroxide conductive solid gel membrane is disposed between the aluminum anode and the air cathode.
Accordingly, the principles of the present invention also provide a method of inhibiting corrosion of a metal anode in a metal/air fuel cell system comprised of a metal anode and an air cathode. The method comprises disposing one or more polymer based solid gel membranes between said anode and said cathode.
In yet a further embodiment of the invention, the electrochemical cell is a proton or hydroxide conducting power source, such as a hydrogen fuel cell system.
In this embodiment, a proton or hydroxide conductive solid gel membrane may be sandwiched between the hydrogen anode and the air cathode, thus separating the hydrogen and the air, while allowing the dii~'usion of proton or hydroxide ions. This to embodiment provides several advantages over prior art proton conducting membranes in that the solid gel membranes of the present invention are much easier and less expensive to produce than earlier membranes and, more importantly, unlike previous membranes, the solid gel membranes of the present invention will function efficiently at room temperature.
15 The principles of the present invention may also be applied to electrochromic devices. Here, the electrochromic materials of the device are contained within solid gel membranes, thus providing the device with the reliability and long lifetime associated with solution phase EC systems, and also the energy-saving memory properties associated with thin-film EC systems.
2o Accordingly, yet another embodiment of the present invention is an electrochromic device wherein electrochromic materials are contained within polymer based solid gel membranes. Typically, such a device will involve two electrode substrates and electrochromic materials contained within solid gel membranes sandwiched there between. The device may optionally include an 25 aqueous or a solid electrolyte disposed between the solid gel membranes.
The electrode substrates may be comprised of such materials as, for example, platinum, gold, conductive glass, such as indium-tin oxide glass, and the like.
BRIEF DESCRIPTION OF THE DRAWINGS
Numerous other advantages and features of the present invention will become readily apparent from the following detailed description of preferred embodiments when read in conjunction with the accompanying drawings, wherein:
FIG. 1 is a schematic depiction of a zinc/air fuel cell incorporating an anode protective membrane and a hydroxide conducting membrane of the present invention;
FIG. 2 is a schematic depiction of another embodiment of a zinc/air fuel cell incorporating both an anode and a cathode protective membrane of the present 1o invention;
FIG. 3 is a schematic depiction of an aluminum/air fuel cell incorporating a hydroxide conductive membrane of the present invention;
FIG. 4 is a schematic depiction of a hydrogen/air fuel cell incorporating a proton or hydroxide conductive membrane of the present invention;
15 FIG. 5 is a schematic depiction of an electrochromic device wherein the electrochromic materials are contained within membranes of the present invention;
FIG. 6 is a schematic depiction of a rechargeable metal/air battery having three electrodes, a porous spacer, and a solid gel membrane incorporated as a separator in accordance with the present invention; and 2o FIG. 7 is a schematic depiction of a rechargeable metal/air battery having an anode, a bifunctional electrode, and a solid gel membrane incorporated as a separator in accordance with the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring now to the drawings, FIG. 1 depicts a typical zinc/air fuel cell, 25 wherein two polymer-based solid gel membranes (1, 2) are disposed between the zinc anode (3) and the air cathode (4). The first is an anode protective membrane (1) and the second is a hydroxide conductive membrane (2). The membranes are not only the source of ionic species, and are highly conductive to that species, but they also provide a protective layer to the electrodes to prevent the usual sources of cell destruction. The membranes prevent diffusion of zinc oxidation product into the electrolyte solution phase, they prevent corrosion of the zinc anode by either the electrolyte solution or air, and they prevent blockage of the cathode air channels by water from the electrolyte solution. The zinc/air system of FIG. 2 includes a protective and conductive solid gel membrane (5, 6) on the surface of the zinc anode (3) and the air cathode (4), and an aqueous electrolyte (7) between the two.
Referring now to FIG. 3, an aluminum/air fuel cell system incorporating a solid gel hydroxide conductive membrane (8) between the aluminum anode (9) and to the air cathode (10) is depicted. As in the zinc/air system, the solid gel membrane of this embodiment serves to prevent the corrosion problems associated with the use of pure liquid electrolyte and also serves as the ionic conducting media.
As illustrated in Figure 4, when applied to the art of hydrogen fuel cells, the principles of the present invention provide a proton or hydroxide conductive membrane that is easy to produce, much less expensive than existing proton conductive membranes and that functions well at room temperature. Because the actual conducting media remains in aqueous solution within the polymer gel backbone, the conductivity of the membrane is comparable to that of liquid electrolytes, which at room temperature is significantly high. In this embodiment of 2o the invention, a proton or hydroxide conductive solid gel membrane ( 11 ) i s sandwiched between the hydrogen anode (12) and the air cathode (13), thereby separating the hydrogen and the air.
As shown in FIG. 5, the principles of the present invention may also be applied to electrochromic systems. Here, the electrochromic materials are dispersed within the solution phase of the polymer gel backbone of a solid gel membrane.
Since the ECM's are in solution, the device exhibits the superior reliability and long life of a solution phase device and in addition, because the ECM's are physically confined, they can not diffuse into the device's bulk electrolyte and the device therefore also exhibits the superior memory of a thin-film type device. As shown, the device includes two electrode substrates (14, 15) having solid gel membrane encapsulated electrochromic materials (16, 17) there between. As illustrated, the device optionally includes an aqueous or solid electrolyte (18) disposed between solid gel membranes ( 16, 17).
Referring to FIG. 6, there is illustrated therein a rechargeable electrochemical cell (100) fabricated from three electrode assemblies, (20, 30, 40) and contained within housing (90). Electrode (20) represents the negative electrode or metal anode; electrode (40) is the positive electrode, i.e. air cathode;
and to electrode (30) is a porous charging electrode. In this embodiment, cathode (40) and charging electrode (30) are separate electrodes, and charging electrode (30) is positioned between cathode (40) and the solid gel separator. As shown in the drawing, the three electrodes (20, 30, 40) are disposed in spaced apart, parallel relationships with one another. Rechargeable electrochemical cell (100) optionally includes liquid (aqueous) electrolyte (80) in contact with each electrode, separator (60), and porous spacer (50) (when employed) typically by immersion.
Metal anode (20) is made of an oxidizable metal, preferably zinc, cadmium, lithium, magnesium, iron, or aluminum, but metal anode (20) is most preferably zinc. Air cathode (40) preferably has a current density of at least 200 mA/cmz. An 2o air cathode suitable for use in the present invention is disclosed in copending, commonly assigned U. S. Patent Application Ser. No. 09/415,449 entitled ELECTROCHEMICAL ELECTRODE FOR FUEL CELL, filed on October 8, 1999. This exemplary air cathode includes a current collector comprising a porous metal foam substrate, which is formed with a network of inteconnected pores.
An active layer, preferably comprising a carbon/polymer blend, and a hydrophobic microporous gas diffusion layer are both disposed on one or more surfaces of the metal foam substrate. The microporous layer is a plastic material such as a fluoropolymer (i.e., PTFE). The cathode also includes a particulate microstructure reinforced by relatively strong bonding provided by sintering a polymeric binder within the three-dimensional interconnected porosity of the metal foam substrate.
The reactive layers are preferably fabricated from the same material as the binder.
It should be noted, however, that other air cathodes may instead be used, depending on the performance capabilities thereof, as will be obvious to those of skill.
The present invention is in no way limited to use of the exemplary cathode described herein.
As shown in FIG. 6, porous charging electrode (30) is positioned in parallel relationship between metal anode (20) and air cathode (40). Any inert conductive to porous material may be used to form porous charging electrode (30).
Examples include, but are not limited to platinum, nickel, nickel oxide, perovskite and its derivatives, carbon, and palladium. In addition, apertures or holes may be drilled into charging electrode (30) to aid with the passage of ions. It is important that the electrodes do not physically contact each other, and a distance therebetween sufFicient to form a gap for the electrolyte must be provided.
In addition; it is sometimes desirable to position porous spacer (50) between charging electrode (30) and air cathode (40) as a means of ensuring sufficient distance between the two electrodes. When porous spacer (50) is included in rechargeable electrochemical cell (100), a gap is formed for the electrolyte on each 2o side of porous spacer (50 ) and each electrode (30) and (40). However, the invention is not limited to structures which include porous spacer (50). Any means of preventing physical contact between the two electrodes may be employed, such as anchoring the electrodes apart in the housing. However, when porous spacer (50) is used, it is typically made of a porous plastic material, such as nylon, and typically has a thickness ranging from about 0.1 mm to about 2 mm.
As depicted, separator (60) is disposed in spaced apart, parallel relationship with electrodes (20, 30, 40) and is positioned between charging electrode (30) and metal anode (20). A gap for the electrolyte is provided on each side of separator (60). Alternatively, but not illustrated, when the separator is radiation-grafted onto one of the three electrodes, the electrode provides a support for the separator, and thus no gap exists between the separator and the electrode on which it is formed.
In accordance with the present invention, separator (60) functions, in part, to prevent shorting between air cathode (40) and metal anode (20).
Separator (60) comprises an ion-conducting, polymer-based solid gel membrane. This membrane comprises, in part, a support material or substrate, which is preferably a woven or nonwoven fabric, such as a polyolefin, polyvinyl alcohol, cellulose, or a polyamide, such as nylon. Alternatively, the 1o substrate/support may be the anode, charging electrode, or cathode (not illustrated).
A polymer-based gel having an ionic species contained within a solution phase thereof, which has been formed on the support material, completes separator (60).
More particularly, the polymer-based gel or film portion of the membrane includes an electrolyte in solution with the polymerization product of a polymerization initiator and one or more water-soluble ethylenically unsaturated amide or acid monomers, preferably methylenebisacrylamide, acrylamide, methacrylic acid, acrylic acid, 1-vinyl-2-pyrrolidinone, or combinations thereof. Other suitable monomers are listed below.
Prior to initiating the polymerization, the ingredients are dissolved in water, 2o and, in this embodiment, an aqueous hydroxide electrolyte solution (e.g.
KOH) having a hydroxide ion concentration ranging from about 0.1 wt. % to about 55 wt.%, but preferably about 37.5 wt. %, is added to produce the ionic species.
Suitable hydroxide electrolytes include, for example, potassium hydroxide, sodium hydroxide, lithium hydroxide, or combinations thereof. Alternatively, the ionic species may come from a neutral aqueous solution prepared from combinations of ammonium chloride, potassium sulfate, and/or sodium chloride. The electrolyte is added to the monomer solution prior to polymerization and remains in solution after the polymerization.
Also prior to the polymerization process, an ionic polymer, such as polysulfone (anionic) or poly(sodium-4-styrenesulfonate) is added to the monomer solution as a reinforcing element. The addition of the reinforcing element enhances the ionic conductivity and mechanical strength of the separator. Optionally, a crosslinking agent, such as methylenebisacrylamide or ethylenebisacrylamide may also be employed during the polymerization. Other crosslinkers and reinforcing element polymers may be used instead, such as one of those listed below, as would be obvious to those of skill.
To form separator (60) depicted in FIG. 6 (and indicated as reference to number (61) in FIG. 7 below), a piece of woven or nonwoven fabric, such as nylon (i.e. a polyamide), for example, is provided as the support, and the selected fabric is soaked in the monomer solution. The solution-coated fabric is cooled, and ammonium persulfate, for example, is optionally added as a polymerization initiator.
Other suitable chemical initiators include alkali metal persulfates and peroxides.
The fabric coated with the monomer film solution is then placed between glass and polyethylene teraphthalate (PET) film. After heating, the monomer solution is further polymerized by irradiating the "sandwiched" plastic/monomer film with UV
light, for example, and the polymer-based gel membrane or separator is produced.
The hydroxide ion (or other ions) remains in solution after the polymerization.
2o Thus, polymerization is preferably carried out at an elevated temperature (up to 130° C) using a chemical polymerization initiator and radiation.
However, polymerization to form the polymer-based gel can also be carried out by one of these alternative methods: heating and using a chemical polymerization initiator (no radiation) or heating plus radiation (no chemical initiator); or radiation at room temperature, depending on the strength of the radiation.
Separator (60), thus formed, has a thickness that is typically about 0.3 mm.
Preferably, the separator will be as thin as 0.1 mm. However, the invention is not limited to separators ranging in thickness from 0.1 to 0.3 mm. It will be obvious to those of skill whether a particular separator is too thick or too thin, based on its effectiveness in a particular application. The separator provides a source of hydroxide (or other) ions and is highly conductive to that ionic species.
It is important to note that unexpectedly high ionic conductivities (up to 0.36 S/cm thus far), but not previously observed in prior art systems have been achieved using the solid gel membrane separator in the rechargeable electrochemical cells of the present invention. This is, in part, because the electrolyte is added to the monomer solution prior to polymerization. After polymerization, the ionic species remains in solution as part of the polymer-based solid gel, which is disposed to on the support or fabric to form the polymer-based solid gel membrane separator (60) (or (61 ) in FIG. 7). This solid gel membrane or separator also prevents penetration of dendritic metal through the separator and therefore protects the negative electrode from dendrite formation during charging. Furthermore, the solid gel separator also prevents destruction of the cell by preventing diffusion of the metal oxidation product into the electrolyte solution.
FIG. 7 shows rechargeable electrochemical cell (110) of the present invention wherein the cathode and charging electrode form single bifunctional electrode (41), i.e. the electrode is used both as the positive electrode and for charging the battery. Optionally, liquid (aqueous) electrolyte (81) may also be 2o included within the housing of the cell. Separator (61) is disposed between anode (21) and bifunctional electrode (41). Electrochemical cell 110 also includes housing (91 ).
This dual electrode/separator configuration depicted in FIG. 7 may be used for several different types of rechargeable battery systems. For example, anode (21 ) may be an oxidizable metal, such as one of those previously listed in connection with FIG. 6 (preferably zinc), and bifunctional electrode (41) may be the previously described air cathode. In another embodiment, anode (21) is zinc or zinc oxide, and bifunctional electrode (41 ) is nickel oxide, manganese dioxide, silver oxide, or WO 00/51198 PCT/fJS00/04881 cobalt oxide. Alternatively, anode (21 ) may be iron or cadmium, and single bifunctional electrode (41) is nickel oxide. In these systems, the ionic species contained in polymer-based gel membrane separator (61) preferably comes from one of the above-listed aqueous alkaline hydroxide solutions and associated hydroxide concentration. However, in the rechargeable metal/air cells of the present invention, a neutral membrane separator (61 ) can alternately be employed wherein the ionic species comes from one of the above-listed neutral aqueous solutions.
An acidic membrane may be used as separator (G 1 ) in acidic systems such as to in rechargeable lead-acid batteries wherein anode (21) is lead and bifunctional electrode (41) is lead oxide. In this embodiment, the ionic species contained in separator (61) comes from an aqueous solution of perchloric acid, sulfuric acid, hydrochloric acid, phosphoric acid, or combinations thereof.
In other rechargeable electrochemical cell configurations, not depicted, but mentioned above, the ion-conducting polymer-based solid gel may be grafted directly onto the anode, charging electrode, cathode, or bifunctional electrode, when one is used. In this case, support for the separator or membrane is provided by the electrode substrate on which the polymer-based solid gel is formed.
The shape of the electrolyte solution volume or housing, which is shown as 2o reference number (90) in FIG. 6 and (91) in FIG. 7, is not constrained to be square or rectangular. It can be circular, elliptical, polygonal, or any desired shape. In addition, the cell housing may be fabricated from any strong chemically inert insulation material, such as plastic conventionally used in electrochemical cells and alkaline batteries.
When in operation, conducting wires (not shown), usually copper strips, are adhered to exposed portions of the metal anode, charging electrode, and cathode and/or bifunctional electrode. These conducting wires are used to apply an external voltage to the cell to recharge the anode. An insulating epoxy is typically used to cover the exposed joints.
EXAMPLES
Preferred embodiments of the present invention are hereinafter described in more detail by means of the following examples that are provided by way of illustration and not by way of limitation. The reactants and reagents used in the reactions described below are readily available materials. Such materials can be conveniently prepared in accordance with conventional preparatory procedures or obtained from commercial sources.
to Example 1 The following procedure was used to prepare a strong polymer film for use in the present invention. 0.75 grams methylenebisacrylamide, 0.56 g acrylamide, 4.70 g methacrylic acid, and 0.25 g poly(sodium 4-styrenesulfonate) were dissolved in 10 milliliters water and then 20 ml 40% KOH was added to the resulting solution, which was maintained at room temperature. 0.05 g ammonium persulfate was then added to the solution. A piece of fabric was soaked in the resulting monomer solution and then sandwiched between a piece of glass and a piece of PET
transparent film. This was heated on a 75 ° C hotplate for 1 minute and then irradiated under strong UV light for 5 minutes, whereby a strong polymer film was 2o formed.
The resulting film is highly conductive of hydroxide ions, making it suitable for use in an alkaline hydrogen fuel cell. Here, the membrane film is sandwiched between an air cathode and a hydrogen anode, separating the air and hydrogen, while allowing the diffusion of hydroxide ions.
Example 2 In this example, a polymer based solid gel membrane was prepared in accordance with the principles of the invention and applied to the surface of a cathode. 0.75 g Methylenebisacrylamide, 0.56 g acrylamide, 4.70 g methacrylic acid, and 1.5 g polysulfone (anionic) were dissolved in 10 ml water and then 20 ml 40% KOH was added to the resulting solution, which was maintained at room temperature. 0.038 g ammonium persulfate dissolved in 1 ml water was added and the resulting solution was poured onto the surface of an air cathode. The cathode was then covered by a piece of PET film and heated on a 75 ° C hotplate for 1 minute and then irradiated under strong UV light, whereby a strong polymer film was formed.
This cathode may be used with an anode prepared as in Example 3, below, or it may be used directly with a plain metal sheet, such as zinc, aluminum, to cadmium, lithium, magnesium, or lead, in the formation of a corresponding metal/air fuel cell battery. Alternatively, the cathode on which the solid gel is grafted, as in Example 2, may form a separator/bifunctional electrode in a rechargeable electrochemical cell (metal/air) in accordance with the present invention, or it may be positioned next to the charging electrode in the rechargeable cell, as mentioned above.
Example 3 A polymer based ion conducting membrane was prepared and applied to the surface of an anode according to the principles of the present invention. 0.75 g methylenebisacrylamide, 1.5 g poly(sodium 4-styrenesulfonate), 5.18 g 1-vinyl-2o pyrrolidinone, and 3.36 g acrylic acid were dissolved in 30 ml NH4C1 and saturated aqueous solution, followed by the addition of 0.1 g ammonium persulfate.
The solution was spread onto the anode surface, and covered by a PET film and then irradiated under strong UV light, whereby a strong polymer film was formed for use as a separator grafted onto the anode. In a fuel cell, the separator/anode is positioned next to the cathode, and in a rechargeable electrochemical cell, it is positioned next to the charging electrode or next to a single bifunctional electrode, when one is employed.
Example 4 A polymer-based solid gel membrane was prepared according to the present invention and processed to form a proton conducting film. 6.4 g 70% perchloric acid, 0.75 g methylenebisacrylamide, 5.18 g acrylic acid, and 0.1 g potassium sulfite (reducing agent) were dissolved in 27 ml water and then 0.1 g ammonium persulfate was added to the solution. A piece of fabric was soaked in the resulting monomer solution and then sandwiched between a piece of glass and a piece of PET
transparent film. This was heated on an 85°C hotplate for 1 minute and then irradiated under strong UV light for 8 minutes, whereby a strong polymer film was to formed.
The resulting film is highly conductive of protons (hydrogen ions), making it suitable for use in a hydrogen fizel cell or for use as a separator in an acidic rechargeable electrochemical cell, such as in a rechargeable lead-acid battery. In a hydrogen fuel cell, the membrane film is sandwiched between an air cathode and a hydrogen anode, separating the air and hydrogen while allowing the diffusion of hydrogen ions.
Example 5 The principles of the present invention may also be applied to electrochromic devices. For example, one or several electrochromic materials are 2o dissolved in an aqueous monomer solution which is then applied to an electrode substrate. The substrate may be comprised of such materials as for example, platinum, gold, conductive glass, e.g., indium-tin oxide glass, or other electro-conductive materials. The solution is polymerized according to either of the above methods wherein the ECM's are contained within the polymer membrane formed on the surface of the substrate. Two such modified electrodes, containing the same or different ECM's, are used in the electrochromic device with one acting as the anode and the other as the cathode. The electrodes may be packed together as a complete display device or they may be separated by a liquid or solid electrolyte.
Example 6 The following procedure was used to prepare a strong polymer film for use as a separator in a rechargeable electrochemical cell. One and a half grams (1.5 g) polysulfone (anionic), 0.75 g methylenebisacrylamide, 0.56 g acrylamide, and 4.70 g methacrylic acid was dissolved in 10 mL water, and maintained at room temperature. Twenty (20) mL 50% KOH was added to the resulting solution. A
piece of nylon fabric commercially available from Frendenberg Nonwovens as FS2213E was then soaked in the monomer solution. The solution was placed in an ice bath, and 0.10 g ammonium persulfate was added to the solution. The separator to was then taken out of the solution and sandwiched between transparent PET
film and glass. The 'sandwiched' separator was then heated on a hot plate at 90 ° C for 20 minutes on each side, then irradiated under strong UV light for 7 minutes on each side. The conductivity of the resulting membrane was 0.11 S/cm.
Examples of other monomers that may be used in the formation of a solid gel membrane and separator of the invention include any water-soluble ethylenically unsaturated amides or acids, including, but not limited to, N-isopropylacrylamide, fumaramide, fumaric acid, N, N-dimethylacrylamide, 3,3-dimethylacrylic acid, and the sodium salt of vinylsulfonic acid.
Other cross-linking agents include, for example, any water-soluble N,N'-alkylidene-bis(ethylenically unsaturated amide).
Examples of polymers other than poly(sodium 4-styrenesulfonate) that may be used as reinforcing elements within the solid gel electrolyte may include any water-soluble or water-swellable polymers, such as, for example, carboxymethyl cellulose, polysulfone (anionic), sodium salt of poly(styrenesulfonic acid-co-malefic acid), and corn starch.
Suitable fabrics onto which the monomer solution may be applied include, for example, woven or non-woven fabrics such as polyolefins, polyamides, polyvinyl alcohol, and cellulose.
With regard to initiation of the polymerization reaction chemical initiators such as, ammonium persulfate, alkali metal persulfates or peroxides may optionally be used in combination with radical generating methods such as radiation, including for example, ultraviolet light, X-ray, 'y-ray, and the like. However, the chemical initiators need not be added if the radiation alone is suf~'iciently powerful to begin the polymerization. As stated above, the polymerization may be conducted at temperatures ranging from room temperature up to about 130° C.
This invention has been described in terms of specific embodiments, set forth in detail. It should be understood, however, that these embodiments are to presented by way of illustration only, and that the invention is not necessarily limited thereto. The principles of the present invention may, for example, also be applied in the preparation of a solid gel membrane for use in such other electrochemical systems as for example, Ni/Cd and Zn/Mn02 cells. Additionally, other monomers, polymers, chemical polymerization initiators, reducing agents, and the like, other than those particularly disclosed herein might be used.
Modifications and variations in any given material or process step will be readily apparent to those skilled in the art without departing from the true spirit and scope of the following claims, and all such modifications and variations are intended to be included within the scope of the present invention.
Field of the Invention This invention relates generally to solid gel membranes, and more particularly to an ionic-conducting polymer-based solid gel membrane.
Background of the Invention Electrochemical devices generally incorporate an electrolyte source to provide the anions or canons necessary to produce an electrochemical reaction.
A
zinc/air system, for example, requires the diffusion of hydroxide anions, and typically will incorporate an aqueous potassium hydroxide solution as the to electrolyte. The lifetime of this battery is however, limited for several reasons.
First, the naked zinc anode is corroded by both the aqueous electrolyte and air Second, the air channels of the air cathode gradually become blocked by water from the electrolyte solution and third, the electrolyte solution becomes contaminated with zinc oxidation product that diffuses from the anode.
Various methods have been used to address the many problems associated with the use of aqueous electrolytes in zinc anode based systems such as zinc/air fuel cells. Additives, for example, have been introduced into the electrolyte solution to extend its lifetime and to protect the anode from corrosion. United States Patent 4,118,551 discloses the use of inorganic additives such as mercury, indium, tin, lead, lead compounds, cadmium or thallium oxide to reduce corrosion of a zinc electrode. Many of these additives however, are expensive and more significantly, are very toxic. United States Patent 4,378,414 discloses the use of a mufti-layer separator between the positive and negative electrodes to reduce corrosion of the anode and contamination of the electrolyte by zinc oxidation products. In addition, hydrophobic materials have been introduced into zinc/air devices to prevent water permeation into the air channels of the cathode. Introduction of hydrophobic materials is however, a difficult process and may result in decreased performance of the cathode.
In addition to zinc/air systems, other metal/air systems, such as aluminum/air, lithium/air, cadmium/air, magnesium/air, and iron/air systems, also have the potential for many different applications due to their theoretically high ampere-hour capacity, voltage, and specific energy. In actual practice however, these very promising theoretical values are greatly reduced due to the corrosion of the metal anode in the electrolyte.
A solid state hydroxide conductive electrolyte polybenzimidazole ("PBI") 1o film is disclosed in United States Patent 5,688,613 and comprises a polymeric support structure having an electrolyte active species dispersed therein, wherein the polymer structure is in intimate contact with both the anode and the cathode.
This PBI film, however, does not absorb water and therefore, does not hold water within the membrane, causing it to dry out quickly.
United States Patent 3,871,918 discloses an electrochemical cell embodying an electrode of zinc powder granules suspended in a gel comprised of methylenebisacrylamide, acrylic acid and acrylamide. Potassium hydroxide serves as the electrolyte, and is contained within the gel.
With regard to devices that rely on the conduction of cations, while there 2o has been a significant amount of research in this area, most proton conducting membranes are very expensive to produce and typically do not function at room temperature. In the 1970's for example, a fully fluorinated polymer membrane, NAFION~ (DuPont, Wilmington, DE USA) was introduced and has served as the basis from which subsequent proton conducting membranes have evolved.
United States Patent 5,468,574 discloses a proton conductive membrane that is characterized as a highly sulfonated polymeric membrane composed of block copolymers of sulfonated polystyrene, ethylene and butylene blocks. In 1997, NASA's Jet Propulsion Laboratory disclosed the development of an improved proton conductive membrane composed of sulfonated poly(ether ether ketone), commonly known as H-SPEEK.
The separator in a cell or battery physically separates and electrically insulates electrodes of different polarity. While serving as a barrier to the transport of active materials of the different electrodes, a separator should also provide ionic conduction. Good ionic conductivity is necessary to ensure that an electrochemical cell/battery is capable of delivering usable amounts of power for a given application.
In a rechargeable electrochemical cell, a separator is also used to prevent short circuiting caused by metal dendrite penetration during recharging. For to example, in rechargeable zinc/air cells, zinc on the surface of the negative zinc electrode (anode) is dissolved as zincate ion into the electrolyte solution during discharge. Then, during the charge, when the charging current is typically below 20 mA/cm2, depending on the particular anode used, the zincate ion forms dendritic zinc, which is needle-like and grows from the negative electrode toward the charging electrode. Unfortunately, these needle-like structures can pierce through conventional separators causing an internal short circuit. The service life of the cell is consequently terminated. In addition to preventing dendrite penetration, the separator must allow for the exchange of electrolytic ions during both discharging and charging of the cell.
2o The most commonly used separators in rechargeable cells are porous insulator films of polyolefins, polyvinyl alcohol (PVA), nylon, or cellophane Acrylic compounds may also be radiation-grafted onto these separators to make them more wettable and permeable to the electrolyte. Although much work has been done to improve the performance of separators, dendrite penetration problems are frequently encountered with these and other conventional separators, as well as problems involving diffusion of reaction products such as the metal oxide to remaining parts of the cell.
With conventional separators, controlling the pore size of the separator is the only effective way to avoid dendrite penetration and prevent product diffusion.
By doing this, however, the ionic conductivity of the separator is also greatly reduced. This creates a bottleneck for high charging-discharging current density operations, important considerations for use in some applications, such as in electrical vehicles.
United States Patent 5,549,988 discloses an electrolyte system separator disposed between the cathode and anode of a rechargeable electrochemical battery.
The electrolyte system includes a polymer matrix prepared from polyacrylic acid or to derivatives thereof. An electrolyte species, such as KOH or HzS04, is then added to the polymer matrix to complete the system. However, as reported in the patent, the measured ionic conductivities of the disclosed electrolyte-polymer films are low, ranging from 0.012 S/cm to 0.066 S/cm. Although these conductivities are acceptable for some applications, they are inadequate for other high rate operations including electrical vehicles.
An electrochemical reaction is also involved in the function of electrochromic devices (ECD's). Electrochromism is broadly defined as a reversible optical absorption change induced in a material by an electrochemical redox process. Typically, an electrochromic device contains two different electrochromic materials (ECM's) having complementary properties; the first is generally reduced, undergoing a color (1)-to-color (2) transition during reduction, while the second material is oxidized, undergoing a similar transition upon the loss of electrons.
Basically, there are two types of electrochromic devices, depending upon the location of the electrochromic materials within the device. In a thin-film type device, the two ECM's are coated onto the two electrodes and remain there during the redox coloration process. In a solution-phase device, both ECM's are dissolved in an electrolyte solution and remain their during the coloration cycle. The solution-phase device is typically more reliable and has a longer lifetime, however, in order to maintain the colored state, an external power source must be continuously applied. As the thin-film type device does not need an external power source to maintain its colored state, power consumption is greatly reduced, making this an advantage for such energy-saving applications as smart windows. The drawback of the thin-film type device is that it has a short lifetime. After a certain number of cycles, ECM films can lose contact with the electrode, or they may no longer be capable of phase change and the device expires.
With regard to solution-phase devices, United States Patent 5,128,799, for to example, discloses a method of reducing the current required to maintain the colored state which involves the addition of gel into the device. While reducing energy consumption however, the addition of the gel into the device also greatly reduces the switching speed of the device. With regard to thin-film devices, attempts to extend the lifetime of the device have included changes to the crystal structure of the film. While such changes have increased the lifetime of thin-film devices to an extent, the typical lifetime of such devices is still not satisfactory.
The foregoing problems thus present major obstacles to the successful development and commercialization of fuel cell technology, a green energy source, and of electrochromic devices such as smart windows and flat panel displays, which 2o have several energy-saving, decorative, and information display applications. With respect to the problems associated with rechargeable electrochemical cells, it is clear that there is a great need for a separator that can provide improved ionic conductivity while providing an effective barrier against the penetration of metal dendrites and the diffusion of reaction products.
Summary of the Invention The present invention provides polymer-based solid gel membranes that contain ionic species within the gel's solution phase and that are highly conductive to anions or canons. In accordance with the principles of the invention, solid gel membranes may be produced for use in such power sources as, for example, metal/air (e.g. zinc/air, cadmium/air, lithium/air, magnesium/air, iron/air, and aluminum/air), Zn/Ni, Zn/IVInOz, Zn/AgO, Fe/Ni, lead-acid, Ni/Cd, and hydrogen fuel cells, as well as for use in electrochromic devices, such as smart windows and flat panel displays. Additionally, the instant polymeric solid gel membranes are useful in rechargeable electrochemical cells, wherein the solid gel membrane is employed as a separator between the charging electrode and the anode.
With respect to a zinc/air fuel cell battery, for example, conductive membranes of the present invention may be used to protect the anode, as well as the to cathode. In such a system, the ionic species is contained within the solution phase of the solid gel membrane, allowing it to behave as a liquid electrolyte without the disadvantages. The gel membrane protects the anode from corrosion (by the electrolyte as well as by air) and prevents zinc oxidation product from the anode from contaminating the electrolyte. With regard to the cathode, as the membrane is itself a solid, there is no water to block the air channels of the cathode. As a result, the system will have an extended lifetime.
As used herein, the term "anode" refers to and is interchangeable with the term "negative electrode". Likewise, "cathode" refers to and is interchangeable with the term "positive electrode".
2o The present invention also includes rechargeable electrochemical cells that use the solid gel membrane as a separator between the anode and charging electrode. Such a separator provides many advantages that conventional separators lack. For example, it provides a smooth impenetrable surface that allows the exchange of ions for both discharging and charging of the cell while preventing fast dendrite penetration and the diffusion of reaction products such as metal oxide to remaining parts of the cell. Furthermore, the measured ionic conductivities of the present solid gel membranes are much higher than those of prior art solid electrolytes or electrolyte-polymer films. For example, the observed conductivity values for the present separators are surprisingly about 0.10 S/cm or more.
Even more surprisingly, ionic conductivities as high as 0.36 S/cm have been measured, and it is possible that higher values still may be observed. Thus, these unique and unprecedented properties distinguish the separator of the present invention from previous designs that merely trap dendrite growth and slow penetration.
Accordingly, the principles of the present invention relate, in one aspect, to a rechargeable electrochemical cell comprising a separator, an anode, a cathode, and a charging electrode. Optionally, a liquid electrolyte, such as one of those mentioned herein and/or commonly known by those of skill in the art, may also be to included in the rechargeable cell. The liquid (aqueous) electrolyte contacts the separator, each electrode, and a porous spacer, if employed. The separator comprises an ion-conducting polymer-based solid gel membrane which includes a support onto which a polymer-based gel having an ionic species contained within a solution phase thereof is formed. The support may be a woven or nonwoven fabric or one of the electrodes.
The polymer-based gel comprises a polymerization product of one or more monomers selected from the group of water soluble ethylenically unsaturated amides and acids. The polymer-based gel also includes a water soluble or water swellable polymer, which acts as a reinforcing element. In addition, a chemical 2o polymerization initiator (listed below) may optionally be included. The ionic species is added to a solution containing the polymerization initiator (if used), the monomer(s), and the reinforcing element prior to polymerization, and it remains embedded in the polymer gel after the polymerization.
Polymerization is carried out at a temperature ranging from room temperature to about 130° C, but preferably at an elevated temperature ranging from about 75° to about 100° C. Higher heating temperatures, such as those ranging from about 95° to about 100° C, provide a stiffer polymer surface, which is a desirable property in rechargeable cell applications. Optionally, the polymerization may be carried out using radiation in conjunction with heating.
Alternatively, the polymerization may be performed using radiation alone without raising the temperature of the ingredients, depending on the strength of the radiation. Examples of radiation types useful in the polymerization reaction include, but are not limited to, ultraviolet light, y-rays or x-rays.
In the rechargeable cell, the cathode and charging electrode may be a single bifunctional electrode or may be individual and separate electrodes. The separator is positioned between the anode and charging electrode. In alkaline systems, the hydroxide ionic species typically comes from an aqueous alkaline solution of to potassium hydroxide, sodium hydroxide, lithium hydroxide, or combinations thereof. Preferably in a potassium hydroxide solution, for example, the base has a concentration ranging from about 0.1 wt. % to about 55 wt. %, and most preferably about 37.5 wt. %. In acidic systems, the proton comes from an aqueous acidic electrolyte solution, such as a solution of perchloric acid, sulfuric acid, hydrochloric acid, or combinations thereof. The concentration of perchloric acid, for example, preferably ranges from about 0.5 wt. % to about 70 wt. %, and most preferably about 13.4 wt. %. The membrane separator may also be used in neutral systems, wherein the ionic species comes from a saturated aqueous neutral solution of ammonium chloride and potassium sulfate; a saturated solution of ammonium 2o chloride, potassium sulfate, and sodium chloride; or a saturated neutral solution of potassium sulfate and ammonium chloride.
When the cathode and charging electrode are individual and separate electrodes, the charging electrode is positioned between the separator and cathode, and a porous spacer is optionally positioned between the charging electrode and cathode.
In another aspect, the invention is a rechargeable electrochemical cell comprising a separator, a metal anode (preferably zinc), an air cathode, and a charging electrode. In this system, the separator is a hydroxide conducting polymer-based solid gel membrane comprising a support onto which a polymer-based gel having a hydroxide species contained within a solution phase thereof is formed. The polymer-based gel comprises polysulfone as a reinforcing element and a polymerization product of a polymerization initiator, methylenebisacrylamide, acrylamide, and methacrylic acid. The hydroxide species comes from an aqueous alkaline solution (ranging from about 0.1 wt. % to about 55 wt. % potassium hydroxide, sodium hydroxide, lithium hydroxide, or a mixture thereof), which is added to the polymerization initiator, methylenebisacrylamide, acrylamide, methacrylic acid, and polysulfone prior to polymerization. The air cathode and to charging electrode may be a single bifunctional electrode or may be individual and separate electrodes. The separator is positioned between the metal anode and charging electrode. The ionic conductivity of the separator typically ranges from about 0.10 S/cm to about 0.36 S/cm, but may be higher.
In another aspect, the present invention is an electrochemical cell comprising first and second electrodes and one or more polymer based solid gel membranes disposed there between. In one embodiment, the electrochemical cell is a zinc/air cell having an anode protective solid gel membrane and a hydroxide conducting solid gel membrane disposed between the zinc anode and the air cathode. In another embodiment of a zinc/air system, both the anode and cathode are protected 2o by a solid gel membrane of the present invention, and an aqueous electrolyte is disposed between the two.
In a further embodiment of this aspect of the invention, the electrochemical cell is an aluminum/air cell, wherein a hydroxide conductive solid gel membrane is applied to the aluminum anode to protect it from corrosion.
In yet a further embodiment of this aspect of the invention, the electrochemical cell is an aluminum/air cell, wherein a hydroxide conductive solid gel membrane is disposed between the aluminum anode and the air cathode.
Accordingly, the principles of the present invention also provide a method of inhibiting corrosion of a metal anode in a metal/air fuel cell system comprised of a metal anode and an air cathode. The method comprises disposing one or more polymer based solid gel membranes between said anode and said cathode.
In yet a further embodiment of the invention, the electrochemical cell is a proton or hydroxide conducting power source, such as a hydrogen fuel cell system.
In this embodiment, a proton or hydroxide conductive solid gel membrane may be sandwiched between the hydrogen anode and the air cathode, thus separating the hydrogen and the air, while allowing the dii~'usion of proton or hydroxide ions. This to embodiment provides several advantages over prior art proton conducting membranes in that the solid gel membranes of the present invention are much easier and less expensive to produce than earlier membranes and, more importantly, unlike previous membranes, the solid gel membranes of the present invention will function efficiently at room temperature.
15 The principles of the present invention may also be applied to electrochromic devices. Here, the electrochromic materials of the device are contained within solid gel membranes, thus providing the device with the reliability and long lifetime associated with solution phase EC systems, and also the energy-saving memory properties associated with thin-film EC systems.
2o Accordingly, yet another embodiment of the present invention is an electrochromic device wherein electrochromic materials are contained within polymer based solid gel membranes. Typically, such a device will involve two electrode substrates and electrochromic materials contained within solid gel membranes sandwiched there between. The device may optionally include an 25 aqueous or a solid electrolyte disposed between the solid gel membranes.
The electrode substrates may be comprised of such materials as, for example, platinum, gold, conductive glass, such as indium-tin oxide glass, and the like.
BRIEF DESCRIPTION OF THE DRAWINGS
Numerous other advantages and features of the present invention will become readily apparent from the following detailed description of preferred embodiments when read in conjunction with the accompanying drawings, wherein:
FIG. 1 is a schematic depiction of a zinc/air fuel cell incorporating an anode protective membrane and a hydroxide conducting membrane of the present invention;
FIG. 2 is a schematic depiction of another embodiment of a zinc/air fuel cell incorporating both an anode and a cathode protective membrane of the present 1o invention;
FIG. 3 is a schematic depiction of an aluminum/air fuel cell incorporating a hydroxide conductive membrane of the present invention;
FIG. 4 is a schematic depiction of a hydrogen/air fuel cell incorporating a proton or hydroxide conductive membrane of the present invention;
15 FIG. 5 is a schematic depiction of an electrochromic device wherein the electrochromic materials are contained within membranes of the present invention;
FIG. 6 is a schematic depiction of a rechargeable metal/air battery having three electrodes, a porous spacer, and a solid gel membrane incorporated as a separator in accordance with the present invention; and 2o FIG. 7 is a schematic depiction of a rechargeable metal/air battery having an anode, a bifunctional electrode, and a solid gel membrane incorporated as a separator in accordance with the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring now to the drawings, FIG. 1 depicts a typical zinc/air fuel cell, 25 wherein two polymer-based solid gel membranes (1, 2) are disposed between the zinc anode (3) and the air cathode (4). The first is an anode protective membrane (1) and the second is a hydroxide conductive membrane (2). The membranes are not only the source of ionic species, and are highly conductive to that species, but they also provide a protective layer to the electrodes to prevent the usual sources of cell destruction. The membranes prevent diffusion of zinc oxidation product into the electrolyte solution phase, they prevent corrosion of the zinc anode by either the electrolyte solution or air, and they prevent blockage of the cathode air channels by water from the electrolyte solution. The zinc/air system of FIG. 2 includes a protective and conductive solid gel membrane (5, 6) on the surface of the zinc anode (3) and the air cathode (4), and an aqueous electrolyte (7) between the two.
Referring now to FIG. 3, an aluminum/air fuel cell system incorporating a solid gel hydroxide conductive membrane (8) between the aluminum anode (9) and to the air cathode (10) is depicted. As in the zinc/air system, the solid gel membrane of this embodiment serves to prevent the corrosion problems associated with the use of pure liquid electrolyte and also serves as the ionic conducting media.
As illustrated in Figure 4, when applied to the art of hydrogen fuel cells, the principles of the present invention provide a proton or hydroxide conductive membrane that is easy to produce, much less expensive than existing proton conductive membranes and that functions well at room temperature. Because the actual conducting media remains in aqueous solution within the polymer gel backbone, the conductivity of the membrane is comparable to that of liquid electrolytes, which at room temperature is significantly high. In this embodiment of 2o the invention, a proton or hydroxide conductive solid gel membrane ( 11 ) i s sandwiched between the hydrogen anode (12) and the air cathode (13), thereby separating the hydrogen and the air.
As shown in FIG. 5, the principles of the present invention may also be applied to electrochromic systems. Here, the electrochromic materials are dispersed within the solution phase of the polymer gel backbone of a solid gel membrane.
Since the ECM's are in solution, the device exhibits the superior reliability and long life of a solution phase device and in addition, because the ECM's are physically confined, they can not diffuse into the device's bulk electrolyte and the device therefore also exhibits the superior memory of a thin-film type device. As shown, the device includes two electrode substrates (14, 15) having solid gel membrane encapsulated electrochromic materials (16, 17) there between. As illustrated, the device optionally includes an aqueous or solid electrolyte (18) disposed between solid gel membranes ( 16, 17).
Referring to FIG. 6, there is illustrated therein a rechargeable electrochemical cell (100) fabricated from three electrode assemblies, (20, 30, 40) and contained within housing (90). Electrode (20) represents the negative electrode or metal anode; electrode (40) is the positive electrode, i.e. air cathode;
and to electrode (30) is a porous charging electrode. In this embodiment, cathode (40) and charging electrode (30) are separate electrodes, and charging electrode (30) is positioned between cathode (40) and the solid gel separator. As shown in the drawing, the three electrodes (20, 30, 40) are disposed in spaced apart, parallel relationships with one another. Rechargeable electrochemical cell (100) optionally includes liquid (aqueous) electrolyte (80) in contact with each electrode, separator (60), and porous spacer (50) (when employed) typically by immersion.
Metal anode (20) is made of an oxidizable metal, preferably zinc, cadmium, lithium, magnesium, iron, or aluminum, but metal anode (20) is most preferably zinc. Air cathode (40) preferably has a current density of at least 200 mA/cmz. An 2o air cathode suitable for use in the present invention is disclosed in copending, commonly assigned U. S. Patent Application Ser. No. 09/415,449 entitled ELECTROCHEMICAL ELECTRODE FOR FUEL CELL, filed on October 8, 1999. This exemplary air cathode includes a current collector comprising a porous metal foam substrate, which is formed with a network of inteconnected pores.
An active layer, preferably comprising a carbon/polymer blend, and a hydrophobic microporous gas diffusion layer are both disposed on one or more surfaces of the metal foam substrate. The microporous layer is a plastic material such as a fluoropolymer (i.e., PTFE). The cathode also includes a particulate microstructure reinforced by relatively strong bonding provided by sintering a polymeric binder within the three-dimensional interconnected porosity of the metal foam substrate.
The reactive layers are preferably fabricated from the same material as the binder.
It should be noted, however, that other air cathodes may instead be used, depending on the performance capabilities thereof, as will be obvious to those of skill.
The present invention is in no way limited to use of the exemplary cathode described herein.
As shown in FIG. 6, porous charging electrode (30) is positioned in parallel relationship between metal anode (20) and air cathode (40). Any inert conductive to porous material may be used to form porous charging electrode (30).
Examples include, but are not limited to platinum, nickel, nickel oxide, perovskite and its derivatives, carbon, and palladium. In addition, apertures or holes may be drilled into charging electrode (30) to aid with the passage of ions. It is important that the electrodes do not physically contact each other, and a distance therebetween sufFicient to form a gap for the electrolyte must be provided.
In addition; it is sometimes desirable to position porous spacer (50) between charging electrode (30) and air cathode (40) as a means of ensuring sufficient distance between the two electrodes. When porous spacer (50) is included in rechargeable electrochemical cell (100), a gap is formed for the electrolyte on each 2o side of porous spacer (50 ) and each electrode (30) and (40). However, the invention is not limited to structures which include porous spacer (50). Any means of preventing physical contact between the two electrodes may be employed, such as anchoring the electrodes apart in the housing. However, when porous spacer (50) is used, it is typically made of a porous plastic material, such as nylon, and typically has a thickness ranging from about 0.1 mm to about 2 mm.
As depicted, separator (60) is disposed in spaced apart, parallel relationship with electrodes (20, 30, 40) and is positioned between charging electrode (30) and metal anode (20). A gap for the electrolyte is provided on each side of separator (60). Alternatively, but not illustrated, when the separator is radiation-grafted onto one of the three electrodes, the electrode provides a support for the separator, and thus no gap exists between the separator and the electrode on which it is formed.
In accordance with the present invention, separator (60) functions, in part, to prevent shorting between air cathode (40) and metal anode (20).
Separator (60) comprises an ion-conducting, polymer-based solid gel membrane. This membrane comprises, in part, a support material or substrate, which is preferably a woven or nonwoven fabric, such as a polyolefin, polyvinyl alcohol, cellulose, or a polyamide, such as nylon. Alternatively, the 1o substrate/support may be the anode, charging electrode, or cathode (not illustrated).
A polymer-based gel having an ionic species contained within a solution phase thereof, which has been formed on the support material, completes separator (60).
More particularly, the polymer-based gel or film portion of the membrane includes an electrolyte in solution with the polymerization product of a polymerization initiator and one or more water-soluble ethylenically unsaturated amide or acid monomers, preferably methylenebisacrylamide, acrylamide, methacrylic acid, acrylic acid, 1-vinyl-2-pyrrolidinone, or combinations thereof. Other suitable monomers are listed below.
Prior to initiating the polymerization, the ingredients are dissolved in water, 2o and, in this embodiment, an aqueous hydroxide electrolyte solution (e.g.
KOH) having a hydroxide ion concentration ranging from about 0.1 wt. % to about 55 wt.%, but preferably about 37.5 wt. %, is added to produce the ionic species.
Suitable hydroxide electrolytes include, for example, potassium hydroxide, sodium hydroxide, lithium hydroxide, or combinations thereof. Alternatively, the ionic species may come from a neutral aqueous solution prepared from combinations of ammonium chloride, potassium sulfate, and/or sodium chloride. The electrolyte is added to the monomer solution prior to polymerization and remains in solution after the polymerization.
Also prior to the polymerization process, an ionic polymer, such as polysulfone (anionic) or poly(sodium-4-styrenesulfonate) is added to the monomer solution as a reinforcing element. The addition of the reinforcing element enhances the ionic conductivity and mechanical strength of the separator. Optionally, a crosslinking agent, such as methylenebisacrylamide or ethylenebisacrylamide may also be employed during the polymerization. Other crosslinkers and reinforcing element polymers may be used instead, such as one of those listed below, as would be obvious to those of skill.
To form separator (60) depicted in FIG. 6 (and indicated as reference to number (61) in FIG. 7 below), a piece of woven or nonwoven fabric, such as nylon (i.e. a polyamide), for example, is provided as the support, and the selected fabric is soaked in the monomer solution. The solution-coated fabric is cooled, and ammonium persulfate, for example, is optionally added as a polymerization initiator.
Other suitable chemical initiators include alkali metal persulfates and peroxides.
The fabric coated with the monomer film solution is then placed between glass and polyethylene teraphthalate (PET) film. After heating, the monomer solution is further polymerized by irradiating the "sandwiched" plastic/monomer film with UV
light, for example, and the polymer-based gel membrane or separator is produced.
The hydroxide ion (or other ions) remains in solution after the polymerization.
2o Thus, polymerization is preferably carried out at an elevated temperature (up to 130° C) using a chemical polymerization initiator and radiation.
However, polymerization to form the polymer-based gel can also be carried out by one of these alternative methods: heating and using a chemical polymerization initiator (no radiation) or heating plus radiation (no chemical initiator); or radiation at room temperature, depending on the strength of the radiation.
Separator (60), thus formed, has a thickness that is typically about 0.3 mm.
Preferably, the separator will be as thin as 0.1 mm. However, the invention is not limited to separators ranging in thickness from 0.1 to 0.3 mm. It will be obvious to those of skill whether a particular separator is too thick or too thin, based on its effectiveness in a particular application. The separator provides a source of hydroxide (or other) ions and is highly conductive to that ionic species.
It is important to note that unexpectedly high ionic conductivities (up to 0.36 S/cm thus far), but not previously observed in prior art systems have been achieved using the solid gel membrane separator in the rechargeable electrochemical cells of the present invention. This is, in part, because the electrolyte is added to the monomer solution prior to polymerization. After polymerization, the ionic species remains in solution as part of the polymer-based solid gel, which is disposed to on the support or fabric to form the polymer-based solid gel membrane separator (60) (or (61 ) in FIG. 7). This solid gel membrane or separator also prevents penetration of dendritic metal through the separator and therefore protects the negative electrode from dendrite formation during charging. Furthermore, the solid gel separator also prevents destruction of the cell by preventing diffusion of the metal oxidation product into the electrolyte solution.
FIG. 7 shows rechargeable electrochemical cell (110) of the present invention wherein the cathode and charging electrode form single bifunctional electrode (41), i.e. the electrode is used both as the positive electrode and for charging the battery. Optionally, liquid (aqueous) electrolyte (81) may also be 2o included within the housing of the cell. Separator (61) is disposed between anode (21) and bifunctional electrode (41). Electrochemical cell 110 also includes housing (91 ).
This dual electrode/separator configuration depicted in FIG. 7 may be used for several different types of rechargeable battery systems. For example, anode (21 ) may be an oxidizable metal, such as one of those previously listed in connection with FIG. 6 (preferably zinc), and bifunctional electrode (41) may be the previously described air cathode. In another embodiment, anode (21) is zinc or zinc oxide, and bifunctional electrode (41 ) is nickel oxide, manganese dioxide, silver oxide, or WO 00/51198 PCT/fJS00/04881 cobalt oxide. Alternatively, anode (21 ) may be iron or cadmium, and single bifunctional electrode (41) is nickel oxide. In these systems, the ionic species contained in polymer-based gel membrane separator (61) preferably comes from one of the above-listed aqueous alkaline hydroxide solutions and associated hydroxide concentration. However, in the rechargeable metal/air cells of the present invention, a neutral membrane separator (61 ) can alternately be employed wherein the ionic species comes from one of the above-listed neutral aqueous solutions.
An acidic membrane may be used as separator (G 1 ) in acidic systems such as to in rechargeable lead-acid batteries wherein anode (21) is lead and bifunctional electrode (41) is lead oxide. In this embodiment, the ionic species contained in separator (61) comes from an aqueous solution of perchloric acid, sulfuric acid, hydrochloric acid, phosphoric acid, or combinations thereof.
In other rechargeable electrochemical cell configurations, not depicted, but mentioned above, the ion-conducting polymer-based solid gel may be grafted directly onto the anode, charging electrode, cathode, or bifunctional electrode, when one is used. In this case, support for the separator or membrane is provided by the electrode substrate on which the polymer-based solid gel is formed.
The shape of the electrolyte solution volume or housing, which is shown as 2o reference number (90) in FIG. 6 and (91) in FIG. 7, is not constrained to be square or rectangular. It can be circular, elliptical, polygonal, or any desired shape. In addition, the cell housing may be fabricated from any strong chemically inert insulation material, such as plastic conventionally used in electrochemical cells and alkaline batteries.
When in operation, conducting wires (not shown), usually copper strips, are adhered to exposed portions of the metal anode, charging electrode, and cathode and/or bifunctional electrode. These conducting wires are used to apply an external voltage to the cell to recharge the anode. An insulating epoxy is typically used to cover the exposed joints.
EXAMPLES
Preferred embodiments of the present invention are hereinafter described in more detail by means of the following examples that are provided by way of illustration and not by way of limitation. The reactants and reagents used in the reactions described below are readily available materials. Such materials can be conveniently prepared in accordance with conventional preparatory procedures or obtained from commercial sources.
to Example 1 The following procedure was used to prepare a strong polymer film for use in the present invention. 0.75 grams methylenebisacrylamide, 0.56 g acrylamide, 4.70 g methacrylic acid, and 0.25 g poly(sodium 4-styrenesulfonate) were dissolved in 10 milliliters water and then 20 ml 40% KOH was added to the resulting solution, which was maintained at room temperature. 0.05 g ammonium persulfate was then added to the solution. A piece of fabric was soaked in the resulting monomer solution and then sandwiched between a piece of glass and a piece of PET
transparent film. This was heated on a 75 ° C hotplate for 1 minute and then irradiated under strong UV light for 5 minutes, whereby a strong polymer film was 2o formed.
The resulting film is highly conductive of hydroxide ions, making it suitable for use in an alkaline hydrogen fuel cell. Here, the membrane film is sandwiched between an air cathode and a hydrogen anode, separating the air and hydrogen, while allowing the diffusion of hydroxide ions.
Example 2 In this example, a polymer based solid gel membrane was prepared in accordance with the principles of the invention and applied to the surface of a cathode. 0.75 g Methylenebisacrylamide, 0.56 g acrylamide, 4.70 g methacrylic acid, and 1.5 g polysulfone (anionic) were dissolved in 10 ml water and then 20 ml 40% KOH was added to the resulting solution, which was maintained at room temperature. 0.038 g ammonium persulfate dissolved in 1 ml water was added and the resulting solution was poured onto the surface of an air cathode. The cathode was then covered by a piece of PET film and heated on a 75 ° C hotplate for 1 minute and then irradiated under strong UV light, whereby a strong polymer film was formed.
This cathode may be used with an anode prepared as in Example 3, below, or it may be used directly with a plain metal sheet, such as zinc, aluminum, to cadmium, lithium, magnesium, or lead, in the formation of a corresponding metal/air fuel cell battery. Alternatively, the cathode on which the solid gel is grafted, as in Example 2, may form a separator/bifunctional electrode in a rechargeable electrochemical cell (metal/air) in accordance with the present invention, or it may be positioned next to the charging electrode in the rechargeable cell, as mentioned above.
Example 3 A polymer based ion conducting membrane was prepared and applied to the surface of an anode according to the principles of the present invention. 0.75 g methylenebisacrylamide, 1.5 g poly(sodium 4-styrenesulfonate), 5.18 g 1-vinyl-2o pyrrolidinone, and 3.36 g acrylic acid were dissolved in 30 ml NH4C1 and saturated aqueous solution, followed by the addition of 0.1 g ammonium persulfate.
The solution was spread onto the anode surface, and covered by a PET film and then irradiated under strong UV light, whereby a strong polymer film was formed for use as a separator grafted onto the anode. In a fuel cell, the separator/anode is positioned next to the cathode, and in a rechargeable electrochemical cell, it is positioned next to the charging electrode or next to a single bifunctional electrode, when one is employed.
Example 4 A polymer-based solid gel membrane was prepared according to the present invention and processed to form a proton conducting film. 6.4 g 70% perchloric acid, 0.75 g methylenebisacrylamide, 5.18 g acrylic acid, and 0.1 g potassium sulfite (reducing agent) were dissolved in 27 ml water and then 0.1 g ammonium persulfate was added to the solution. A piece of fabric was soaked in the resulting monomer solution and then sandwiched between a piece of glass and a piece of PET
transparent film. This was heated on an 85°C hotplate for 1 minute and then irradiated under strong UV light for 8 minutes, whereby a strong polymer film was to formed.
The resulting film is highly conductive of protons (hydrogen ions), making it suitable for use in a hydrogen fizel cell or for use as a separator in an acidic rechargeable electrochemical cell, such as in a rechargeable lead-acid battery. In a hydrogen fuel cell, the membrane film is sandwiched between an air cathode and a hydrogen anode, separating the air and hydrogen while allowing the diffusion of hydrogen ions.
Example 5 The principles of the present invention may also be applied to electrochromic devices. For example, one or several electrochromic materials are 2o dissolved in an aqueous monomer solution which is then applied to an electrode substrate. The substrate may be comprised of such materials as for example, platinum, gold, conductive glass, e.g., indium-tin oxide glass, or other electro-conductive materials. The solution is polymerized according to either of the above methods wherein the ECM's are contained within the polymer membrane formed on the surface of the substrate. Two such modified electrodes, containing the same or different ECM's, are used in the electrochromic device with one acting as the anode and the other as the cathode. The electrodes may be packed together as a complete display device or they may be separated by a liquid or solid electrolyte.
Example 6 The following procedure was used to prepare a strong polymer film for use as a separator in a rechargeable electrochemical cell. One and a half grams (1.5 g) polysulfone (anionic), 0.75 g methylenebisacrylamide, 0.56 g acrylamide, and 4.70 g methacrylic acid was dissolved in 10 mL water, and maintained at room temperature. Twenty (20) mL 50% KOH was added to the resulting solution. A
piece of nylon fabric commercially available from Frendenberg Nonwovens as FS2213E was then soaked in the monomer solution. The solution was placed in an ice bath, and 0.10 g ammonium persulfate was added to the solution. The separator to was then taken out of the solution and sandwiched between transparent PET
film and glass. The 'sandwiched' separator was then heated on a hot plate at 90 ° C for 20 minutes on each side, then irradiated under strong UV light for 7 minutes on each side. The conductivity of the resulting membrane was 0.11 S/cm.
Examples of other monomers that may be used in the formation of a solid gel membrane and separator of the invention include any water-soluble ethylenically unsaturated amides or acids, including, but not limited to, N-isopropylacrylamide, fumaramide, fumaric acid, N, N-dimethylacrylamide, 3,3-dimethylacrylic acid, and the sodium salt of vinylsulfonic acid.
Other cross-linking agents include, for example, any water-soluble N,N'-alkylidene-bis(ethylenically unsaturated amide).
Examples of polymers other than poly(sodium 4-styrenesulfonate) that may be used as reinforcing elements within the solid gel electrolyte may include any water-soluble or water-swellable polymers, such as, for example, carboxymethyl cellulose, polysulfone (anionic), sodium salt of poly(styrenesulfonic acid-co-malefic acid), and corn starch.
Suitable fabrics onto which the monomer solution may be applied include, for example, woven or non-woven fabrics such as polyolefins, polyamides, polyvinyl alcohol, and cellulose.
With regard to initiation of the polymerization reaction chemical initiators such as, ammonium persulfate, alkali metal persulfates or peroxides may optionally be used in combination with radical generating methods such as radiation, including for example, ultraviolet light, X-ray, 'y-ray, and the like. However, the chemical initiators need not be added if the radiation alone is suf~'iciently powerful to begin the polymerization. As stated above, the polymerization may be conducted at temperatures ranging from room temperature up to about 130° C.
This invention has been described in terms of specific embodiments, set forth in detail. It should be understood, however, that these embodiments are to presented by way of illustration only, and that the invention is not necessarily limited thereto. The principles of the present invention may, for example, also be applied in the preparation of a solid gel membrane for use in such other electrochemical systems as for example, Ni/Cd and Zn/Mn02 cells. Additionally, other monomers, polymers, chemical polymerization initiators, reducing agents, and the like, other than those particularly disclosed herein might be used.
Modifications and variations in any given material or process step will be readily apparent to those skilled in the art without departing from the true spirit and scope of the following claims, and all such modifications and variations are intended to be included within the scope of the present invention.
Claims (60)
1. A rechargeable electrochemical cell comprising a separator, an anode, a cathode, and a charging electrode, wherein said separator comprises an ion-conducting polymer-based solid gel membrane comprising a support onto which a polymer-based gel having an ionic species contained within a solution phase thereof is formed, wherein said polymer-based gel comprises a polymerization product of one or more monomers selected from the group of water soluble ethylenically unsaturated amides and acids, and a reinforcing element selected from the group of water soluble and water swellable polymers, wherein said ionic species comes from an aqueous solution and is added to said one or more monomers, and said reinforcing element prior to polymerization, wherein said cathode and said charging electrode may be a single bifunctional electrode or may be individual and separate electrodes, and wherein said separator is positioned between said anode and said charging electrode.
2. The rechargeable electrochemical cell of claim 1, wherein said separator has an ionic conductivity of at least about 0.10 S/cm.
3. The rechargeable electrochemical cell of claim 1, wherein said one or more monomers is selected from the group of methylenebisacrylamide, acrylamide, methacrylic acid, acrylic acid, 1-vinyl-2-pyrrolidinone, N-isopropylacrylamide, fumaramide, fumaric acid, N, N-dimethylacrylamide, 3,3-dimethylacrylic acid, the sodium salt of vinylsulfonic acid, and combinations thereof.
4. The rechargeable electrochemical cell of claim 1, wherein said reinforcing element is selected from the group of poly(sodium 4-styrenesulfonate), carboxymethyl cellulose, polysulfone (anionic), sodium salt of poly(styrenesulfonic acid-co-maleic acid), and corn starch.
5. The rechargeable electrochemical cell of claim 4, wherein said polymer-based gel comprises said polymerization product of (a) methylenebisacrylamide, acrylamide, and methacrylic acid;
(b) methylenebisacrylamide, acrylic acid, 1-vinyl-2-pyrrolidinone and a reducing agent;
(c) methylenebisacrylamide, acrylic acid, and a reducing agent.
(b) methylenebisacrylamide, acrylic acid, 1-vinyl-2-pyrrolidinone and a reducing agent;
(c) methylenebisacrylamide, acrylic acid, and a reducing agent.
6. The rechargeable electrochemical cell of claim 1, wherein said polymerization is carried out using radical generating radiation selected from the group of X-ray, y-ray, and ultraviolet radiation at a temperature ranging from room temperature up to about 130° C.
7. The rechargeable electrochemical cell of claim 6, wherein a chemical polymerization initiator selected from the group of ammonium persulfate, alkali metal persulfates and peroxides is added to said one or more monomers and said reinforcing element prior to polymerization.
8. The rechargeable electrochemical cell of claim 1, wherein said polymerization is carried out at a temperature ranging from room temperature to about 130° C, optionally using radical generating radiation selected from the group of X-ray, y-ray, and ultraviolet radiation, and wherein a chemical polymerization initiator selected from the group of ammonium persulfate, alkali metal persulfates and peroxides is added to said one or more monomers and said reinforcing element prior to polymerization.
9. The rechargeable electrochemical cell of claim 1, wherein said cathode and said charging electrode are individual and separate electrodes, and wherein said charging electrode is positioned between said separator and said cathode.
10. The rechargeable electrochemical cell of claim 9, further comprising a porous spacer positioned between said charging electrode and said cathode.
11. The rechargeable electrochemical cell of claim 9, wherein said anode is a metal selected from the group of zinc, cadmium, lithium, magnesium, iron, and aluminum, and said cathode is an air cathode.
12. The rechargeable electrochemical cell of claim 11, wherein said charging electrode is selected from the group of platinum, nickel, nickel oxide, perovskite and its derivatives, carbon, and palladium.
13. The rechargeable electrochemical cell of claim 12, wherein said anode is zinc.
14. The rechargeable electrochemical cell of claim 12, further comprising a porous spacer positioned between said charging electrode and said air cathode.
15. The rechargeable electrochemical cell of claim 12, wherein said ionic species comes from an aqueous alkaline solution of potassium hydroxide, sodium hydroxide, lithium hydroxide, or combinations thereof, and wherein said hydroxide has a concentration ranging from about 0.1 wt. % to about 55 wt. %.
16. The rechargeable electrochemical cell of claim 15, wherein said hydroxide has a concentration of about 37.5 wt. %.
17. The rechargeable electrochemical cell of claim 15, wherein said separator has an ionic conductivity of at least about 0.10 S/cm.
18. The rechargeable electrochemical cell of claim 12, wherein said ionic species come from a neutral aqueous solution comprising:
(a) ammonium chloride and potassium sulfate;
(b) ammonium chloride, potassium sulfate, and sodium chloride; or (c) potassium sulfate and ammonium chloride.
(a) ammonium chloride and potassium sulfate;
(b) ammonium chloride, potassium sulfate, and sodium chloride; or (c) potassium sulfate and ammonium chloride.
19. The rechargeable electrochemical cell of claim 1, wherein said cathode and said charging electrode are a single bifunctional electrode.
20. The rechargeable electrochemical cell of claim 19, wherein said anode is a metal selected from the group of zinc, cadmium, lithium, magnesium, iron, and aluminum, and said single bifunctional electrode is an air cathode.
21. The rechargeable electrochemical cell of claim 20, wherein said ionic species comes from an aqueous alkaline solution of potassium hydroxide, sodium hydroxide, lithium hydroxide, or a mixture thereof, and wherein said hydroxide has a concentration ranging from about 0.1 wt. % to about 55 wt. %.
22. The rechargeable electrochemical cell of claim 21, wherein said hydroxide has a concentration of about 37.5 wt.
23. The rechargeable electrochemical cell of claim 21, wherein said separator has an ionic conductivity of at least about 0.10 S/cm.
24. The rechargeable electrochemical cell of claim 20, wherein said ionic species come from a neutral aqueous solution comprising:
(a) ammonium chloride and potassium sulfate;
(b) ammonium chloride, potassium sulfate, and sodium chloride; or (c) potassium sulfate and ammonium chloride.
(a) ammonium chloride and potassium sulfate;
(b) ammonium chloride, potassium sulfate, and sodium chloride; or (c) potassium sulfate and ammonium chloride.
25. The rechargeable electrochemical cell of claim 20, wherein said anode is zinc.
26. The rechargeable electrochemical cell of claim 19, wherein said anode is zinc or zinc oxide, and said single bifunctional electrode is selected from the group of nickel oxide, manganese dioxide, silver oxide, and cobalt oxide.
27. The rechargeable electrochemical cell of claim 26, wherein said ionic species comes from an aqueous alkaline solution of potassium hydroxide, sodium hydroxide, lithium hydroxide, or a mixture thereof, and wherein said hydroxide has a concentration ranging from about 0.1 wt. % to about 55 wt. %.
28. The rechargeable electrochemical cell of claim 27, wherein said hydroxide has a concentration of about 37.5 wt.
29. The rechargeable electrochemical cell of claim 28, wherein said separator has an ionic conductivity of at least about 0.10 S/cm.
30. The rechargeable electrochemical cell of claim 19, wherein said anode is selected from the group of iron and cadmium, and said single bifunctional electrode is nickel oxide.
31. The rechargeable electrochemical cell of claim 30, wherein said ionic species comes from an aqueous alkaline solution of potassium hydroxide, sodium hydroxide, lithium hydroxide, or a mixture thereof, and wherein said hydroxide has a concentration ranging from about 0.1 wt. % to about 55 wt. %.
32. The rechargeable electrochemical cell of claim 31, wherein said hydroxide has a concentration of about 37.5 wt.
33. The rechargeable electrochemical cell of claim 31, wherein said separator has an ionic conductivity of at least about 0.10 S/cm.
34. The rechargeable electrochemical cell of claim 19, wherein said anode is lead, and said single bifunctional electrode is lead oxide.
35. The rechargeable electrochemical cell of claim 34, wherein said ionic species comes from an aqueous acidic solution of perchloric acid, sulfuric acid, hydrochloric acid, phosphoric acid, or combinations thereof.
36. The rechargeable electrochemical cell of claim 35, wherein said separator has an ionic conductivity of at least about 0.10 S/cm.
37. The rechargeable electrochemical cell of claim 1, wherein said separator is formed directly onto said anode, said charging electrode, or said cathode, whereby said support is provided by said anode, by said charging electrode, or by said cathode, respectively.
38. The rechargeable electrochemical cell of claim 1, wherein said support is a woven or non-woven fabric selected from the group of polyamides, polyolefins, polyvinyl alcohol, and cellulose.
39. The rechargeable electrochemical cell of claim 1, further comprising an aqueous electrolyte in contact with said separator, said anode, said cathode, and said charging electrode.
40. A rechargeable electrochemical cell comprising a separator, a metal anode, an air cathode, and a charging electrode, wherein said separator comprises a hydroxide conducting polymer-based solid gel membrane comprising a support onto which a polymer-based gel having a hydroxide species contained within a solution phase thereof is formed, wherein said polymer-based gel comprises polysulfone and a polymerization product of methylenebisacrylamide, acrylamide, and methacrylic acid, wherein said hydroxide species comes from an aqueous alkaline solution having a concentration ranging from about 0.1 wt. % to about 55 wt. %
potassium hydroxide, sodium hydroxide, lithium hydroxide, or a mixture thereof, wherein said hydroxide species is added to said methylenebisacrylamide, acrylamide, and methacrylic acid, and said polysulfone prior to polymerization, wherein said air cathode and said charging electrode may be a single bifunctional electrode or may be individual and separate electrodes, wherein said separator is positioned between said metal anode and said charging electrode, wherein said polymerization is carried out using radical generating radiation selected from the group of x-ray, y-ray, and ultraviolet radiation; and wherein the ionic conductivity of said separator is at least about 0.10 S/cm.
potassium hydroxide, sodium hydroxide, lithium hydroxide, or a mixture thereof, wherein said hydroxide species is added to said methylenebisacrylamide, acrylamide, and methacrylic acid, and said polysulfone prior to polymerization, wherein said air cathode and said charging electrode may be a single bifunctional electrode or may be individual and separate electrodes, wherein said separator is positioned between said metal anode and said charging electrode, wherein said polymerization is carried out using radical generating radiation selected from the group of x-ray, y-ray, and ultraviolet radiation; and wherein the ionic conductivity of said separator is at least about 0.10 S/cm.
41. The rechargeable electrochemical cell of claim 40, wherein a polymerization initiator is added to said methylenebisacrylamide, acrylamide, methacrylic acid, and said hydroxide species prior to polymerization.
42. The rechargeable electrochemical cell of claim 40, further comprising an aqueous liquid electrolyte in contact with said separator, said anode, said cathode, and said charging electrode.
43. A polymer based solid gel membrane for use in an electrochemical cell, said membrane having an ionic species contained within a solution phase of said polymer based gel, wherein said polymer based gel comprises the polymerization product of a polymerization initiator, a monomer selected from the group of water soluble ethylenically unsaturated amides and acids, and a reinforcing element selected from the group of water soluble and water swellable polymers, wherein said ionic species comes from an aqueous solution and is added to said polymerization initiator, said monomer, and said reinforcing element prior to polymerization, and wherein said polymer based solid gel membrane is formed on a matrix of a woven or non-woven fabric, on a surface of an anode, or on a surface of a cathode.
44. The polymer based solid gel membrane according to claim 43, wherein said monomer is selected from the group of methylenebisacrylamide, acrylamide, methacrylic acid, 1-vinyl-2-pyrrolidione, N-isopropylacrylamide, fumaramide, fumaric acid, N, N-dimethylacrylamide, 3,3-dimethylacrylic acid, and the sodium salt of vinylsulfonic acid, and combinations thereof.
45. The polymer based solid gel membrane according to claim 43, wherein said reinforcing element is selected from the group of poly(sodium 4-styrenesulfonate), carboxymethyl cellulose, polysulfone (anionic), sodium salt of poly(styrenesulfonic acid-co-malefic acid), and corn starch.
46. The polymer based solid gel membrane according to claim 45, wherein the polymer based gel comprises the polymerization product of a polymerization initiator and:
(a) methylenebisacrylamide, acrylamide, methacrylic acid, poly(sodium 4-styrenesulfonate);
(b) methylenebisacrylamide, acrylamide, methacrylic acid, and polysulfone (anionic);
(c) methylenebisacrylamide, poly(sodium 4-styrenesulfonate), acrylic acid, 1-vinyl-2-pyrrolidione and a reducing agent; or (d) methylenebisacrylamide, acrylic acid and a reducing agent.
(a) methylenebisacrylamide, acrylamide, methacrylic acid, poly(sodium 4-styrenesulfonate);
(b) methylenebisacrylamide, acrylamide, methacrylic acid, and polysulfone (anionic);
(c) methylenebisacrylamide, poly(sodium 4-styrenesulfonate), acrylic acid, 1-vinyl-2-pyrrolidione and a reducing agent; or (d) methylenebisacrylamide, acrylic acid and a reducing agent.
47. An electrochemical cell comprising first and second electrodes and one or more polymer based solid gel membranes according to claim 43 disposed there between.
48. The electrochemical cell according to claim 47 wherein the first electrode is a zinc anode and the second electrode is an air cathode.
49. The electrochemical cell of claim 48 wherein a first protective polymer based solid gel membrane is disposed on the zinc anode and a second hydroxide conducting polymer based solid gel membrane is disposed between said first membrane and said cathode.
50. The electrochemical cell of claim 48 wherein a first protective polymer based solid gel membrane is disposed on said anode and a second protective polymer based solid gel membrane is disposed on said cathode, and said electrochemical cell further comprises an aqueous electrolyte disposed between said first and second membranes.
51. The electrochemical cell of claim 47 wherein the first electrode is an aluminum anode and the second electrode is an air cathode and a hydroxide conducting polymer based solid gel membrane is disposed there between.
52. The electrochemical cell of claim 47 wherein the first electrode is a hydrogen anode and the second electrode is an air cathode and a proton conductive polymer based solid gel membrane is disposed there between.
53. The electrochemical cell of claim 47 wherein the first electrode is a hydrogen anode and the second electrode is an air cathode and a hydroxide conductive polymer based solid gel membrane is disposed there between.
54. An electrochromic device wherein electrochromic materials are contained within a solution phase of a polymer based solid gel membrane.
55. An electrochromic device according to claim 54, comprising first and second electrode substrates and first and second polymer based solid gel membranes disposed there between, each of said membranes having an electrochromic material contained within a solution phase thereof.
56. The electrochromic device according to claim 55, further comprising an electrolyte active species disposed between said first and second polymer based solid gel membranes.
57. The electrochromic device according to claim 55 wherein said first and second electrode substrates are comprised of platinum, gold, or a conductive glass.
58. The electrochromic device according to claim 57 wherein the conductive glass is indium-tin oxide glass.
59. A method of inhibiting corrosion of a metal anode in a metal/air fuel cell system comprised of a metal anode and an air cathode, said method comprising disposing one or more polymer based solid gel membranes having an ionic species contained within a solution phase thereof, between said anode and said cathode, wherein said polymer based gel comprises the polymerization product of a polymerization initiator, a monomer selected from the group of water soluble ethylenically unsaturated amides and acids, and a reinforcing element selected from the group of water soluble and water swellable polymers, wherein said ionic species is added to said polymerization initiator, said monomer, and said reinforcing element prior to polymerization, and wherein said polymer based solid gel membrane is formed on a surface of said metal anode.
60. A method according to claim 59 wherein said metal/air fuel cell system is one of an aluminum/air, a zinc/air, a cadmium/air, a lithium/air, a magnesium/air, or an iron/air fuel cell system.
Applications Claiming Priority (5)
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US09/259,068 US6605391B2 (en) | 1999-02-26 | 1999-02-26 | Solid gel membrane |
US09/259,068 | 1999-02-26 | ||
US09/482,126 US6358651B1 (en) | 1999-02-26 | 2000-01-11 | Solid gel membrane separator in rechargeable electrochemical cells |
US09/482,126 | 2000-01-11 | ||
PCT/US2000/004881 WO2000051198A2 (en) | 1999-02-26 | 2000-02-25 | Solid gel membrane |
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CA2362298A1 true CA2362298A1 (en) | 2000-08-31 |
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Application Number | Title | Priority Date | Filing Date |
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CA002362298A Abandoned CA2362298A1 (en) | 1999-02-26 | 2000-02-25 | Solid gel membrane |
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US (2) | US6358651B1 (en) |
EP (1) | EP1155467A2 (en) |
JP (1) | JP2002538585A (en) |
KR (1) | KR100852461B1 (en) |
CN (1) | CN1184711C (en) |
AU (1) | AU772935B2 (en) |
BR (1) | BR0008506A (en) |
CA (1) | CA2362298A1 (en) |
HK (1) | HK1043876A1 (en) |
MX (1) | MXPA01008664A (en) |
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- 2000-01-11 US US09/482,126 patent/US6358651B1/en not_active Expired - Fee Related
- 2000-02-24 TW TW089103224A patent/TW463405B/en not_active IP Right Cessation
- 2000-02-25 WO PCT/US2000/004881 patent/WO2000051198A2/en not_active Application Discontinuation
- 2000-02-25 CN CNB008043353A patent/CN1184711C/en not_active Expired - Fee Related
- 2000-02-25 JP JP2000601703A patent/JP2002538585A/en active Pending
- 2000-02-25 AU AU35030/00A patent/AU772935B2/en not_active Ceased
- 2000-02-25 EP EP00913617A patent/EP1155467A2/en not_active Withdrawn
- 2000-02-25 CA CA002362298A patent/CA2362298A1/en not_active Abandoned
- 2000-02-25 BR BR0008506-5A patent/BR0008506A/en not_active Application Discontinuation
- 2000-02-25 KR KR1020017010896A patent/KR100852461B1/en not_active IP Right Cessation
-
2001
- 2001-08-24 MX MXPA01008664 patent/MXPA01008664A/en not_active Application Discontinuation
- 2001-11-30 US US10/013,016 patent/US20020102465A1/en not_active Abandoned
-
2002
- 2002-05-21 HK HK02103818.2A patent/HK1043876A1/en unknown
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US20020102465A1 (en) | 2002-08-01 |
WO2000051198A2 (en) | 2000-08-31 |
WO2000051198A9 (en) | 2002-03-28 |
WO2000051198A3 (en) | 2001-01-11 |
MXPA01008664A (en) | 2002-02-01 |
CN1341283A (en) | 2002-03-20 |
US6358651B1 (en) | 2002-03-19 |
EP1155467A2 (en) | 2001-11-21 |
HK1043876A1 (en) | 2002-09-27 |
KR100852461B1 (en) | 2008-08-19 |
KR20020020873A (en) | 2002-03-16 |
AU772935B2 (en) | 2004-05-13 |
BR0008506A (en) | 2002-02-05 |
JP2002538585A (en) | 2002-11-12 |
CN1184711C (en) | 2005-01-12 |
TW463405B (en) | 2001-11-11 |
AU3503000A (en) | 2000-09-14 |
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