DE4327114A1 - Gel-type electrolyte materials for uses in photoelectrochemical systems and method for synthesis of these materials and for applying coatings with these materials - Google Patents
Gel-type electrolyte materials for uses in photoelectrochemical systems and method for synthesis of these materials and for applying coatings with these materialsInfo
- Publication number
- DE4327114A1 DE4327114A1 DE4327114A DE4327114A DE4327114A1 DE 4327114 A1 DE4327114 A1 DE 4327114A1 DE 4327114 A DE4327114 A DE 4327114A DE 4327114 A DE4327114 A DE 4327114A DE 4327114 A1 DE4327114 A1 DE 4327114A1
- Authority
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- Germany
- Prior art keywords
- mol
- mixtures
- electrolyte
- redox
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- Prior art date
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- 230000015572 biosynthetic process Effects 0.000 title claims description 3
- 239000002001 electrolyte material Substances 0.000 title claims 3
- 238000000034 method Methods 0.000 title claims 3
- 238000000576 coating method Methods 0.000 title claims 2
- 238000003786 synthesis reaction Methods 0.000 title claims 2
- 239000000463 material Substances 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 18
- -1 tetrafluoroborate Chemical compound 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 4
- 229920001223 polyethylene glycol Polymers 0.000 claims 4
- 150000003839 salts Chemical class 0.000 claims 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 3
- 239000003349 gelling agent Substances 0.000 claims 3
- 229920002554 vinyl polymer Polymers 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- 229910003844 NSO2 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 2
- 150000004703 alkoxides Chemical class 0.000 claims 2
- 150000001450 anions Chemical class 0.000 claims 2
- 238000009835 boiling Methods 0.000 claims 2
- 150000001768 cations Chemical class 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 2
- 150000002576 ketones Chemical class 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 claims 2
- 239000002808 molecular sieve Substances 0.000 claims 2
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 claims 2
- 239000011591 potassium Substances 0.000 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 2
- XAMMKFSEEQGBIC-UHFFFAOYSA-N tetra(propan-2-yl)azanium Chemical compound CC(C)[N+](C(C)C)(C(C)C)C(C)C XAMMKFSEEQGBIC-UHFFFAOYSA-N 0.000 claims 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 125000004386 diacrylate group Chemical group 0.000 claims 1
- 238000003618 dip coating Methods 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- UGFMBZYKVQSQFX-UHFFFAOYSA-N para-methoxy-n-methylamphetamine Chemical compound CNC(C)CC1=CC=C(OC)C=C1 UGFMBZYKVQSQFX-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 229920000921 polyethylene adipate Polymers 0.000 claims 1
- 239000004926 polymethyl methacrylate Substances 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 claims 1
- 238000007650 screen-printing Methods 0.000 claims 1
- 239000011877 solvent mixture Substances 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000010345 tape casting Methods 0.000 claims 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 239000011135 tin Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000000499 gel Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Conductive Materials (AREA)
Abstract
Description
Ionenleitende Materialien mit einer gelartigen Struktur dienen als Elektrolyte in photoelektrochemischen Systemen, insbesondere in Dünnschichtsystemen. Sie verknüpfen die günstigen Eigenschaften der flüssigen Elektrolyte auf der Basis organischer Lösungsmittel wie hohe Ionenleitfähigkeit und die Fähigkeit zu schnellem Stofftransport mit den Vorzügen von gelartigen Materialien wie geringerer Dampfdruck bzw. Flüchtigkeit oder leichteres Prozessing bei der Montage der Systeme.Ion-conducting materials with a gel-like structure serve as electrolytes in photoelectrochemical systems, especially in thin film systems. she link the favorable properties of the liquid electrolytes on the basis organic solvents such as high ion conductivity and the ability to rapid mass transfer with the advantages of gel-like materials such as less Vapor pressure or volatility or easier processing when installing the Systems.
Für die Funktion des Elektrolyten in photoelektrochemischen Zellanordnungen wurden bisher ausschließlich (dünn-)flüssige Gemische auf der Basis von Wasser oder einem organischen Lösungsmittel wie Azetonitril, Propylencarbonat, Ethylencarbonat, Alkohole wie Ethanol, Methanol, 2-Propanol bzw. Gemische dieser Komponenten beschrieben. Diese enthalten als Leit- oder Grundelektrolyt Lithiumsalze wie z. B. Lithiumiodid, Quartäre Alkylammoniumiodide, Perchlorsäure (HClO₄). Als Redoxsysteme werden unter anderem die Systeme Iod/Iodid, Brom/Bromid, Chinon/Hydrochinon beschrieben, die in Form z. B. von elementarem Iod bzw. Brom sowie entsprechenden im Lösungsmittel ausreichend löslichen Halogenidsalzen wie z. B. LiBr, Lil zugemischt werden.For the function of the electrolyte in photoelectrochemical cell arrangements So far, only (thin) liquid mixtures based on water have been used or an organic solvent such as acetonitrile, propylene carbonate, Ethylene carbonate, alcohols such as ethanol, methanol, 2-propanol or mixtures thereof Components described. These contain as a conductive or basic electrolyte Lithium salts such as B. lithium iodide, quaternary alkyl ammonium iodides, perchloric acid (HClO₄). The iodine / iodide systems, Bromine / bromide, quinone / hydroquinone described in the form of e.g. B. of elementary Iodine or bromine and the correspondingly sufficiently soluble in the solvent Halide salts such as B. LiBr, Lil can be added.
Die Aufgabe des Elektrolyten ist ein Ausgleich der durch die photochemisch induzierte Redoxreaktion entstehenden Konzentrationsgradienten der Redoxpartner an den Elektroden durch Ionenleitung bzw. durch (diffusiven) Massentransport. Hierzu sollte der Elektrolyt die Eigenschaften eines möglichst guten elektronischen Isolators mit denen eines hohen Ionenleitungsvermögen und der Fähigkeit zum raschem Transport der Redoxspezies (z. B. Iodid und Iod) verknüpfen. Durch diese Funktion ist das dauerhafte Arbeiten der photoelektrochemischen Anordnung überhaupt erst möglich, da andernfalls sehr rasch eine so große Konzentrationspolarisation der Redoxpartner auftritt, daß der Stromfluß durch die Zelle auf einen sehr geringen Wert sinkt und zum Erliegen kommt.The job of the electrolyte is to compensate for that by photochemically induced redox reaction resulting concentration gradients of the redox partners at the electrodes by ion conduction or by (diffusive) mass transport. For this purpose, the electrolyte should have the properties of the best possible electronic Isolators with those of high ion conductivity and the ability to rapid transport of the redox species (e.g. iodide and iodine). Through this Function is the permanent working of the photoelectrochemical arrangement only possible at all, otherwise a large one would very quickly Concentration polarization of the redox partner occurs that the current flow through the Cell sinks to a very low value and comes to a standstill.
Ein großes Problem bei der Konstruktion regenrativer photoelektrochemischer Dünnschichtzellen ist bisher die hohe Flüchtigkeit der Lösungsmittel, die die Basis der Elektrolyte darstellen. Im Falle einer Leckage der Anordnung kommt es entweder zum raschen Auslaufen des Elektrolyten oder aber zum langsameren Ausdampfen. Die Performanz der Zelle nimmt in jedem falle mehr oder minder rasch ab und kommt gegebenenfalls ganz zum Erliegen. Auch durch Nachfüllen von frischem Elektrolyt ist es unmöglich, die ursprüngliche Performanz wiederherzustellen,da irreversible Vorgänge an der aktiven Elektrode ablaufen könne, wenn diese nicht mehr benetzt ist. Im Falle, daß der Elektrolyt gesundheitsschädliche Substanzen enthält, tritt bei Leckagen ein zusätzliches Sicherheitsrisiko für die Umwelt auf.A big problem in the construction of regenerative photoelectrochemical Until now, thin-film cells have been based on the high volatility of the solvents of the electrolytes. In the event of an arrangement leakage, it either occurs for rapid leakage of the electrolyte or for slower evaporation. In any case, the performance of the cell decreases more or less rapidly may come to a complete standstill. Also by refilling fresh ones Electrolyte it is impossible to restore the original performance since irreversible processes can take place on the active electrode if it is not is more wetted. In the event that the electrolyte harmful substances contains, there is an additional safety risk for the environment in the event of leakages.
Die oben beschriebenen Problematiken können ganz oder zumindest teilweise verringert oder gelöst werden, wenn es gelingt, die flüssigen Elektrolytgemische durch gelartige Elektrolyte zu ersetzen. Diese weisen einen deutlich geringeren Dampfdruck, ein weites Temperaturstabilitätsfenster und eine hohe Viskosität auf, so daß Leckagen in der Versiegelung der Zellanordnungen sich weniger auf die Funktion auswirken.The problems described above can be wholly or at least partially be reduced or dissolved if the liquid electrolyte mixtures succeed to be replaced by gel-like electrolytes. These have a significantly lower one Vapor pressure, a wide temperature stability window and a high viscosity, so that leaks in the sealing of the cell assemblies affect the Impact function.
Gelartige Ionenleiter werden in der Literatur bereits vielfach beschrieben.
Grundsätzlich müssen hier zwei verschiedene Ansätze unterschieden werden:
einerseits Gele aus organischen Lösungsmitteln und rein organischen Polymeren
und andererseits organischanorganische Kompositgele. Bei ersteren ist die
Gelbildung alleine auf die Quellung eines Polymers unter Aufnahme des Solvens
und homogener Vermischung mit diesem bedingt. Bei letzteren kommt es zur
Hydrolyse und Kondensation der anorganischen Komponente (z. B.
Alkoxidverbindungen von Übergangsmetallverbindungen oder Silizium), wobei
teilweise Bindungen zu einer organischen Komponente, z. B. einem Diol oder
Polyether, geknüpft werden, die zu einer echten chemische Verbindung der
anorganischen Polykondensate und der organischen Polymere bzw. Oligomere
führen. In beiden Fällen werden z. B. Säuren wie Trifluormethylsulfonsäure als
Protonenspender oder Lithiumverbindungen, häufig Lithiumperchlorat (LiClO₄)
zugemischt, um eine entsprechende Ionenleitfähigkeit zu erzielen. Die folgenden
Literaturzitate zu Gelelektrolyten mit organischen Polymeren als Gelbildner stellen
nur eine Auswahl aus der umfangreichen Literatur dar:
Z. Ogumi, Y. Uchimoto, Z. Takehara, Polymeric materials science and engineering,
62, 363, (1990), "Preparation and characterization of ionically-conductive thin
films using plasma polymerization".
W. I. Archer, R. D. Armstrong, Electrochmica Acta, 26, 167, (1981), "Stability of
some lithium ion conducting polymeric solid electrolytes in the presence of lithium
electrodes".
F. Croce, S. Passerini, A. Selvaggi, B. Scosati, Solid State Ionics, 40140, 375,
(1990), "Properties and applications of lithium ion-conducting polymers".
K. M. Abraham, M. Alamgir, J. Electrochem. Soc., 137(5), 1657, (1990),
"Li⁺-conductive solid polymer electrolytes with liquid-like conductivity".
M. Armand, Ann. Rev. Mater. Sci., 16, 24561, (1986), "Polymer electrolytes".
X. Huang, et al., Solid State Ionics 51, 69, (1992), "Electrical properities of a single
lithium-ion conductor PMSEO-PLPMS".
M. Duval, M. Gauthier, A. Blanger, P. E. Harvey, B. Kapfer, G. Vassort, Makromol.
Chem., Macromol. Symp., 24, 151, (1989).
O. Bohnke, C. Rousselot, P. A. Gillet, C. Truche, J. Electrochem. Soc., 139,1862,
(1992), "Gel electrolyte for solid state electrochemical cell".
R. Huq, G. C. Farrington, R. Koksbang, P. E. Tonder, Solid State Ionics 57 , 277,
(1992), "Influence of plasticizers on the electrochemical and chemical stability of a
Li⁺polymer electrolyte".
J. Pzyluski, W. Wieczorek Materials Science and Engineering, B13, 335, (1992),
"New concepts in the study of solid polymeric electrolytes".Gel-like ion conductors have already been widely described in the literature. Basically, two different approaches have to be distinguished here: on the one hand gels from organic solvents and purely organic polymers and on the other hand organic-inorganic composite gels. In the former, the gel formation is due solely to the swelling of a polymer with the absorption of the solvent and homogeneous mixing with it. The latter leads to the hydrolysis and condensation of the inorganic component (e.g. alkoxide compounds of transition metal compounds or silicon), some bonds to an organic component, e.g. B. a diol or polyether, which lead to a real chemical compound of the inorganic polycondensates and the organic polymers or oligomers. In both cases, e.g. B. acids such as trifluoromethylsulfonic acid as a proton donor or lithium compounds, often mixed lithium perchlorate (LiClO zu) to achieve a corresponding ionic conductivity. The following literature citations on gel electrolytes with organic polymers as gel formers represent only a selection from the extensive literature:
Z. Ogumi, Y. Uchimoto, Z. Takehara, Polymeric materials science and engineering, 62, 363, (1990), "Preparation and characterization of ionically-conductive thin films using plasma polymerization".
WI Archer, RD Armstrong, Electrochmica Acta, 26, 167, (1981), "Stability of some lithium ion conducting polymeric solid electrolytes in the presence of lithium electrodes".
F. Croce, S. Passerini, A. Selvaggi, B. Scosati, Solid State Ionics, 40140, 375, (1990), "Properties and applications of lithium ion-conducting polymers".
KM Abraham, M. Alamgir, J. Electrochem. Soc., 137 (5), 1657, (1990), "Li⁺-conductive solid polymer electrolytes with liquid-like conductivity".
M. Armand, Ann. Rev. Mater. Sci., 16, 24561, (1986) "Polymer electrolytes".
X. Huang, et al., Solid State Ionics 51, 69, (1992) "Electrical properities of a single lithium-ion conductor PMSEO-PLPMS".
M. Duval, M. Gauthier, A. Blanger, PE Harvey, B. Kapfer, G. Vassort, Makromol. Chem., Macromol. Symp., 24, 151, (1989).
O. Bohnke, C. Rousselot, PA Gillet, C. Truche, J. Electrochem. Soc., 139, 1862, (1992) "Gel electrolyte for solid state electrochemical cell".
R. Huq, GC Farrington, R. Koksbang, PE Tonder, Solid State Ionics 57, 277, (1992), "Influence of plasticizers on the electrochemical and chemical stability of a lithium polymer electrolyte".
J. Pzyluski, W. Wieczorek Materials Science and Engineering, B13, 335, (1992), "New concepts in the study of solid polymeric electrolytes".
In folgenden Literaturzitaten sind organisch-anorganische Komposite als
Gelelektrolyte mit ionischer Leitfähigkeit beschrieben:
P. Judeinstein et al., Solid State Ionics, 28-30, 1722, (1988), "An <all-gel<
electrochromic device".
D. Ravaine et al., Journal of Non-Crystalline Solids, 82, 210-19, (1986).
Y. Charbouillot et al., Journal of Non-Crystalline Solids, 103, 325-30,(1988),
"Aminosils: New solid state protonic materials by the sol-gel process".
L. C. Klein, S.-F. Ho, Glasses for electronic applications, 221-33, (1991), "Lithium
ion conducting silicate gels: synthesis and characterization".
H. Schmidt et al., Proceedings of the second int. symp. on polymer electrolytes
(Siena, 06/89), 325, "ORMOLYTEs (ORganically MOdified electroLYTEs): Solid
state protonic conductors by the sol-gel process".
M. Popall, H. Schmidt, "Electrical and electrochemical applications of Ormocers"
in Proceedings TEC-88-Materiaux, Grenoble (1988).The following citations describe organic-inorganic composites as gel electrolytes with ionic conductivity:
P. Judeinstein et al., Solid State Ionics, 28-30, 1722, (1988), "An <all-gel <electrochromic device".
D. Ravaine et al., Journal of Non-Crystalline Solids, 82, 210-19, (1986).
Charbouillot, Y. et al., Journal of Non-Crystalline Solids, 103, 325-30, (1988), "Aminosils: New solid state protonic materials by the sol-gel process".
LC Klein, S.-F. Ho, Glasses for electronic applications, 221-33, (1991), "Lithium ion conducting silicate gels: synthesis and characterization".
H. Schmidt et al., Proceedings of the second int. Symp. on polymer electrolytes (Siena, 06/89), 325, "ORMOLYTEs (ORganically MOdified electroLYTEs): Solid state protonic conductors by the sol-gel process".
M. Popall, H. Schmidt, "Electrical and electrochemical applications of Ormocers" in Proceedings TEC-88-Materiaux, Grenoble (1988).
Claims (9)
- a) organischen Lösungsmitteln aus der folgenden Gruppe: Alkohole (wie Methanol, Ethanol, 2-Propanol, 1-Propanol, 1-Butanol, Ethylenglykol, Diethylenglykol, Glycerol), Ketone (Dimethylketon, Methylethylketon), Ethylencarbonat, Propylencarbonat, Acetonitril, Diethylether, Tetrahydrofuran, Wasser, sowie Gemische aus diesen Lösungsmitteln in Mischungsverhältnissen derart, daß diese sich bei Temperaturen zwischen 10°C und dem Siedepunkt des jeweiligen Gemisches nicht entmischen, mit Wassergehalten der organischen Lösungsmittel zwischen 0.005 und 1.0 Gew.-%, die nötigenfalls durch Trocknung z. B. über Molekularsiebe eingestellt werden,
- b) Salzen in Konzentrationen von 0.05 bis 2.0 mol/l, vorz. 0.2 bis 0.8 mol/l, mit
Kationen aus der folgenden Gruppe:
Wasserstoff, Lithium, Natrium, Kalium, Ammonium, quartäre Alkylammoniumsalze wie Tetramethylammonium, Tetraethylammonium, Tetraisopropylammonium, Tetra-n-propylammonium, Tetra-1-butylammonium und Anionen aus der folgenden Gruppe:
Chlorid, Bromid, Iodid, Nitrat, Sulfat, Perchlorat, Tetrafluoroborat, Trifluormethylsulfonat ((CF₃)SO₃⁻), Ditrifluormethylsulfonamid (NSO₂(CF₃)₂²), sowie Gemische dieser Salze, - c) Redoxkomponenten aus der folgenden Gruppe:
elementares Brom, elementares Iod, Chinon und Hydrochinon, , andere organische Redoxsysteme wie Methylviologen, sowie Gemische dieser Redoxkomponenten, in Konzentrationen von 0.001 bis 0.5 mol/l, vorz. 0.01 bis 0.1 mol/l, - d) Wasser in Anteilen von 0.005 bis 2.0 Gew.-%,
- e) Gelbildnern in Konzentrationen zwischen 0.001 und 50 Mol-% aus der
Gruppe:
Polyethylenoxid, Polypropylenoxid, Polyethylenglykole (Diethylenglykol, Tetraethylenglykol und höhere Polyethylenglykole), Po lyacrylnitril, Polyvinylsulfat, Polyvinyldifluorid, Polyvinylphosphat, Po ly(methacrylsäure)polyethylenoxid, Polyethylenadipat, Poly(methylmethacrylat)- Polymer PMMA, Ethylenglykoldimethylacrylat, Polyacrylamid, Polyethylen glykolmonomethylether, Cellulose, Polyacetat, CPE d. h. Cross-linked- Polyether, Polyethylenglykoldiacrylat, Polyvinylpyrrolidon.
- a) organic solvents from the following group: alcohols (such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, ethylene glycol, diethylene glycol, glycerol), ketones (dimethyl ketone, methyl ethyl ketone), ethylene carbonate, propylene carbonate, acetonitrile, diethyl ether, Tetrahydrofuran, water, and mixtures of these solvents in mixing ratios such that they do not separate at temperatures between 10 ° C and the boiling point of the respective mixture, with water contents of the organic solvents between 0.005 and 1.0 wt .-%, if necessary by drying z . B. adjusted via molecular sieves,
- b) salts in concentrations of 0.05 to 2.0 mol / l, pref. 0.2 to 0.8 mol / l, with cations from the following group:
Hydrogen, lithium, sodium, potassium, ammonium, quaternary alkylammonium salts such as tetramethylammonium, tetraethylammonium, tetraisopropylammonium, tetra-n-propylammonium, tetra-1-butylammonium and anions from the following group:
Chloride, bromide, iodide, nitrate, sulfate, perchlorate, tetrafluoroborate, trifluoromethylsulfonate ((CF₃) SO₃⁻), ditrifluoromethylsulfonamide (NSO₂ (CF₃) ₂²), and mixtures of these salts, - c) Redox components from the following group:
elemental bromine, elemental iodine, quinone and hydroquinone,, other organic redox systems such as methyl viologen, as well as mixtures of these redox components, in concentrations of 0.001 to 0.5 mol / l, preferably 0.01 to 0.1 mol / l, - d) water in proportions of 0.005 to 2.0% by weight,
- e) gelling agents in concentrations between 0.001 and 50 mol% from the group:
Polyethylene oxide, polypropylene oxide, polyethylene glycols (diethylene glycol, tetraethylene glycol and higher polyethylene glycols), polyacrylonitrile, polyvinyl sulfate, polyvinyl difluoride, polyvinyl phosphate, poly (methacrylic acid) polyethylene oxide, polyethylene adipate, poly (methyl methacrylate) - polymer PMMA, ethylene glycol, ethylene glycol, methylene methacrylate, methylene methacrylate, methylene methacrylate, methylene methacrylate, methylene methacrylate, methylene methacrylate, methylene methacrylate, methylene methacrylate, , CPE ie cross-linked polyether, polyethylene glycol diacrylate, polyvinylpyrrolidone.
- a) organischen Lösungsmitteln aus der folgenden Gruppe:
Alkohole (wie Methanol, Ethanol, 2-Propanol, 1-Propanol, 1-Butanol, Ethylenglykol, Diethylenglykol, Glycerol), Ketone (Dimethylketon, Methylethylketon), Ethylencarbonat, Propylencarbonat, Acetonitril, Diethylether, Tetrahydrofuran, Wasser sowie Gemische aus diesen Lösungsmitteln in Mischungsverhältnissen derart, daß diese sich bei Temperaturen zwischen 10°C und dem Siedepunkt des jeweiligen Gemisches nicht entmischen, mit Wassergehalten der organischen Losungsmittel zwischen 0.005 und 1.0 Gew.-%, die nötigenfalls durch Trocknung z. B. über Molekularsiebe eingestellt werden, - b) Salzen in Konzentrationen von 0.05 bis 2.0 mol/l, vorz. 0.2 bis 0.8 mol/l, mit
Kationen aus der folgenden Gruppe:
Wasserstoff, Lithium, Natrium, Kalium, Ammonium, quartäre Alkylammoniumsalze wie Tetramethylammonium, Tetraethylammonium, Tetraisopropylammonium, Tetra-n-propylammonium, Tetra-1-butylammonium und Anionen aus der folgenden Gruppe:
Chlorid, Bromid, Iodid, Nitrat, Sulfat, Perchlorat, Tetrafluoroborat, Trifluormethylsulfonat ((CF₃)SO₃⁻), Ditrifluormethylsulfonamid (NSO₂(CF₃)₂²2-),
sowie Gemische dieser Salze, - c) Redoxkomponenten aus der folgenden Gruppe:
elementares Brom, elementares Iod, Chinon und Hydrochinon, andere organische Redoxsysteme wie Methylviologen, sowie Gemische dieser Redoxkomponenten, in Konzentrationen von 0.001 bis 0.5 mol/l, vorz. 0.01 bis 0.1 mol/l, - d) Wasser in Anteilen von 0.005 bis 2.0 Gew.-%,
- e) einer oder mehreren gemischten Alkoxidverbindung (Methylat, Ethylat,
Isopropylat, 1-Propylat, 1-Butylat) von Elementen wie Titan, Zirkon, Silicium,
Aluminium, Zinn, Zink, Wolfram, Molybdän in Anteilen von 0.01 bis 5.0 mol/l,
vorz. 0.1 bis 1.0 mol/l. Alternativ können hier kommerzielle Verbindungen oder
solche, die frisch aus Alkoholen und z. B. Halogeniden erzeugt wurden,
verwendet werden.
Die Alkoxide können teilweise z. B. mit verdünnten Säuren vorhydrolysiert bzw. vorkondensiert eingesetzt werden oder aber nach dem Einbringen in das Elektolytgemisch vorhydrolysiert bzw. vorkondensiert werden.
- a) organic solvents from the following group:
Alcohols (such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, ethylene glycol, diethylene glycol, glycerol), ketones (dimethyl ketone, methyl ethyl ketone), ethylene carbonate, propylene carbonate, acetonitrile, diethyl ether, tetrahydrofuran, water and mixtures of these solvents in Mixing ratios such that they do not separate at temperatures between 10 ° C and the boiling point of the respective mixture, with water contents of the organic solvents between 0.005 and 1.0 wt .-%, if necessary by drying z. B. adjusted via molecular sieves, - b) salts in concentrations of 0.05 to 2.0 mol / l, pref. 0.2 to 0.8 mol / l, with cations from the following group:
Hydrogen, lithium, sodium, potassium, ammonium, quaternary alkylammonium salts such as tetramethylammonium, tetraethylammonium, tetraisopropylammonium, tetra-n-propylammonium, tetra-1-butylammonium and anions from the following group:
Chloride, bromide, iodide, nitrate, sulfate, perchlorate, tetrafluoroborate, trifluoromethylsulfonate ((CF₃) SO₃⁻), ditrifluoromethylsulfonamide (NSO₂ (CF₃) ₂²2-),
as well as mixtures of these salts, - c) Redox components from the following group:
elemental bromine, elemental iodine, quinone and hydroquinone, other organic redox systems such as methyl viologen, as well as mixtures of these redox components, in concentrations of 0.001 to 0.5 mol / l, pref. 0.01 to 0.1 mol / l, - d) water in proportions of 0.005 to 2.0% by weight,
- e) one or more mixed alkoxide compounds (methylate, ethylate, isopropylate, 1-propylate, 1-butylate) of elements such as titanium, zirconium, silicon, aluminum, tin, zinc, tungsten, molybdenum in proportions of 0.01 to 5.0 mol / l, ex. 0.1 to 1.0 mol / l. Alternatively, commercial compounds or those fresh from alcohols and e.g. B. halides were used.
The alkoxides can partially z. B. pre-hydrolyzed or pre-condensed with dilute acids or pre-hydrolyzed or pre-condensed after introduction into the electrolyte mixture.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4327114A DE4327114A1 (en) | 1993-08-12 | 1993-08-12 | Gel-type electrolyte materials for uses in photoelectrochemical systems and method for synthesis of these materials and for applying coatings with these materials |
| AU76127/94A AU7612794A (en) | 1993-08-12 | 1994-08-11 | Photovoltaic cell with a photo-sensitised, semiconducting metal oxide coating |
| PCT/EP1994/002684 WO1995005670A1 (en) | 1993-08-12 | 1994-08-11 | Photovoltaic cell with a photo-sensitised, semiconducting metal oxide coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4327114A DE4327114A1 (en) | 1993-08-12 | 1993-08-12 | Gel-type electrolyte materials for uses in photoelectrochemical systems and method for synthesis of these materials and for applying coatings with these materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4327114A1 true DE4327114A1 (en) | 1995-03-30 |
Family
ID=6495044
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4327114A Withdrawn DE4327114A1 (en) | 1993-08-12 | 1993-08-12 | Gel-type electrolyte materials for uses in photoelectrochemical systems and method for synthesis of these materials and for applying coatings with these materials |
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| DE (1) | DE4327114A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0924724A2 (en) * | 1997-12-16 | 1999-06-23 | Fuji Photo Film Co., Ltd. | Photoelectric conversion device and photo-electrochemical cell |
| GR1003816B (en) * | 2001-04-02 | 2002-02-21 | Orel Boris | Photo-electrochemical solid state cell use for the photovoltaic conversion of solar energy |
| WO2003054894A1 (en) | 2001-12-21 | 2003-07-03 | Sony International (Europe) Gmbh | A polymer gel hybrid solar cell |
| DE102016202988A1 (en) * | 2016-02-25 | 2017-08-31 | Robert Bosch Gmbh | Organic electrolyte, use of the electrolyte and hybrid supercapacitor containing the electrolyte |
-
1993
- 1993-08-12 DE DE4327114A patent/DE4327114A1/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0924724A2 (en) * | 1997-12-16 | 1999-06-23 | Fuji Photo Film Co., Ltd. | Photoelectric conversion device and photo-electrochemical cell |
| EP0924724A3 (en) * | 1997-12-16 | 2001-10-17 | Fuji Photo Film Co., Ltd. | Photoelectric conversion device and photo-electrochemical cell |
| GR1003816B (en) * | 2001-04-02 | 2002-02-21 | Orel Boris | Photo-electrochemical solid state cell use for the photovoltaic conversion of solar energy |
| WO2003054894A1 (en) | 2001-12-21 | 2003-07-03 | Sony International (Europe) Gmbh | A polymer gel hybrid solar cell |
| AU2002358761B2 (en) * | 2001-12-21 | 2008-05-22 | Sony Corporation | A polymer gel hybrid solar cell |
| DE102016202988A1 (en) * | 2016-02-25 | 2017-08-31 | Robert Bosch Gmbh | Organic electrolyte, use of the electrolyte and hybrid supercapacitor containing the electrolyte |
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