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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/62—Quaternary ammonium compounds
  • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
  • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
• • 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
  • H01G9/004—Details
  • H01G9/022—Electrolytes; Absorbents
• • 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
  • H01G9/004—Details
  • H01G9/022—Electrolytes; Absorbents
  • H01G9/035—Liquid electrolytes, e.g. impregnating materials
• • 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
  • H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
• • 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
• • 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
  • Y02E60/13—Energy storage using capacitors

Definitions

• the present invention relates to electrolyte formulations comprising at least one imidazolium fluorotricyanoborate or pyrrolidinium fluorotricyanoborate and their use in an electrochemical and/or optoelectronic device such as a photovoltaic cell, a light emitting device, an electrochromic or photo- electrochromic device, an electrochemical sensor and/or biosensor, preferably their use in a dye or quantum dot sensitized solar cell.
• Electrolyte formulations form a crucial part of electrochemical and/or optoelectronic devices and the performance of the device largely depends on the physical and chemical properties of the various components of these electrolytes.
• electrolytes is used herein in the sense of electrolyte formulation as defined below and will be used equally to electrolyte formulation within the disclosure.
• Ionic liquids or liquid salts are typically ionic species which consist of an organic cation and a generally inorganic anion usually having melting points below 373 K.
• Various binary ionic liquid electrolytes have recently been applied to dye-sensitized solar cells.
• WO 2007/093961 and WO 2009/083901 describe so far the best power conversion efficiencies in ionic liquid-based electrolytes for DSC containing a significant quantity of organic salts with tetracyanoborate (TCB) anions.
• TBC tetracyanoborate
• electrolytes based on ionic liquids with improved DSC efficiency especially at a temperature below room temperature and well above the temperature at which liquid freezing and precipitation may take place (i.e. in the range of 0°C to 20°C).
• the object of the invention is therefore to provide electrolyte formulations for electrochemical and/or optoelectronic devices with increased power conversion efficiency such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor, especially for dye or quantum dot sensitized solar cells, especially preferably for dye sensitized solar cells over a broad temperature range, particularly additionally at low temperature.
• Low temperature is defined as the temperature range between 0°C and 20°C.
• formulations comprising fluorotricyanoborate anions reduce the Nernst diffusion resistance of redox-couple species (e.g. I " and ”) and charge transfer resistance at the counter electrode at low
• the present invention therefore relates firstly to an electrolyte formulation comprising at least one compound of formula (I)
• Kf is an organic cation selected from the group of Imidazolium Pyrrolidinium
• R 1 to R 0 each, independently of one another, denote
• straight-chain or branched alkenyl having 2 to 20 C atoms and one or more double bonds which optionally may be fluorinated or perfluorinated, straight-chain or branched alkynyl having 2 to 20 C atoms and one or more triple bonds which optionally may be fluorinated or perfluorinated or straight-chain or branched alkoxyalkyl having 2 to 8 C atoms.
• the present invention is therefore a selection invention out of the
• the electrolyte formulations may include or comprise, essentially consist of or consist of the said necessary or optional constituents.
• a straight-chain or branched alkyl having 1-20 C atoms denotes an alkyl group having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 C atoms, for example methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n-pentyl, 1-, 2- or 3-methylbutyl, 1 ,1-, 1 ,2- or 2,2-dimethylpropyl, -ethylpropyl, n-hexyl, n-heptyl, n-octyl, ethylhexyl, n-nonyl, n-decyl, n- undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hex
• perfluorinated means that all H atoms are substituted by F atoms in the given alkyl group.
• fluorinated means that at least one H atom of the given alkyl group is substituted by an F atom.
• a straight-chain or branched alkenyl having 2 to 20 C atoms, in which a plurality of double bonds may also be present, is, for example, allyl, 2- or 3- butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, isopentenyl, hex- enyl, heptenyl, octenyl, -C 9 H 17 , -Ci 0 Hi 9 to -C20H39, preferably allyl, 2- or 3- butenyl, isobutenyl, sec-butenyl, furthermore preferably 4-pentenyl, isopentenyl or hexenyl, which may be optionally fluorinated or perfluorinated.
• a straight-chain or branched alkynyl having 2 to 20 C atoms, in which a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2- propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, hept- ynyl, octynyl, -C9H15, -C 10 H 17 to -C20H37, preferably ethynyl, 1- or 2-propyn- yl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl, which may be optionally fluorinated or perfluorinated.
• a straight-chain or branched alkoxyalkyl having 2 to 12 C atoms is, for example, methoxymethyl, 1-methoxyethyl, 1-methoxypropyl, 1-methoxy-2- methyl-ethyl, 2-methoxy-propyl, 2-methoxy-2-methyl-propyl, 1- methoxybutyl, 1-methoxy-2,2-dimethyl-ethyl, 1-methoxy-pentyl, 1- methoxyhexyl, 1-methoxy-heptyl, ethoxymethyl, 1-ethoxyethyl, 1- ethoxypropyl, 1-ethoxy-2-methyl-ethyl, 1-ethoxybutyl, 1-ethoxy-2,2- dimethyl-ethyl, 1-ethoxypentyl, 1-ethoxyhexyl, 1-ethoxyheptyl,
• butoxymethyl 1-butoxyethyl, 1-butoxypropyl or 1-butoxybutyl. Particularly preferred is methoxymethyl, 1-methoxyethyl, 2-methoxy-propyl, 1- methoxypropyl, 2-methoxy-2-methyl-propyl or 1-methoxybutyl.
• the substituents R 1 and R 4 are each, independently of one another, preferably straight-chain or branched alkyl having 1 to 20 C atoms, which optionally may be fluorinated or perfluorinated or straight-chain or branched alkoxyalkyl having 2 to 8 C atoms with the assumption that R 1 and R 4 are not perfluorinated at the same time, particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl. They are very particularly preferably methyl, ethyl, n-butyl or n-hexyl. In pyrrolidinium or imidazolium, the two substituents R and R are preferably different.
• suitable substituents R 2 , R 3 and R 5 to R 10' of compounds of the formula (I), besides H for, are preferably: C to C 20 -alkyl groups, in particular C r to C 6 -alkyl groups.
• the substituents R 2 , R 3 , R 5' to R 10 are in each case, independently of one another, in particular H, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl.
• R 5 of the imidazolium ring is particularly preferably H, methyl, ethyl, isopropyl, propyl or n-butyl, particularly preferably H or methyl.
• R 2' and R 3 of the imidazolium ring are preferably H.
• the substituents R 2 , R 3 , R 5 to R 10 of the pyrrolidinium ring are preferably H.
• Preferred 1 ,1-dialkylpyrrolidinium cations are, for example, 1 ,1-dimethyl- pyrrolidinium, 1-methyl-1-ethylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, 1 -methyl-1 -butylpyrrolidinium, 1 -methyl-1 -pentylpyrrolidinium, 1 -methyl-1 - hexylpyrrolidinium, 1 -methyl-1 -heptylpyrrolidinium, 1 -methyl-1 -octylpyrroli- dinium, 1 -methyl-1 -nonylpyrrolidinium, 1 -methyl-1 -decylpyrrolidinium, 1 ,1- diethylpyrrolidinium, 1 -ethyl-1 -propylpyrrolidinium, 1 -ethyl-1 -butylpyrrolidinium, 1 -ethyl-1 -pentyl
• 1-butyl-1 -methylpyrrolidinium or 1-propyl-1-methyl- pyrrolidinium are, for example, 1-(2- methoxyethyl)-1 -methylpyrrolidinium, 1 -(2-methoxyethyl)-1 -ethyl- pyrrolidinium, 1-(2-methoxyethyl)-1-propylpyrrolidinium, 1 -(2-methoxyethyl)- 1 -butylpyrrolidinium , 1 -(2-ethoxyethyl)-1 -methylpyrrolidinium,
• Preferred 1 ,3-dialkylimidazolium cations are, for example, 1-ethyl-3-methyl- imidazolium, 1-methyl-3-propylimidazolium, 1-methyl-2,3- dimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-propyl-2,3- dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-butyl-3-methyl- imidazolium, 1-methyl-3-pentylimidazolium, 1-ethyl-3-propylimidazolium, 1-butyl-3-ethylimidazolium, 1-ethyl-3-pentylimidazolium, 1-butyl-3-propyl- imidazolium, 1 ,3-dimethylimidazolium, 1 ,3-diethylimidazolium, 1 ,3- dipropylimidazolium, 1,
• Preferred 1-alkoxyalkyl-3-alkylimidazolium cations are, for example 1-(2- methoxyethyl)-3-methylimidazolium, 1-(2-methoxyethyl)-3-ethylimidazolium, 1 -(2-methoxyethyl)-3-propylimidazolium, 1 -(2-methoxyethyl)-3-butyl- imidazolium, 1-(2-ethoxyethyl)-3-methylimidazolium, 1-ethoxymethyl-3- methylimidazolium.
• Preferred 1-alkenyl-3-alkylimidazolium cations are, for example 1-allyl-3- methyl-imidazolium or 1-allyl-2,3-dimethylimidazolium.
• an electrolyte is any substance containing free ions that make the substance electrically conductive.
• the most typical electrolyte is an ionic solution, but molten electrolytes and solid electrolytes are also possible.
• An electrolyte formulation according to the invention is therefore an electrically conductive medium, basically due to the presence of at least one substance that is present in a dissolved and or in molten state i.e. supporting an electric conductivity via motion of ionic species.
• electrolyte may be used for the term electrolyte formulation as well comprising all ingredients as disclosed for the electrolyte formulation.
• the electrolyte formulation according to the invention comprise at least one compound of formula (I) with the given formula for imidazolium as described or preferably described above.
• the present invention relates further to an electrolyte formulation comprising at least one compound of formula (I) as described above in which Kt + of the compound of formula (I) is
• R 5 is H or straight- chain or branched alkyl having 1 to 4 C atoms and R r and R are each independently of one another straight chain or branched alkyl having 1-20 C atoms or straight-chain or branched alkenyl having 3 C atoms.
• the present invention relates also to an electrolyte formulation comprising at least one compound of formula (I) in which K of the compound of formula (I) is
• R 2' , R 3' , R 5' to R 10' are H and R 1' and R 4 are each independently of one another straight chain or branched alkyl having 1-20 C atoms.
• the electrolyte formulation according to the invention comprise at least one compound of formula (I) with the given formula for imidazolium and the definitions of the substituents R r to R 5 or particularly preferred meanings of dialkylimidazolium or 1-alkoxyalkyl-3- alkylimidazolium as described above.
• Typical molar concentrations of the fluorotricyanoborate anion in the electrolyte formulations range from 0.1 to 5.5 M, preferably from 0.8 to 3.5 M. This molar concentration in the electrolyte may be achieved with one or more compounds of formula (I) or with mixtures comprising at least one compound of formula (I) and at least one inorganic salt with the
• Inorganic salts with fluorotricyanoborate anions are for example lithium fluorotricyanoborate, sodium fluorotricyanoborate, potassium
• the molar concentration is achieved with at least one compound of formula (I) as described or preferably described above.
• the molar concentration refer to the concentration at 25°C.
• Other components of the electrolyte formulation are one or several further salts, solvents, iodine and others, as indicated further below.
• the electrolyte formulation is a binary system, it comprises two salts, one further salt and a compound of formula (I) as described above. If the electrolyte formulation is a ternary system, it comprises two further salts and a compound of formula (I) as described above.
• Amounts of further, generally optional components (additives) indicated below, such as N-containing compounds having unshared electron pairs, iodine, solvents, polymers, and nanoparticles, for example, are not considered therein.
• the same percentages apply to ternary or quaternary systems which means the total of the further salts has to be used in the given ranges, e.g. two further ionic liquids are comprised in e.g. 90-20 weight.% in the electrolyte formulation according to the invention.
• the electrolyte formulation comprises at least one further salt with organic cations comprising a quaternary nitrogen and an anion selected from a halide ion, such as F " , CI ' , , a polyhalide ion, a fluoroalkanesulfonate, a
• fluoroalkanecarboxylate a tri(fluoroalkylsulfonyl)methide, a
• bis(fluoroalkylsulfonyl)imide a nitrate, a hexafluorophosphate, a tris- , bis- and mono-(fluoroalkyl)fluorophosphate, a tetrafluoroborate, a dicyanamide, a tricyanomethide, a tetracyanoborate, a thiocyanate, an alkylsulfonate or an alkylsulfate, with fluoroalkane having 1 to 20 C atoms, preferably perfluorinated, fluoroalkyi having 1 to 20 C atoms and alkyl having 1 to 20 C atoms. Fluoroalkane or fluoroalkyi is preferably perfluorinated.
• the further salts are selected from salts comprising anions such as iodide, thiocyanate or tetracyanoborate, particularly preferred further salts are iodides.
• the cation of the at least one further salt or of a preferred further salt may be selected amongst organic compounds comprising a quaternary nitrogen atom, preferably cyclic organic cations such as pyridinium, imidazolium, triazolium, pyrrolidinium or morpholinium.
• the organic cations may be selected from the definitions for the cations of the compounds of formula (I). Therefore, according to another preferred embodiment of the present invention, the electrolyte formulation comprises at least one compound of formula (I) as described above and at least one further iodide in which the organic cations are independently selected from the group of,
• the at least one further salt are 1 -ethyl-3- methylimidazolium iodide, 1-propyl-3-methylimidazolium iodide, 1-butyl-3- methyl-imidazolium iodide, 1-hexyl-3-methylimidazolium iodide, 1 ,3- dimethyl-imidazolium iodide, 1-allyl-3-methylimidazolium iodide, N-butyl-N- methyl-pyrrolidinium iodide or ⁇ , ⁇ -dimethyl-pyrrolidinium iodide.
• guanidinium thiocyanate may be added to the electrolyte formulation according to the invention.
• the electrolyte formulation of the invention preferably comprises iodine (l 2 ). Preferably, it comprises from 0.0005 to 7 mol/dm 3 , more preferably 0.01 to 5 mol/dm 3 and most preferably from 0.05 to 1 mol/dm 3 of l 2 .
• the electrolyte formulation of the present invention further comprises at least one compound containing a nitrogen atom having non-shared electron pairs.
• compounds having non-shared electron pairs include imidazole and its derivatives, particularly benzimidazole and its derivatives.
• the electrolyte formulation of the present invention comprises less than 50 vol.% of an organic solvent.
• the electrolyte formulation comprises less than 40%, more preferably less than 30%, still more preferably less than 20% and even less than 10 %.
• the electrolyte formulation comprises less than 5% of an organic solvent.
• it is substantially free of an organic solvent. Percentages are indicated on the basis of weight %. Organic solvents, if present in such amounts as indicated above, may be selected from those disclosed in the literature.
• the solvent if present, has a boiling point higher than 160 degrees centigrade, more preferably higher than 190 degrees such as propylene carbonate, ethylene carbonate, butylene carbonate, gamma-butyrolactone, gamma- valerolactone, glutaronitrile, adiponitrile, N-methyloxazolidinone, N- methylpyrrolidinone, ⁇ , ⁇ '-dimethylimidazolidinone, N,N-dimethylacetamide, cyclic ureas preferably 1 ,3-dimethyl-2-imidazolidinone or 1 ,3-dimethyl- 3,4,5,6-tetrahydro-2(1H)-pyrimidinone, glymes preferably tetraglyme, sulfolane, sulfones which are preferably asymmetrically substituted such as 2-ethanesulfonyl-propane, 1-ethanesulfonyl-2-methyl
• a solvent is present in the electrolyte formulation, there may further be comprised a polymer as gelling agent, wherein the polymer is
• polyvinylidenefluoride polyvinylidene-hexafluropropylene, polyvinylidene- hexafluoropropylene-chlorotrifluoroethylene copolymers, nation,
• polyethylene oxide polymethylmethacrylate, polyacrylonitrile,
• polypropylene polystyrene, polybutadiene, polyethyleneglycol,
• polyvinylpyrrolidone polyaniline, polypyrrole, polythiophene.
• the purpose of adding these polymers to electrolyte formulations is to make liquid electrolytes into quasi-solid or solid electrolytes, thus improving solvent retention, especially during aging.
• the electrolyte formulation of the invention may further comprise metal oxide nanoparticles like SiO 2 , TiO 2 , AI 2 O 3 , MgO or ZnO, for example, which are also capable of increasing solidity and thus solvent retention.
• the electrolyte formulation of the invention has many applications. For example, it may be used in an optoelectronic and/or electrochemical device such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor. Also the use in electrochemical batteries is possible, for example in a lithium ion battery or a double layer capacitor.
• an optoelectronic and/or electrochemical device such as a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor.
• electrochemical batteries for example in a lithium ion battery or a double layer capacitor.
• the present invention therefore relates further to the use of the electrolyte formulation as described in detail above in an electrochemical and/or optoelectronic device which is a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an electrochemical sensor and/or biosensor.
• the electrolyte formulation may be used in dye sensitized solar cells.
• the present invention therefore relates furthermore to an electrochemical and/or optoelectronic device which is a photovoltaic cell, a light emitting device, an electrochromic or photo-electrochromic device, an
• electrochemical sensor and/or biosensor comprising an electrolyte formulation comprising at least one compound of formula (I)
• Kt + is an organic cation selected from the group of,
• R 1 to R 0 each, independently of one another, denote
• straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds which optionally may be fluorinated or perfluorinated, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds which optionally may be fluorinated or perfluorinated or straight-chain or branched alkoxyalkyl having 2 to 8 C atoms.
• the device of the present invention is a dye or quantum dot sensitized solar cell, particularly preferably a dye sensitized solar cell.
• Quantum dot sensitized solar cells are disclosed in US 6,861 ,722, for example.
• a dye is used to absorb the sunlight to convert into the electrical energy. Examples of dyes are disclosed in EP 0 986 079 A2, EP 1 180 774 A2 or EP 1 507 307 A1.
• Preferred dyes are organic dyes such as MK- , MK-2 or MK-3 (its
• Y123 (CAS no. 1312465-92-1), bipyridin-Ruthenium dyes such as N3 (CAS no. 141460-19-7), N719 (CAS no. 207347-46-4), Z907 (CAS no. 502693- 09-6), C101 (CAS no. 1048964-93-7), C106 (CAS no. 1152310-69-4), K19 (CAS no. 847665-45-6) or terpyridine-Ruthenium dyes such as N749 (CAS no. 359415-47-7).
• bipyridin-Ruthenium dyes such as N3 (CAS no. 141460-19-7), N719 (CAS no. 207347-46-4), Z907 (CAS no. 502693- 09-6), C101 (CAS no. 1048964-93-7), C106 (CAS no. 1152310-69-4), K19 (CAS no. 847665-45-6) or terpyridine-Ruthenium dyes such as N749 (CAS no. 359415-
• Particularly preferred dyes are Z907 or Z907Na which are both an amphiphilic ruthenium sensitizer.
• the dye is coadsorbed with a phosphinic acid.
• a preferred example of a phosphinic acid is bis(3,3-dimethyl-butyl)-phosphinic acid (DINHOP) as disclosed in M. Wang et al, Dalton Trans., 2009, 10015- 10020.
• the dye Z907Na means NaRu(2,2'-bipyridine-4-carboxylic acid-4'- carboxylate)(4,4'-dinonyl-2,2'-bipyridine)(NCS) 2 .
• a dye-sensitized solar cell comprises a photo-electrode, a counter electrode and, between the photo-electrode and the counter electrode, an electrolyte formulation or a charge transporting material, and wherein a sensitizing dye is absorbed on the surface of the photo-electrode, on the side facing the counter electrode.
• the device comprises a semiconductor, the electrolyte formulation as described above and a counter electrode.
• the semiconductor is based on material selected from the group of Si, Ti0 2 , Sn02, Fe 2 0 3 , W0 3 , ZnO, Nb 2 0 5 , CdS, ZnS, PbS, Bi 2 S 3 , CdSe, GaP, InP, GaAs, CdTe, CulnS 2 , and/or CulnSe 2 .
• the semiconductor comprises a mesoporous surface, thus increasing the surface optionally covered by a dye and being in contact with the electrolyte.
• the semiconductor is present on a glass support or plastic or metal foil.
• the support is conductive.
• the device of the present invention preferably comprises a counter electrode.
• a counter electrode for example, fluorine doped tin oxide or tin doped indium oxide on glass (FTO- or ITO-glass, respectively) coated with Pt, carbon of preferably conductive allotropes, polyaniline or poly (3,4- ehtylenedioxythiophene) (PEDOT).
• Metal substrates such as stainless steel or titanium sheet may be possible substrates beside glass.
• the device of the present invention may be manufactured as the
• the DSC does not require high conductivity of the liquid electrolyte.
• the sensitized semiconducting material serves as a photoanode.
• the counter electrode is a cathode.
• the present invention provides a method for preparing a photoelectric cell comprising the step of bringing the electrolyte formulation of the invention in contact with a surface of a semiconductor, said surface optionally being coated with a sensitizer.
• the semiconductor is selected from the materials given above, and the sensitizer is preferably selected from quantum dots and/or a dye as disclosed above, particularly preferably selected from a dye.
• the electrolyte formulation may simply be pured on the semiconductor.
• it is applied to the otherwise completed device already comprising a counter electrode by creating a vacuum in the internal lumen of the cell through a hole in the counter electrode and adding the electrolyte formulation as disclosed in the reference of Wang et al., J. Phys. Chem. B 2003, 107, 14336.
• Ethyl-3-methylimidzolium tetracyanoborate and 1-ethyl-3- methylimidazolium fluorotricyanoborate are synthesized according to WO 2004/072089, examples 9 and 12 and E. Bernhardt et al., Z. Anorg. Allg. Chem., 2003, 629, 677-685.
• Table 1 gives specific parameters of the ionic liquids used:
• electrolyte formulations are synthesized to demonstrate the unexpected advantage of electrolyte formulations according to the invention relative to electrolyte formulations of the prior art containing emim TCB.
• the electrolyte formulations are prepared through mixing of one or more of 1 ,3-dimethylimidazolium iodide (mmiml), 1-ethyl-3-methylimidazolium iodide (emiml) and 1-methyl-3-propylimidazolium iodide (pmiml), 1 -alIyl-3- methylimidazolium iodide (amim I), 1-hydroxymethyl-3-methylimidazolium iodide (mohmim I), 1 , -dimethylpyrrolidinium iodide (mmpll),
• Electrolyte 1 given in the molar ratio:
• Electrolyte 2 given in the molar ratio:
• Electrolyte 3 given in the molar ratio:
• Electrolyte 6 given in the molar ratio:
• Electrolyte 7 given in the molar ratio:
• Electrolyte 8 given in the molar ratio:
• Electrolyte 9 given in the molar ratio:
• Electrolyte 12 given in the molar ratio:
• Electrolyte 13 given in the molar ratio:
• Electrolyte 16 given in the molar ratio: 36 mmim I, 8 pmim I, 12 amim I, 8 hmim I, 8 mmpl I, 72 emim
• the dye sensitized solar cells are fabricated as disclosed in US 5,728,487 or WO 2007/093961 :
• a double-layer, mesoporous TiO 2 electrode was prepared as disclosed in Wang P et al., J. Phys. Chem. B 2003, 107, 14336, in particular page 14337, in order to obtain a photoanode consisting of a double layer structure.
• a transparent nanoporous TiO 2 electrode a screen printing paste containing terpineol solvent and nanoparticulate TiO 2 of anatase phase with 20 nm diameter was deposited on a transparent conductive substrate to 5 mm x 5 mm squared shape by using a hand printer. The paste was dried for 10 minutes at 120 degrees Celsius.
• Another screen printing paste containing TiO 2 with 400 nm diameter was then deposited on top of the nanoporous layer to prepare an opaque layer.
• the double layer film was then sintered at 500 degrees Celsius for an hour with the result of an underlying transparent layer (7 microns thick) and a top opaque layer (4 microns thick).
• the electrode was immersed in 40 mM aqueous solution of TiCI 4 (Merck) for 30 minutes at 70 degrees Celsius and then rinsed with pure water sufficiently.
• TiCI 4 -treated electrode was dried at 500 degrees Celsius for 30 minutes just before dye sensitization.
• the counter electrode was prepared with thermal pyrolysis method as disclosed in the reference above.
• a droplet of 5 mM solution of platinic acid (Merck) was casted at 8 ⁇ / ⁇ 2 and dried on a conductive substrate.
• the dye sensitized solar cell was assembled by using 30 micron thick Bynel (DuPont, USA) hot-melt film to seal up by heating. The internal space was filled with each of the electrolyte
• the dye Z907 is an amphiphilic ruthenium sensitizer Ru(2,2'-bipyridine 4,4'- dicarboxylic acid) (4,4'-dinonyl-2,2'-bipyridine)(NCS) 2 or
• photomask of 4 mm x 4 mm is placed on top of the devices fabricated according to example 3 to define the light projection area.
• the cell gap is in the range of 25 to 30 micron.
• Energy conversion efficiency is generally the ratio between the useful output of an energy conversion machine and the input of light radiation, in energy terms, determined by using adjustable resistant load to optimize the electric power output.
• Table 2 documents that electrolytes comprising fluorotricyanoborate as anion perform better or equal than electrolytes comprising TCB as anion if the same cation is used.
• the measurements of Electrolytes 2, 3, 7 and 8 and 10, 11, 15 and 16 were again repeated to confirm this statement.
• Example 3 repetition of some electrolytes mentioned above in
• Electrolyte 2 given in the molar ratio:
• Electrolyte 3 given in the molar ratio:
• Electrolyte 7 given in the molar ratio:
• Electrolyte 8 given in the molar ratio:
• Table 3 summarizes the results of the measurements of the above cited electrolyte formulations according to Example 2 with 0.3 mM 2907 as dye
• Table 4 summarizes the results of the measurements of the above cited electrolyte formulations according to Example 2 with 0.3 mM Z907 as dye and 0.075mM DINHOP

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