WO2004095481A1 - Photoelectrochemical solar cell made from nanocomposite organic-inorganic materials - Google Patents
Photoelectrochemical solar cell made from nanocomposite organic-inorganic materials Download PDFInfo
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- WO2004095481A1 WO2004095481A1 PCT/GR2004/000023 GR2004000023W WO2004095481A1 WO 2004095481 A1 WO2004095481 A1 WO 2004095481A1 GR 2004000023 W GR2004000023 W GR 2004000023W WO 2004095481 A1 WO2004095481 A1 WO 2004095481A1
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 12
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 9
- 239000011147 inorganic material Substances 0.000 title claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000011521 glass Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 6
- 230000005611 electricity Effects 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 13
- 239000000499 gel Substances 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 238000003797 solvolysis reaction Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims 2
- 238000005520 cutting process Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 239000011343 solid material Substances 0.000 claims 1
- 238000003892 spreading Methods 0.000 claims 1
- 230000002459 sustained effect Effects 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- 238000001311 chemical methods and process Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000013504 Triton X-100 Substances 0.000 description 4
- 229920004890 Triton X-100 Polymers 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- -1 silicon alkoxide Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000089 atomic force micrograph Methods 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- ZVZFHCZCIBYFMZ-UHFFFAOYSA-N 6-methylheptoxybenzene Chemical compound CC(C)CCCCCOC1=CC=CC=C1 ZVZFHCZCIBYFMZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- 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
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- 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
Definitions
- the present invention refers to the construction of a Photoelectrochemical Solar Cell (henceforth called PECSC) of solid type, based on new nanocomposite organic- inorganic materials, which, in their majority, are deposited by purely chemical processes under ambient conditions, aiming at its use for photovoltaic applications, that is for converting Solar Energy into Electrical Energy (henceforth PV, or PV conversion) and, generally, for the conversion of light signals into electrical signals.
- PECSC Photoelectrochemical Solar Cell
- the scientific background of the invention belongs to the discipline of Physics and Chemistry while its technological applications belong to the Energy Sector and to the Electronics Sector, since a PV device is an optoelectronic sensor of light.
- PECSC Photoelectrochemical Solar Cell
- the present invention uses new improved materials made by different processes from those of the above-mentioned patent. Specifically, in the present invention a different process is used for the synthesis and deposition of titanium dioxide. In the present invention, the active surface of TiO 2 is increased, accordingly increasing the quantity of the adsorbed organic photosensitizer and the overall efficiency of the cell. Corresponding efficiency increase is achieved also by the use of a solid gel electrolyte where solvents are incorporated in the structure of the electrolyte that enhance electric conductivity. Explanation of the drawings and short description of the cell.
- Drawing 1 shows a crossectional view of the proposed PECSC: (1) Negative electrode made of transparent electroconductive glass; (2) Film of mesoporous titania with adsorbed dye; (3) Solid gel containing redox couple; (4) Positive electrode made of transparent electroconductive glass with deposited thin platinum layer.
- Drawing 2 shows flat and three-dimensional AFM image of a titania film.
- Drawing 3 shows adsorption spectrum of a titania film without (1) and with (2) adsorbed dye (its structure appears in the insert), and Drawing 4 shows an I-V characteristic curve of the PECSC.
- the cell consists of the following parts, which appear in the crossectional drawing #1: (1) A glass plate with deposited thin transparent film of Tin Dioxide doped with fluorine (SnO 2 :F), which gives glass surface electroconductive properties and which is commercially available, or a glass plate with deposited thin transparent film of Indium Oxide doped with Tin (ITO), which is commercially available, or any other type of transparent electroconductive plate which is commercially available and which provides electric conductivity with surface resistance ⁇ 100 Ohm, preferably ⁇ 20 Ohm; (2) A layer of titanium dioxide (TiO 2 ) of mesoporous structure, made of nanocrystalls of anatase or mixture of anatase and rutile, in the form of thin transparent film of controlled thickness, which is synthesized and deposited by chemical processes, as described below.
- SiO 2 Tin Dioxide doped with fluorine
- ITO Indium Oxide doped with Tin
- a commercially available organometallic ruthenium complex ct5-bis(isotMocyanato)bis(2,2 , -bipyridyl-4,4'-dicarboxylato)-ruthenium(II) ( cf. insert of drawing #3), which acts as a photosensitizer of TiO 2 , is adsorbed, by dipping in a solution of the complex; (3) a layer of solid gel electrolyte, made by the sol-gel route as described below; and (4) a second SnO 2 :F plate or ITO or any other transparent electroconductive plate, same as that of component #1, which makes the second electrode that completes the cell.
- a thin layer of platinum (Pt) can be deposited by thermal evaporation under vacuum, which acts as a catalyst increasing cell efficiency.
- the transparent conductive glass plates which are used as substrates in the construction of the PECSC, are cut into the desired dimensions from a commercially available larger sample. Their cleaning is made in an ultrasonic bath, usually of alcohol. Cleaning process lasts about 30 min. Then the glasses are dried by blowing dry clean air or dry clean inert gas. Two such glass plates are used as substrate positive and negative electrodes.
- One of the two clean transparent conductive electrodes will be used as positive electrode or, alternatively, will be covered by a thin platinum layer, which is deposited by thermal evaporation under vacuum (appr. 10 " Torr).
- the Pt layer can be very thin so as the cell to be semi-transparent and thus to be used in PV windows. It can also be deposited as a thick opaque reflective layer, so as to increase the probability of photon absorption by the photosensitizer. In that case, the cell is opaque and acts exclusively as PV cell.
- Deposition of mesoporous TiO? film Deposition of thin Titania (TiO 2 ) films on the transparent conductive glass electrode is made by purely chemical processes by employing a colloidal solution where controlled solvolysis and polymerization of titanium isopropoxide takes place. Specifically, in a premeasured volume of ethanol, we add a premeasured quantity of a surfactant by the commercial name Triton X-100 [polyoxyethylene-(l ⁇ ) isooctylphenyl ether], or other surfactant of the Triton family, or any other surfactant of any other category, preferably non-ionic, at a weight percentage that varies according to the chosen composition.
- Triton X-100 polyoxyethylene-(l ⁇ ) isooctylphenyl ether
- any other surfactant of any other category preferably non-ionic
- the same material can be deposited by centrifugation or by simple casting.
- the film is left to dry under ambient conditions and then it is introduced into a warm oven, where it is calcined at 550°C for 10 min. Heating at such high temperature results in burning all organic content so that the remaining film consists only of TiO 2 nanoparticles.
- the process of dipping and calcination is repeated a few more times, producing successive titanium dioxide layers, till a satisfactory thickness is achieved.
- Thin films are completely transparent while thick films might become opaque, due to extensive scattering of light. Films made by the above procedure consist of TiO 2 nanoparticles of 10-30 nm average diameter.
- the characterization was made by microscopy methods, such as Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM), already mentioned above.
- SEM Scanning Electron Microscopy
- TEM Transmission Electron Microscopy
- AFM Atomic Force Microscopy
- Such an AFM image is attached (Drawing #2).
- Application of the film is made only on the one (conductive) side of the glass plate. For this reason, in case of dipping, the other side is temporarily covered by a protective tape.
- Attachment of the dye on the TiO 2 surface is made by chemical bonding by means of the carboxylate groups and is achieved after adsorption on titania nanocrystallites, for example, by dipping in an ethanolic solution of the dye. Adsorption is verified by absorption spectrophotometry. Under the above conditions, maximum optical density of the TiO 2 /photosensitizer system reached with transparent titania films is 0.80, that corresponds to 84% absorption of incident light, at the absorption maximum (cf. Drawing #3). This percentage can be increased or decreased by controlling thickness of TiO 2 films. At any rate, this percentage is the maximum internationally achieved for transparent titania films and it owes to the synthesis and deposition method used, as described above. This method endows titania films with extensive porous structure and active surface towards adsorption and bonding of the photosensitizer molecules.
- the thus prepared electrode makes the negative electrode of the Solar Cell.
- Such substances are either surfactants or ethyleneglycol oligomers or polymers, incorporated either by simple mixture or by chemical bonding with the -O-M-O- network.
- an organic solvent which is also incorporated in the gel, takes part in the formation of the organic subphase and allows increase of ionic conductivity.
- a redox couple is added to the colloidal solution, I 3 7T by preference. This couple is produced in the presence of I 2 and of an iodide salt XI, where X + is an elemental or an organic cation.
- the colloidal solution slowly gels after AcOH addition.
- AcOH acts as a gel-control factor through ester formation M-O-Ac (cf. U. Lavrencic-Stangar, B.
- Example 1 As a substrate for deposition of titania film we used a glass plate bearing a SnO 2 :F layer (negative electrode). As a substrate for deposition of a thin layer of platinum we used a glass plate bearing a SnO 2 :F layer (positive electrode). On the positive electrode we deposit by thermal evaporation under vacuum a semi- transparent Pt layer of a thickness of about 200nm. On the negative electrode we deposit the colloidal solution from which the titania film will be produced after calcination. The colloidal solution is made as follows: 3g EtOH are mixed with 0.71g Triton X-100. Then we add 0.64g AcOH and 0.36g Titanium Isopropoxide under vigorous stirring and ambient conditions.
- TMOS Tetramethoxysilane
- TMOS i.e. Si(OCH 3 ) 4
- 0.05M I 2 and 0.5M KI the mixture is continuously stirred for 12 hours. Then it is ready to be applied.
- the PECSC is completed with the attachment of the positive electrode which is simply done by pressing by hand the two electrodes against each other, sandwiching between them the above mixture. Electric conducts are made using silver paste. For this reason, a small part of the negative electrode is protected against TiO 2 deposition so as to make contact which underlying the Sn ⁇ 2 :F layer.
- Example 2 A PECSC with the same components, as that of Example 1, the same proportions of the employed reagents and the same methods of preparation but propylene carbonate been substituted by a 1:1 mixture of propylene carbonate and ethylene carbonate, under illumination by simulated Solar Radiation of 100 mW/cm 2 , produces 11.6 mA/cm 2 short circuit current, 0.62 volts open circuit voltage, fill factor 0.69 and overall efficiency 5.0%.
- Example 3 A PECSC with the same components, the same proportion of used reagents and the same preparation procedures as those used in Example 1 but with propylene carbonate been substituted by poly(ethyleneglycol)-200, when illuminated by simulated Solar Radiation of 100 mW/cm 2 , produces 12.4 mA/cm 2 short circuit current, 0.61 volts open circuit voltage, fill factor 0.7 and overall efficiency 5.3%.
- Example 4 A PECSC with the same components, the same proportion of used reagents and the same preparation procedures as those used in Example 1, but propylene carbonate been substituted by propylene carbonate containing a few drops of pyridine, when illuminated by simulated Solar Radiation of 100 mW/cm 2 , produces 8.4 mA/cm 2 short circuit current, 0.69 volts open circuit voltage, fill factor 0.68 and overall efficiency 3.9%.
- Example 5 A PECSC with the same components, the same proportion of used reagents and the same preparation procedures as those used in Example 1, but KI been substituted by l-memyl-3-propylimidazolium iodide, when illuminated by simulated Solar Radiation of 100 mW/cm 2 , produces 12,9 mA/cm 2 short circuit current, 0.65 volts open circuit voltage, fill factor 0.66 and overall efficiency 5.4%.
- Example 6 The components of the cell, the proportion of the employed reagents and the preparation procedures are the same as for Example 1 but the sol which contains the redox couple is made under the following procedure: 0.75g Ureasil 230, a bis- triethoxysilane precursor by the chemical formula
- Example 7 In the examples 1-6, the SnO 2 :F glasses are substituted by ITO glasses. The obtained cells have an overall efficiency of about 20% less than those made of SnO 2 :F glasses.
- Example 8 In the examples 1-6, we change the procedure of deposition of TiO 2 films by modifying the Triton X-100 content in the original sol. The mesoporous structure of nanocrystalline titania is affected and this affects adsorption capacity towards the dye photosensitizer. Optimum results are obtained with the surfactant content employed in Examples 1-6
- the above PECSC can be used as an independent energy source for supplying isolated devices or by connection to the Electricity Network.
- Low energy consumption apparatus such as quartz watches or small calculators can be powered by a combination of small size cells.
- the above PECSC can be also used as light sensor where the presence of light is signaled by an electric signal. The semi-transparency of the cell allows it to be applied as photovoltaic window.
Abstract
We describe the structure of a solid photoelectrochemical solar cell which consists of thin layers of nanocomposite organic-inorganic materials and can be used for converting solar energy into electricity. Main components of the cell, whose cross section is shown in Drawing # 1 is: (1) a commercially available transparent electroconductive glass plate; (2) a mesoporous nanocrystalline titanium dioxide layer in the form of a thin transparent film of controlled thickness, which is synthesized and deposited by chemical processes, as described above. On this layer a commercially available ruthenium organometallic complex is attached, which acts as a photosensitizer of TiO2; (3) a layer of a solid gel electrolyte made of a nanocomposite organic-inorganic material incorporating I2 and I-, synthesized by chemical procedures as above described; and (4) a positive electrode made of commercially available electroconductive glass plate, where a thin layer of platinum may be deposited, which completes the cell.
Description
PHOTOE ECTROCHEMICAL SOLAR CELL MADE FROM NANOCOMPOSITE ORGANIC-INORGANIC MATERIALS
Introduction The present invention refers to the construction of a Photoelectrochemical Solar Cell (henceforth called PECSC) of solid type, based on new nanocomposite organic- inorganic materials, which, in their majority, are deposited by purely chemical processes under ambient conditions, aiming at its use for photovoltaic applications, that is for converting Solar Energy into Electrical Energy (henceforth PV, or PV conversion) and, generally, for the conversion of light signals into electrical signals. The scientific background of the invention belongs to the discipline of Physics and Chemistry while its technological applications belong to the Energy Sector and to the Electronics Sector, since a PV device is an optoelectronic sensor of light. There are already known versions of PECSC, as those published in international journals (cf. O'Reagan,B.; Graetzel, M. Nature, 1991, 353,737 και Nazeeruddin,M.K.; Kay, A.; Rodicio .; Humphry-Baker,R.; Mueller,E.; Liska,P.; Vlachopoulos,N.; GraetzeLM.; J.Am.Chem. Soc. 1993, 115, 6382). These above works refer to a liquid cell with solid electrodes, where the synthesis methods and the type of materials used are different from those of the present invention. The present invention refers to a totally solid cell deposited in the form of a multilayer film. It is also an evolution from a cell that has been published in international journals (cf. E. Stathatos, P. Lianos, U. Lavrencic-Stangar, B. Orel, Adv.Mater., 2002, 14, No5, 354) and is protected by a former Greek patent (OBI, No. 1003816). The present invention uses new improved materials made by different processes from those of the above-mentioned patent. Specifically, in the present invention a different process is used for the synthesis and deposition of titanium dioxide. In the present invention, the active surface of TiO2 is increased, accordingly increasing the quantity of the adsorbed organic photosensitizer and the overall efficiency of the cell. Corresponding efficiency increase is achieved also by the use of a solid gel electrolyte where solvents are incorporated in the structure of the electrolyte that enhance electric conductivity.
Explanation of the drawings and short description of the cell.
Drawing 1 shows a crossectional view of the proposed PECSC: (1) Negative electrode made of transparent electroconductive glass; (2) Film of mesoporous titania with adsorbed dye; (3) Solid gel containing redox couple; (4) Positive electrode made of transparent electroconductive glass with deposited thin platinum layer. Drawing 2 shows flat and three-dimensional AFM image of a titania film. Drawing 3 shows adsorption spectrum of a titania film without (1) and with (2) adsorbed dye (its structure appears in the insert), and Drawing 4 shows an I-V characteristic curve of the PECSC.
Follows a short description of the proposed solar cell. The cell consists of the following parts, which appear in the crossectional drawing #1: (1) A glass plate with deposited thin transparent film of Tin Dioxide doped with fluorine (SnO2:F), which gives glass surface electroconductive properties and which is commercially available, or a glass plate with deposited thin transparent film of Indium Oxide doped with Tin (ITO), which is commercially available, or any other type of transparent electroconductive plate which is commercially available and which provides electric conductivity with surface resistance <100 Ohm, preferably <20 Ohm; (2) A layer of titanium dioxide (TiO2) of mesoporous structure, made of nanocrystalls of anatase or mixture of anatase and rutile, in the form of thin transparent film of controlled thickness, which is synthesized and deposited by chemical processes, as described below. On this titania layer, a commercially available organometallic ruthenium complex, ct5-bis(isotMocyanato)bis(2,2,-bipyridyl-4,4'-dicarboxylato)-ruthenium(II) ( cf. insert of drawing #3), which acts as a photosensitizer of TiO2, is adsorbed, by dipping in a solution of the complex; (3) a layer of solid gel electrolyte, made by the sol-gel route as described below; and (4) a second SnO2:F plate or ITO or any other transparent electroconductive plate, same as that of component #1, which makes the second electrode that completes the cell. Alternatively, on this second electrode, a thin layer of platinum (Pt) can be deposited by thermal evaporation under vacuum, which acts as a catalyst increasing cell efficiency.
Detailed description of each part, chemical syntheses and construction of the cell
Preparation of the electroconductive transparent plates that are used as electrodes. The transparent conductive glass plates, which are used as substrates in the construction of the PECSC, are cut into the desired dimensions from a commercially available larger sample. Their cleaning is made in an ultrasonic bath, usually of alcohol. Cleaning process lasts about 30 min. Then the glasses are dried by blowing dry clean air or dry clean inert gas. Two such glass plates are used as substrate positive and negative electrodes.
Preparation of the positive electrode. One of the two clean transparent conductive electrodes will be used as positive electrode or, alternatively, will be covered by a thin platinum layer, which is deposited by thermal evaporation under vacuum (appr. 10" Torr). The Pt layer can be very thin so as the cell to be semi-transparent and thus to be used in PV windows. It can also be deposited as a thick opaque reflective layer, so as to increase the probability of photon absorption by the photosensitizer. In that case, the cell is opaque and acts exclusively as PV cell.
Deposition of mesoporous TiO? film. Deposition of thin Titania (TiO2) films on the transparent conductive glass electrode is made by purely chemical processes by employing a colloidal solution where controlled solvolysis and polymerization of titanium isopropoxide takes place. Specifically, in a premeasured volume of ethanol, we add a premeasured quantity of a surfactant by the commercial name Triton X-100 [polyoxyethylene-(lθ) isooctylphenyl ether], or other surfactant of the Triton family, or any other surfactant of any other category, preferably non-ionic, at a weight percentage that varies according to the chosen composition. Then we add an excess of acetic acid (AcOH) and, finally, a premeasured volume of titanium isopropoxide, under vigorous stirring. All above reagents are commercial. The evolution of the above mixture is conversion into a gel (sol-gel process) through chemical reactions that lead to solvolysis and inorganic polymerization of titanium isopropoxide, that is, formation of -O-Ti-O- networks. Before completion of this procedure and while formation of TiO2 oligomers is advanced, the conductive glass plate is dipped into the above colloidal solution and withdrawn at constant and controlled speed, resulting in
formation of a homogeneous film made of nanocomposite organic-inorganic material. Alternatively, the same material can be deposited by centrifugation or by simple casting. The film is left to dry under ambient conditions and then it is introduced into a warm oven, where it is calcined at 550°C for 10 min. Heating at such high temperature results in burning all organic content so that the remaining film consists only of TiO2 nanoparticles. The process of dipping and calcination is repeated a few more times, producing successive titanium dioxide layers, till a satisfactory thickness is achieved. Thin films are completely transparent while thick films might become opaque, due to extensive scattering of light. Films made by the above procedure consist of TiO2 nanoparticles of 10-30 nm average diameter. The characterization was made by microscopy methods, such as Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM), already mentioned above. Such an AFM image is attached (Drawing #2). Application of the film is made only on the one (conductive) side of the glass plate. For this reason, in case of dipping, the other side is temporarily covered by a protective tape.
Presentation and deposition of the organic photosensitizer. TiO? nanocrystallites absorb light only in the Near UV, therefore it is necessary to photosensitize it in the visible, in order to exploit visible light. For this reason we use a commercially available organometallic dye which has been proven to have a satisfactory capacity of injecting, when excited, electrons into the conduction band of TiO2. We propose a ruthenium complex with the chemical structure -bis(isothiocyanato)bis(2,2'- bipyridyl-4,4,-dicarboxylato)-ruthenium(II) (cf. insert of drawing #3). Attachment of the dye on the TiO2 surface is made by chemical bonding by means of the carboxylate groups and is achieved after adsorption on titania nanocrystallites, for example, by dipping in an ethanolic solution of the dye. Adsorption is verified by absorption spectrophotometry. Under the above conditions, maximum optical density of the TiO2/photosensitizer system reached with transparent titania films is 0.80, that corresponds to 84% absorption of incident light, at the absorption maximum (cf. Drawing #3). This percentage can be increased or decreased by controlling thickness of TiO2 films. At any rate, this percentage is the maximum internationally achieved for transparent titania films and it owes to the synthesis and deposition method used, as described above. This method endows titania films with extensive porous structure
and active surface towards adsorption and bonding of the photosensitizer molecules. The thus prepared electrode makes the negative electrode of the Solar Cell.
Presentation of the nanocomposite organic-inorganic gel. Synthesis and deposition of the gel electrolyte. The electrolyte we propose to intervene between the two electrodes already described, in order to close the circuit and complete the cell is the following: we must prepare a colloidal solution which contains a silicon alkoxide, or a titanium alkoxide or an alkoxide of another metal, which in the presence of AcOH and ambient humidity is polymerized yielding a -O-M-O- network, where M is a metal or Si. Gel formation is due to (inorganic) polymerization -O-M-O-. In the colloidal solution we add an organic material which is incorporated in the gel and forms an organic subphase, which provides ionic conductivity. Such substances are either surfactants or ethyleneglycol oligomers or polymers, incorporated either by simple mixture or by chemical bonding with the -O-M-O- network. In addition, we add an organic solvent, which is also incorporated in the gel, takes part in the formation of the organic subphase and allows increase of ionic conductivity. Finally, a redox couple is added to the colloidal solution, I37T by preference. This couple is produced in the presence of I2 and of an iodide salt XI, where X+ is an elemental or an organic cation. The colloidal solution slowly gels after AcOH addition. AcOH acts as a gel-control factor through ester formation M-O-Ac (cf. U. Lavrencic-Stangar, B. Orel, Adv.Mater., 2002, 14, No5, 354; E. Stathatos, P. Lianos, B.Orel, A.Surca Vuk and R. Jesse, Langmuir, 2003, 19, 7587) or through slow water production by interaction between AcOH and alcohol.
Completion of the Cell. When gelling of the above solution is sufficiently advanced but while it is still a fluid, one drop is cast on the negative electrode (i.e. the glass plate that bears the titania and the adsorbed dye). Then the two electrodes are brought in contact by squeezing them together. The material is spread over the whole active surface of the electrodes. As gelling is completed, the two electrodes are strongly held together and they are not detached even under stress. Attachment is obtained by -O- M-O- bonds. Electric contacts with the two electrodes are obtained by electroconductive paste, or by epoxy paste enriched with silver grains or by copper adhesive tape, all commercially available.
Examples of PECSC's
Example 1. As a substrate for deposition of titania film we used a glass plate bearing a SnO2:F layer (negative electrode). As a substrate for deposition of a thin layer of platinum we used a glass plate bearing a SnO2:F layer (positive electrode). On the positive electrode we deposit by thermal evaporation under vacuum a semi- transparent Pt layer of a thickness of about 200nm. On the negative electrode we deposit the colloidal solution from which the titania film will be produced after calcination. The colloidal solution is made as follows: 3g EtOH are mixed with 0.71g Triton X-100. Then we add 0.64g AcOH and 0.36g Titanium Isopropoxide under vigorous stirring and ambient conditions. After 30 min stirring a drop of this colloidal solution is placed on the negative electrode and it is stretched over the film by using a glass blade. After drying for five minutes, it is introduced in a preheated oven and it is calcined at 550°C for ten minutes. Then we take it out from the oven and we let it cool at ambient conditions. This procedure is repeated ten times. In this way we obtain a thin transparent film of about l-2μm thick. The titania film thus obtained is mesoporous and it has the structure seen in the attached AFM image (drawing #2). Then the film is dipped into an ethanol solution of czs-bis(isothiocyanato)bis(2,2'- bipyridyl-4,4'-dicarboxylato)-ruthenium(II) at concentration 5xl0"5M. The dye is adsorbed and attached on the titania mesoporous film which becomes colored. The related absorption spectrum is presented in drawing #3. Maximum absorbance in the visible is 0.80 (84%). On this electrode we then place one drop of the fluid gel that bears the redox couple. This sol is prepared under ambient conditions as follows: 1.5ml propylene carbonate are mixed with 1 ml Triton X-100. Then we add 0.35g Tetramethoxysilane [abbreviated TMOS, i.e. Si(OCH3)4] and 0.65ml AcOH under vigorous stirring. Last, we add 0.05M I2 and 0.5M KI and the mixture is continuously stirred for 12 hours. Then it is ready to be applied. The PECSC is completed with the attachment of the positive electrode which is simply done by pressing by hand the two electrodes against each other, sandwiching between them the above mixture. Electric conducts are made using silver paste. For this reason, a small part of the negative electrode is protected against TiO2 deposition so as to make contact which underlying the Snθ2:F layer. When the above cell is illuminated by simulated solar radiation of an intensity of 100 mW/cm2, it produces a short circuit current of
11.8mA/cm2 an open circuit voltage of 0.60volts, with a fill factor of 0.69 and overall efficiency 4.9%.
Example 2 A PECSC with the same components, as that of Example 1, the same proportions of the employed reagents and the same methods of preparation but propylene carbonate been substituted by a 1:1 mixture of propylene carbonate and ethylene carbonate, under illumination by simulated Solar Radiation of 100 mW/cm2, produces 11.6 mA/cm2 short circuit current, 0.62 volts open circuit voltage, fill factor 0.69 and overall efficiency 5.0%.
Example 3 A PECSC with the same components, the same proportion of used reagents and the same preparation procedures as those used in Example 1 but with propylene carbonate been substituted by poly(ethyleneglycol)-200, when illuminated by simulated Solar Radiation of 100 mW/cm2, produces 12.4 mA/cm2 short circuit current, 0.61 volts open circuit voltage, fill factor 0.7 and overall efficiency 5.3%.
Example 4 A PECSC with the same components, the same proportion of used reagents and the same preparation procedures as those used in Example 1, but propylene carbonate been substituted by propylene carbonate containing a few drops of pyridine, when illuminated by simulated Solar Radiation of 100 mW/cm2, produces 8.4 mA/cm2 short circuit current, 0.69 volts open circuit voltage, fill factor 0.68 and overall efficiency 3.9%.
Example 5 A PECSC with the same components, the same proportion of used reagents and the same preparation procedures as those used in Example 1, but KI been substituted by l-memyl-3-propylimidazolium iodide, when illuminated by simulated Solar Radiation of 100 mW/cm2, produces 12,9 mA/cm2 short circuit current, 0.65 volts open circuit voltage, fill factor 0.66 and overall efficiency 5.4%.
Example 6 The components of the cell, the proportion of the employed reagents and the preparation procedures are the same as for Example 1 but the sol which contains the redox couple is made under the following procedure: 0.75g Ureasil 230, a bis- triethoxysilane precursor by the chemical formula
is mixed with l,75g sulfolane.
Then we add 0.7g AcOH and 0.05M I2 + 0.5M KI under vigorous stirring. After 24 hours stirring the colloidal solution is ready for application. The obtained cell, when illuminated by simulated Solar Radiation of 100 mW/cm2, produces 13,9 mA cm2 short circuit current, 0.64 volts open circuit voltage, fill factor 0.70 and overall efficiency 5.3%. The corresponding I-V curve is shown in drawing #4.
Example 7. In the examples 1-6, the SnO2:F glasses are substituted by ITO glasses. The obtained cells have an overall efficiency of about 20% less than those made of SnO2:F glasses.
Example 8. In the examples 1-6, we change the procedure of deposition of TiO2 films by modifying the Triton X-100 content in the original sol. The mesoporous structure of nanocrystalline titania is affected and this affects adsorption capacity towards the dye photosensitizer. Optimum results are obtained with the surfactant content employed in Examples 1-6
Applications
The above PECSC can be used as an independent energy source for supplying isolated devices or by connection to the Electricity Network. Low energy consumption apparatus, such as quartz watches or small calculators can be powered by a combination of small size cells. The above PECSC can be also used as light sensor where the presence of light is signaled by an electric signal. The semi-transparency of the cell allows it to be applied as photovoltaic window.
Claims
1. A method of construction of a photoelectrochemical solar cell made from and of nanocomposite organic-inorganic materials, deposited as fluid gels, subsequently, transformed into solid gels, composed into a self sustained photovoltaic apparatus for production of electric energy, which method consists of the following steps: [1] cutting a transparent electroconductive SnO2:F, or ITO or other electrode from a commercially available plate [2] deposition on this electrode of a mesoporous nanocrystalline TiO2 film, either of anatase or a mixture of anatase with rutile, by using the following procedures: (a) solvolysis and polymerization of titanium isopropoxide without added water in the presence of an organic acid and a surfactant which acts as template; (b) deposition of the material "a" as nanocomposite organic- inorganic film on the transparent electroconductive glass; (c) calcination of the above material at high temperature; and (d) adsorption of the ruthenium organometallic complex cz5-bis(isothiocyanato)bis(2,2,-bipyridyl-4,4'- dicarboxylato)-ruthenium(H) or any other equivalent commercially available substance which acts as a photosensitizer of titanium dioxide; [3] Synthesis of the gel containing a redox couple which will be deposited on the TiQ∑/dye surface. This gel electrolyte consists of a nanocomposite organic-inorganic material incorporating I2 and an iodide salt which is synthesized by solvolysis and polymerization of derivatives of alkoxysilanes or alkoxytitanates or of alkoxides of other metals, according to the sol-gel method in the absence of water, in the presence of organic acid and, possibly, in the presence of surfactant and organic solvents; and [4] deposition of a drop of the gel of the step 3, while it is still a fluid on the top of the electrode supporting the
TiO /dye system and then sandwiching and spreading it between the above and the counter electrode, where, by choice, a thin layer of Pt can be deposited.
2. A photoelectrochemical solar cell composed of nanocomposite organic- inorganic materials, made by the steps and the procedures of claim 1, composed into a self-sustained photovoltaic device that transforms light energy into electric energy. The proposed device is an improved version compared to former types of photoelectrochemical solar cells since: (1) it is composed of solid materials; (2) it contains a layer of nanocrystalline TiO2 with small size nanocrystallites of high active area made in the way described in claim 1; and (3) uses a nanocomposite organic-inorganic gel electrolyte synthesized as described in claim 1.
3. Use of the photoelectrochemical solar cell of claim 2 as a self-sustained device for the conversion of light into electricity for any application requiring either small or high power, including its application as photovoltaic window either in apparatuses or in buildings.
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| EP04727951A EP1654746A1 (en) | 2003-04-21 | 2004-04-16 | Photoelectrochemical solar cell made from nanocomposite organic-inorganic materials |
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| GR20030100186A GR1004545B (en) | 2003-04-21 | 2003-04-21 | Solar photo-electrochemical cell made of composite organic/inorganic/nan0-sstructure materials |
| GR20030100186 | 2003-04-21 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MD2730C2 (en) * | 2003-08-05 | 2005-12-31 | Институт Прикладной Физики Академии Наук Молдовы | Photoelectrochemical solar cell |
| FR2881880A1 (en) * | 2005-02-04 | 2006-08-11 | Imra Europ Sa Sa | Solid-state photovoltaic device for house roof, has monolithic layer with pores in form of channels transversally extending across thickness of layer, having inner surface covered by absorber layer, and filled with semiconductor layer |
| JP2007273984A (en) * | 2006-03-31 | 2007-10-18 | Aisin Seiki Co Ltd | Photovoltaic cell device |
| US20110203644A1 (en) * | 2010-02-22 | 2011-08-25 | Brite Hellas Ae | Quasi-solid-state photoelectrochemical solar cell formed using inkjet printing and nanocomposite organic-inorganic material |
| CN103943367A (en) * | 2013-01-23 | 2014-07-23 | 尼克·卡诺伯罗斯 | Scalable production of dye-sensitized solar cells using inkjet printing |
| CN109705767B (en) * | 2018-12-29 | 2021-06-04 | 苏州度辰新材料有限公司 | Structural white packaging adhesive film for solar cell module |
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| US5558849A (en) * | 1992-05-20 | 1996-09-24 | E. I. Du Pont De Nemours And Company | Process for making inorganic gels |
| EP1116769A2 (en) * | 2000-01-17 | 2001-07-18 | Fuji Photo Film Co., Ltd. | Electrolyte composition, electrochemical cell and ionic liquid crystal monomer |
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- 2003-04-21 GR GR20030100186A patent/GR1004545B/en unknown
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- 2004-04-16 WO PCT/GR2004/000023 patent/WO2004095481A1/en not_active Application Discontinuation
- 2004-04-16 EP EP04727951A patent/EP1654746A1/en not_active Withdrawn
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|---|---|---|---|---|
| US5558849A (en) * | 1992-05-20 | 1996-09-24 | E. I. Du Pont De Nemours And Company | Process for making inorganic gels |
| EP1116769A2 (en) * | 2000-01-17 | 2001-07-18 | Fuji Photo Film Co., Ltd. | Electrolyte composition, electrochemical cell and ionic liquid crystal monomer |
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| GROSELJ N ET AL: "Dye sensitised solar cell with a sol-gel type of electrolyte", 2001, MONTREAL, QUE., CANADA, ECOLE POLYTECHNIQUE DE MONTREAL, CANADA, 2001, pages 426 - 427, XP008027787 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MD2730C2 (en) * | 2003-08-05 | 2005-12-31 | Институт Прикладной Физики Академии Наук Молдовы | Photoelectrochemical solar cell |
| FR2881880A1 (en) * | 2005-02-04 | 2006-08-11 | Imra Europ Sa Sa | Solid-state photovoltaic device for house roof, has monolithic layer with pores in form of channels transversally extending across thickness of layer, having inner surface covered by absorber layer, and filled with semiconductor layer |
| JP2007273984A (en) * | 2006-03-31 | 2007-10-18 | Aisin Seiki Co Ltd | Photovoltaic cell device |
| US20110203644A1 (en) * | 2010-02-22 | 2011-08-25 | Brite Hellas Ae | Quasi-solid-state photoelectrochemical solar cell formed using inkjet printing and nanocomposite organic-inorganic material |
| CN103943367A (en) * | 2013-01-23 | 2014-07-23 | 尼克·卡诺伯罗斯 | Scalable production of dye-sensitized solar cells using inkjet printing |
| CN109705767B (en) * | 2018-12-29 | 2021-06-04 | 苏州度辰新材料有限公司 | Structural white packaging adhesive film for solar cell module |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1654746A1 (en) | 2006-05-10 |
| GR1004545B (en) | 2004-04-30 |
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