WO2004095481A1 - Cellule solaire photoelectrochimique fabriquee a partir de materiaux organiques-inorganiques nanocomposites - Google Patents

Cellule solaire photoelectrochimique fabriquee a partir de materiaux organiques-inorganiques nanocomposites Download PDF

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Publication number
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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Prior art keywords
organic
deposited
nanocomposite
commercially available
layer
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Application number
PCT/GR2004/000023
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English (en)
Inventor
Panagiotis Lianos
Elias Stathatos
Boris Orel
Original Assignee
Panagiotis Lianos
Elias Stathatos
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Filing date
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Application filed by Panagiotis Lianos, Elias Stathatos filed Critical Panagiotis Lianos
Priority to EP04727951A priority Critical patent/EP1654746A1/fr
Publication of WO2004095481A1 publication Critical patent/WO2004095481A1/fr

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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
    • H01G9/2004—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, 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
    • 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.

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  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Environmental & Geological Engineering (AREA)
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Abstract

L'invention concerne la structure d'une cellule solaire photoélectrochimique solide constituée de couches minces de matériaux organiques-inorganiques nanocomposites et pouvant être utilisée pour convertir l'énergie solaire en électricité. Les composants principaux de la cellule, dont la section transversale est présentée dans le dessin 1 sont : (1) une plaque de verre électroconductrice disponible dans le commerce ; (2) une couche mésoporeuse de dioxyde de titane nanocristallin se présentant sous forme d'une couche transparente mince d'épaisseur contrôlée, laquelle est synthétisée et déposée par traitements chimiques, tel que décrit dans l'invention. Sur ladite couche est fixé un complexe organométallique de ruthénium disponible dans le commerce, lequel sert de photosensibilisateur de TiO2 ; (3) une couche d'un électrolyte gel solide constituée d'un matériau organique-inorganique nanocomposite comprenant I2 et I-, synthétisée suivant des procédés chimiques ; et (4) une électrode positive constituée d'une plaque de verre électroconductrice disponible dans le commerce, une couche mince de platine pouvant être déposée, laquelle complète la cellule.
PCT/GR2004/000023 2003-04-21 2004-04-16 Cellule solaire photoelectrochimique fabriquee a partir de materiaux organiques-inorganiques nanocomposites WO2004095481A1 (fr)

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GR20030100186 2003-04-21
GR20030100186A GR1004545B (el) 2003-04-21 2003-04-21 Ηλιακη φωτοηλεκτροχημικη κυψελιδα παρασκευαζομενη απο συνθετα οργανικα/ανοργανα νανοδομημενα υλικα

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD2730C2 (ro) * 2003-08-05 2005-12-31 Институт Прикладной Физики Академии Наук Молдовы Celulă solară fotoelectrochimică
FR2881880A1 (fr) * 2005-02-04 2006-08-11 Imra Europ Sa Sa Dispositif photovoltaique solide avec une couche monolithique de materiau semi-conducteur comprenant des pores sous forme de canaux
JP2007273984A (ja) * 2006-03-31 2007-10-18 Aisin Seiki Co Ltd 光電池デバイス
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 (zh) * 2013-01-23 2014-07-23 尼克·卡诺伯罗斯 使用喷墨印刷的染料敏化太阳能电池的变批量生产
CN109705767B (zh) * 2018-12-29 2021-06-04 苏州度辰新材料有限公司 一种用于太阳能电池组件的结构型白色封装胶膜

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5558849A (en) * 1992-05-20 1996-09-24 E. I. Du Pont De Nemours And Company Process for making inorganic gels
EP1116769A2 (fr) * 2000-01-17 2001-07-18 Fuji Photo Film Co., Ltd. Composition d'électrolyte, cellule électrochimique et monomère liquide cristallin ionique

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
US5558849A (en) * 1992-05-20 1996-09-24 E. I. Du Pont De Nemours And Company Process for making inorganic gels
EP1116769A2 (fr) * 2000-01-17 2001-07-18 Fuji Photo Film Co., Ltd. Composition d'électrolyte, cellule électrochimique et monomère liquide cristallin ionique

Non-Patent Citations (3)

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Title
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 *
NIEDERBERGER M ET AL: "Benzyl alcohol and titanium tetrachloride-a versatile reaction system for the nonaqueous and low-temperature preparation of crystalline and luminescent titania nanoparticles", CHEM. MATER. (USA), CHEMISTRY OF MATERIALS, OCT. 2002, AMERICAN CHEM. SOC, USA, vol. 14, no. 10, October 2002 (2002-10-01), pages 4364 - 4370, XP001176684, ISSN: 0897-4756 *
STATHATOS E ET AL: "DYE-SENSITIZED PHOTOELECTROCHEMICAL CELL USING A NANOCOMPOSITE SIO2/POLY(ETHYLENE GLYCOL) THIN FILM AS ELECTROLYTE SUPPORT. CHARACTERIZATION BY TIME-RESOLVED LUMINESCENCE AND CONDUCTIVITY MEASUREMENTS", JOURNAL OF PHYSICAL CHEMISTRY. B, MATERIALS, SURFACES, INTERFACES AND BIOPHYSICAL, WASHINGTON, DC, US, vol. 105, 2001, pages 3486 - 3492, XP001011482, ISSN: 1089-5647 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD2730C2 (ro) * 2003-08-05 2005-12-31 Институт Прикладной Физики Академии Наук Молдовы Celulă solară fotoelectrochimică
FR2881880A1 (fr) * 2005-02-04 2006-08-11 Imra Europ Sa Sa Dispositif photovoltaique solide avec une couche monolithique de materiau semi-conducteur comprenant des pores sous forme de canaux
JP2007273984A (ja) * 2006-03-31 2007-10-18 Aisin Seiki Co Ltd 光電池デバイス
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 (zh) * 2013-01-23 2014-07-23 尼克·卡诺伯罗斯 使用喷墨印刷的染料敏化太阳能电池的变批量生产
CN109705767B (zh) * 2018-12-29 2021-06-04 苏州度辰新材料有限公司 一种用于太阳能电池组件的结构型白色封装胶膜

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EP1654746A1 (fr) 2006-05-10

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