WO2015166120A1 - Organic thermoelectric device, thermoelectric system, method for producing the device, coating for enclosure, enclosure and hybrid solar thermoelectric system - Google Patents

Organic thermoelectric device, thermoelectric system, method for producing the device, coating for enclosure, enclosure and hybrid solar thermoelectric system Download PDF

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Publication number
WO2015166120A1
WO2015166120A1 PCT/ES2015/000059 ES2015000059W WO2015166120A1 WO 2015166120 A1 WO2015166120 A1 WO 2015166120A1 ES 2015000059 W ES2015000059 W ES 2015000059W WO 2015166120 A1 WO2015166120 A1 WO 2015166120A1
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WIPO (PCT)
Prior art keywords
elements
organic semiconductor
semiconductor polymer
substrate
thermoelectric
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PCT/ES2015/000059
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Spanish (es)
French (fr)
Inventor
Mario CULEBRAS RUBIO
Clara María GÓMEZ CLARI
Andrés CANTARERO SÁEZ
De Lima Mauricio Morais
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Universitat De València
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Publication of WO2015166120A1 publication Critical patent/WO2015166120A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/856—Thermoelectric active materials comprising organic compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/053—Energy storage means directly associated or integrated with the PV cell, e.g. a capacitor integrated with a PV cell

Definitions

  • thermoelectric device Organic thermoelectric device, thermoelectric system, method for manufacturing the device, cladding for enclosure, enclosure and thermoelectric solar hybrid system Technical sector
  • the present invention concerns, in general, in a first aspect, an organic thermoelectric device, formed by conductive organic semiconductor polymer elements of a single type of carriers arranged on a substrate, and more particularly a planar configuration device with their hot and cold faces arranged, respectively, at opposite ends of the semiconductor polymer elements, which are elongated.
  • a second aspect of the invention concerns a thermoelectric system that includes two or more devices such as those of the first aspect.
  • the present invention concerns a method for manufacturing the device.
  • a fourth aspect of the invention concerns a cladding covering comprising the device of the first aspect.
  • a fifth aspect of the present invention concerns an enclosure that includes the coating of the fourth aspect.
  • thermoelectric solar hybrid system comprising a solar panel and, associated therewith, the device of the first aspect.
  • the present invention is particularly applicable to the production of energy in large-scale applications, being implemented in large areas, such as windows and building walls or solar panels.
  • Peltier modules used in refrigeration systems.
  • Peltier modules used in refrigeration systems.
  • the use of these devices for applications in large areas is completely unfeasible.
  • thermoelectric device in the application US20110094556 a thermoelectric device is described with a planar configuration in its thermoelectric elements constituted by short thermoelectric tracks arranged on a rigid substrate, alternating elements of material of type n with elements of material of type p, which are not organic materials.
  • the substrate is trapped, together with another series of elements and layers of insulating materials, between an upper and a lower layer that constitute the hot and cold faces of the device, or vice versa.
  • thermoelectric device micrometric scale thermoelectric device (microgenerator), which is not suitable for applications on large surfaces.
  • the device proposed in said application can only be constituted by silicon nanowires as thermoelectric elements, being necessary, in particular, the use of n-type and p-type silicon nanowires, not considering the use of organic materials.
  • the temperature difference must be from the center of the device to the ends, which, taking into account the reduced size of the device (about 5x5 mm 2 ), It makes it difficult to achieve a very large temperature difference.
  • thermoelectric conversion device that does use a single type of organic semiconductor, type p in this case, using semiconductor polymers, such as PEDOT, PA ⁇ I, Polypyrrole, etc., with the possibility of incorporating a flexible substrate, and that meets the characteristics of the preamble of claim 1 of the present invention.
  • the semiconductor polymer elements have a vertical conformation, as can be seen in Figure 1, such elements being arranged on the substrate in a substantially perpendicular direction, with one of its ends fixed to the substrate and its opposite ends fixed to an insulating layer, thus adopting a sandwich structure that traps, between the substrate and the insulating layer, the semiconductor polymer elements, where the substrate and the insulating layer constitute, respectively, the hot and cold faces of the device, or vice versa.
  • the difference in temperature to be converted into voltage must occur between said hot and cold faces, which are separated from each other by a short distance, which makes it always necessary to dissipate heat in the cold face to maintain an acceptable temperature difference.
  • Such heat dissipation of the cold face is even more necessary if one takes into account that the semiconductor polymer elements used are of a single type of doping, which means that the electrical connections between them are made from the cold face to the hot face, and as the metal used in such electrical joints is much better conductor of heat than the thermoelectric semiconductor, and has a very small length, such metal quickly heats the cold part, due to a better heat transmission between the cold part and hot, so much efficiency is lost.
  • WO2013065856A1 are prepared by mechanical coating methods, and the manufacturing process contains numerous stages that make it complicated, which translates into a considerable increase in the processing cost of the device. Explanation of the invention.
  • thermoelectric device that, among others, improves the efficiency of the known, allows keeping cold and hot parts far enough away so as not to have the need of dissipating heat from the cold part, and is suitable for large-scale applications.
  • an organic thermoelectric device comprising:
  • first and a few second ends of the organic semiconductor polymer elements constitute, respectively, a cold part and a hot part of the device, or are attached or arranged adjacent thereto.
  • the organic semiconductor polymer elements have a planar conformation, are elongated in one direction and are arranged coplanarly on the substrate , according to an arrangement in which the first and second ends of the organic semiconductor polymer elements are located on two respective opposite ends of the substrate.
  • the hot and cold parts are constituted by the portions of the substrate itself where the ends of the elongate elements or tracks of organic semiconductor polymer are arranged.
  • the substrate is flexible, and for another less preferred embodiment, it is rigid.
  • the aforementioned two organic semiconductor polymer elements with which the first and second electrodes are respectively connected are the two end elements of the series constituting said serial connection of organic semiconductor polymer elements, although obviously if they are connected the first and second electrodes in other elements of the series other than the two extreme elements the device also works, although obtaining a smaller voltage difference than that existing between the two external elements, so this last less efficient connection is also contemplated as a less preferred embodiment of the device proposed by the present invention.
  • first and second electrodes are connected to the free ends of said end elements of the series, since this is where a greater voltage difference will occur.
  • the mentioned first and second electrodes are constituted, according to an embodiment example, by at least some respective portions of two of the connecting elements. According to another embodiment, the first and second electrodes are additional connection elements to said connection elements.
  • the elongated organic semiconductor polymer elements have rectangular shapes.
  • the directions in which the organic semiconductor polymer elements are elongated are parallel to each other.
  • the elongated organic semiconductor polymer elements are equally spaced apart in a transverse direction.
  • said elongated organic semiconductor polymer elements are transverse spaced apart, varying distances.
  • the width of the organic semiconductor polymer elements is within a range from one or several nanometers to one or several centimeters, and as regards the length and width values of such polymer elements, and the relationship between the two, these may be considered appropriate for the desired application, although taking into account that the preferred application is related to large-scale surfaces, longitudinal distances of one or several meters is preferred.
  • the electrical connections that is to say the aforementioned connection elements, which interconnect in series the elements of Organic semiconductor polymers, from the hot to the cold part, are long enough to dissipate the heat on their own during the journey, thus heat is not transmitted to the cold part.
  • the polymer elements are also very long, so they also do not transmit heat from the hot part to the cold part. Therefore, it is not necessary to use a heat sink in the cold part.
  • the device also includes a protective and sealing layer above at least the elements arranged on the substrate, for protection and isolation against adverse environmental conditions.
  • thermoelectric system that includes two or more devices such as those of the first aspect, electrically connected in series or in parallel and with their substrates physically mounted one above the other, so that a higher voltage is generated. output than with a single device.
  • the present invention concerns a method for manufacturing the device of the first aspect by performing the following steps:
  • metal or electrically conductive compound such as Gold, Steel, ITO or Graphite
  • connection elements in such a way that they interconnect in series the organic semiconductor polymer elements, by means of a good conductor or component, such as any electrical conductor metal, such as Copper, silver, gold, indium , aluminum etc.
  • interconnecting elements connect the ends of the organic semiconductor polymer elements arranged in the cold part with those arranged in the hot part, it is of interest that the heat of the hot part does not propagate to the cold part, whereby, for this purpose, it is desirable to make such connecting elements, generally formed in the form of tracks, as long as possible so that the heat dissipates during the path from one part to the other, so that the transmission is not transmitted heat from the hot part to the cold part and, therefore, a temperature difference is always generated between the hot and cold parts.
  • the method comprises performing, after said step c), an optimization step of the doped semiconductor polymer of the conductive organic semiconductor polymer elements, by reduction or oxidation of the semiconductor using chemical methods, that is by treatment with an oxidizing agent or reducer, or by electrochemical methods, that is, by using an electrochemical cell.
  • the method comprises, after stage c) or after the stage of optimization of the doping, if necessary, the realization of a stage d) of elimination of excess material of semiconductor of organic semiconductor polymer, leaving only arranged on the substrate the elongated organic semiconductor polymer elements and the connection elements.
  • any polymer solution such as PMMA (Polymethylmethacrylate), which can be applied, for example, by spray, such as by means of an insulation sealant spray.
  • PMMA Polymethylmethacrylate
  • step a this is carried out by thermal evaporation or by any other method that deposits a metal on a substrate.
  • the substrate is flexible, made for example of at least one of the following materials: Polyethelene Terephthalate (PET), polyurethane, polypropylene and polyethylene, or a combination thereof.
  • PET Polyethelene Terephthalate
  • polyurethane polyurethane
  • polypropylene polypropylene
  • polyethylene polyethylene
  • the substrate is rigid, made for example of at least one of the following materials: glass, quartz and thermoset polymeric resins, or a combination thereof.
  • the polymers used are of type p, since today n-type polymers are very unstable and very low efficiency, so it is not practical to implement them in devices. Obviously, if the stability and efficiency of type n increases considerably in the future, your choice will be as preferred as those of type p.
  • a fourth aspect of the invention concerns a cladding covering comprising the device of the first aspect.
  • the coating comprises two or more thermoelectric devices electrically connected in series or in parallel.
  • said cladding is: a sheet to be superimposed on one or more facades of a building (for example, by placing the hot part on a facade where the sun falls and the cold part on a shadow facade), a board, panel, etc.
  • a fifth aspect of the present invention concerns an enclosure that includes the coating of the fourth aspect.
  • said enclosure is a wall, a panel, a window, a door, a curtain, etc.
  • a sixth aspect of the present invention concerns a thermoelectric solar hybrid system, comprising a solar panel and, associated therewith, the device of the first aspect, providing the hot part in an area in contact with the panel and the cold part in a position away from the areas of the panel where the sun's rays affect, thus complementing, with the energy obtained by the thermoelectric device, the production of energy obtained by the solar panel.
  • the hybrid system comprises two or more thermoelectric devices electrically connected in series or in parallel.
  • the present invention is particularly applicable to energy production in large-scale thermoelectric applications, since the proposed thermoelectric device, due to its low production cost, is ideal for energy production in large areas.
  • Figure 1 is a schematic representation, at a functional level, of the device proposed by the first aspect of the present invention
  • Figure 2 illustrates the manufacturing method proposed by the third aspect of the invention, according to an exemplary embodiment, representing the results of each of the steps of the method until the final product is achieved, that is the device of the first aspect of the present invention, as seen in view (d);
  • Figure 3 is a graph showing the experimental measurements obtained, relating voltage generated as a function of temperature difference between hot part and cold part of a prototype constructed of the device proposed by the first aspect;
  • Figure 4 illustrates, in perspective and schematically, the enclosure proposed by the fifth aspect of the present invention, for an exemplary embodiment
  • FIG. 5 illustrates, also in perspective and schematically, the thermoelectric solar hybrid system proposed by the sixth aspect of the present invention, according to an exemplary embodiment. Detailed description of some embodiments
  • thermoelectric junctions of a pon-type organic semiconductor such as PEDOT, PA ⁇ I, polypyrrole, polycarbazole, etc.
  • a series of polymer tracks E of a thickness of microns or nanometers, as shown in Figure 1, electrically connected in series by means of the connecting elements T, so that the current generated by the temperature difference flows through of the cold and hot ends C of the device, generating a voltage V between the electrodes U1 and U2.
  • a pon-type organic semiconductor such as PEDOT, PA ⁇ I, polypyrrole, polycarbazole, etc.
  • a third aspect of the invention concerns a manufacturing method of the device D.
  • This manufacturing method consists of four stages, according to an embodiment example, as shown in Figure 2, which represents the different intermediate products (views (a), (b) and (c)) and final (view (d)), obtained after the application of each of the respective stages of the method.
  • the first stage, or stage a) is the creation on a substrate S of the drawing that is to be coated with the conductive polymer.
  • This particular drawing or pattern must be made of a metal or conductive compound that is not electrochemically active, such as steel or gold.
  • a layer of GL gold consisting of 16 gold tracks of a thickness of 2 mm separated 2 mm from each other has been deposited by metallic evaporation, although in Figure 2 (a) 6 gold tracks have been illustrated only as a schematic representation.
  • the organic conductor semiconductor polymer PS of a single type of carriers is synthesized, by electropolymerization, on the metal or electrical conductor compound GL, following said predetermined pattern, and after that the layer of metal or electrical conductor compound GL, that is, in this case, the gold layer.
  • the substrate S is used as the working electrode in the second stage.
  • a three electrode cell has been used: a working electrode, consisting of the substrate with the gold pattern, an auxiliary electrode with a mesh of platinum, an Ag / AgCI reference electrode and a potentiostat.
  • the electrochemical solution was composed of the monomer of the conductive polymer, in this case ethylenedioxythiophene (EDOT) and 1-Butyl-3-methylimdazole hexafluorophosphate in acetonitrile.
  • EDOT ethylenedioxythiophene
  • 1-Butyl-3-methylimdazole hexafluorophosphate in acetonitrile.
  • the electropolymerization is carried out at -3 mA so that the gold pattern is coated by the polymer being synthesized, in the case of the experimental prototype, PEDOT: PF6.
  • the gold layer is subsequently removed, in this case with royal water, so that only the conductive polymer PS remains on the PET substrate S as shown in Figure 2 (b).
  • the third stage, or stage c) (see Figure 2 (c)), consists in making the contacts between the semiconductor polymer tracks (hot and cold part junctions), that is, providing the connecting elements T so that Connect in series the elements of organic semiconductor polymers E, by means of an element or compound that is a good conductor of electricity.
  • the connecting elements T so that Connect in series the elements of organic semiconductor polymers E, by means of an element or compound that is a good conductor of electricity.
  • the method comprises performing, after step c), an optimization step of the dopedness of the PS semiconductor polymer of the conductive organic semiconductor polymer elements, by reduction or oxidation of the semiconductor using chemical or electrochemical methods.
  • stage d consists in the elimination of the excess material of organic semiconductor polymer PS, only the elongated organic semiconductor polymer elements E and the connection elements T being arranged on the substrate S, as can be seen in Figure 2 (d), thus the device D being formed.
  • the hot and cold parts are constituted, for the exemplary embodiment of Figure 2, by the portions of the substrate S itself where the ends of the elements or tracks are arranged.
  • elongated organic semiconductor polymer E elongated organic semiconductor polymer
  • a substrate S can be made with conductive tracks of a width of microns or even nanometers, which leads to an increase in the number of polymer tracks per unit area. This increase in the number of tracks per unit area will increase the voltage produced per unit temperature difference (Seebeck voltage).
  • Seebeck voltage Several devices can also be mounted in series, one on top of the other, so that the power generated will be multiplied.
  • thermoelectric parameters by chemical reduction with hydrazine, according to a study that the present inventors have made, starting from a semiconductor polymer with a Seebeck coefficient of 413 ⁇ / ⁇ until obtaining an optimized semiconductor polymer with a Seebeck coefficient of 91 ⁇ / ⁇
  • the results are encouraging because, as shown in Figure 3, about 25 mV have been achieved (for the case of the optimized polymer) with a temperature difference of 60 ° C with only one device layer and only 16 tracks of conductive polymer
  • the coating proposed by the fourth aspect of the invention comprises, according to an exemplary embodiment, the device D as illustrated in Figure 2 (d) or, advantageously, with a greater number of polymer track elements E and with dimensions appropriate to the support on which it is intended to be arranged.
  • the enclosure proposed by the fifth aspect of the invention is illustrated in Figure 4, for an exemplary embodiment for which it comprises a wall J on which the lining of the fourth aspect constituted by the device D.
  • Figure 4 for clarity, the different elements that form the device D have not been illustrated although, obviously, these are as illustrated in Figure 2 (d), in greater or lesser number and with greater or lesser dimensions.
  • FIG. 5 illustrates the thermoelectric solar hybrid system proposed by the sixth aspect of the present invention, for which it comprises a solar panel K (in general a photovoltaic panel) on which solar rays R, and, associated therewith, the thermoelectric device D, to complement the energy production of the solar panel K, the hot face C of the device D being in contact with the solar panel K, and the cold face F in a shaded area, in this case behind panel K, so that between both sides C, F there is a temperature difference ⁇ sufficient for the thermoelectric device D to generate an appreciable voltage.
  • a solar panel K in general a photovoltaic panel
  • the thermoelectric device D to complement the energy production of the solar panel K
  • the hot face C of the device D being in contact with the solar panel K
  • the cold face F in a shaded area, in this case behind panel K, so that between both sides C, F there is a temperature difference ⁇ sufficient for the thermoelectric device D to generate an appreciable voltage.
  • the hybrid system comprises two or more thermoelectric devices D electrically connected in series or in parallel.

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Abstract

The invention relates to a device comprising: a substrate (S); long and flat elements (E) consisting of organic semiconductor polymer that conducts a single type of carrier, and arranged on the substrate (S) in a coplanar manner, the ends thereof being arranged on two respective opposite ends of the substrate (S), and respectively forming a cold part (F) and a hot part (C), or being connected or arranged adjacently to same; connection elements (T) which interconnect in series to the elements (E) made of organic semiconductor polymers; and a first (U1) and a second (U2) electrode. The thermoelectric system includes two or more thermoelectric devices (D). The method is suitable for producing the device. The coating and the hybrid system are provided with at least one thermoelectric device (D), and the enclosure is provided with the coating.

Description

Dispositivo termoeléctrico orgánico, sistema termoeléctrico, método para la fabricación del dispositivo, revestimiento para cerramiento, cerramiento v sistema híbrido solar termoeléctrico Sector de la técnica  Organic thermoelectric device, thermoelectric system, method for manufacturing the device, cladding for enclosure, enclosure and thermoelectric solar hybrid system Technical sector
La presente invención concierne, en general, en un primer aspecto, a un dispositivo termoeléctrico orgánico, formado por unos elementos de polímero semiconductor orgánico conductor de un solo tipo de portadores dispuestos sobre un sustrato, y más en particular a un dispositivo de configuración planar con sus caras fría y caliente dispuestas, respectivamente, en los extremos opuestos de los elementos de polímero semiconductor, los cuales son alargados.  The present invention concerns, in general, in a first aspect, an organic thermoelectric device, formed by conductive organic semiconductor polymer elements of a single type of carriers arranged on a substrate, and more particularly a planar configuration device with their hot and cold faces arranged, respectively, at opposite ends of the semiconductor polymer elements, which are elongated.
Un segundo aspecto de la invención concierne a un sistema termoeléctrico que incluye dos o más dispositivos como los del primer aspecto.  A second aspect of the invention concerns a thermoelectric system that includes two or more devices such as those of the first aspect.
En un tercer aspecto, la presente invención concierne a un método para la fabricación del dispositivo.  In a third aspect, the present invention concerns a method for manufacturing the device.
Un cuarto aspecto de la invención concierne a un revestimiento para cerramiento que comprende el dispositivo del primer aspecto.  A fourth aspect of the invention concerns a cladding covering comprising the device of the first aspect.
Un quinto aspecto de la presente invención concierne a un cerramiento que incluye el revestimiento del cuarto aspecto.  A fifth aspect of the present invention concerns an enclosure that includes the coating of the fourth aspect.
Un sexto aspecto de la presente invención concierne a un sistema híbrido solar termoeléctrico, que comprende un panel solar y, asociado al mismo, el dispositivo del primer aspecto.  A sixth aspect of the present invention concerns a thermoelectric solar hybrid system, comprising a solar panel and, associated therewith, the device of the first aspect.
La presente invención es particularmente aplicable a la producción de energía en aplicaciones a gran escala, implementándose en grandes superficies, como por ejemplo ventanas y muros de edificios o en paneles solares.  The present invention is particularly applicable to the production of energy in large-scale applications, being implemented in large areas, such as windows and building walls or solar panels.
Estado de la técnica anterior Prior art
Actualmente existen dispositivos comerciales basados en B¡3Te2 llamados módulos Peltier utilizados en sistemas de refrigeración. La utilización de estos dispositivos para aplicaciones en grandes superficies resulta completamente inviable.  There are currently commercial B¡3Te2-based devices called Peltier modules used in refrigeration systems. The use of these devices for applications in large areas is completely unfeasible.
También existen ciertos prototipos orgánicos que utilizan semiconductores orgánicos tipo n y p, dispuestos alternadamente. Tal es el caso del dispositivo propuesto en la solicitud de patente US20130042899, el cual incluye dos sustratos que constituyen, respectivamente, las caras fría y caliente del dispositivo, y que incluye pares de miembros semiconductores de dopajes distintos atrapados entre ambos sustratos, y que se aplican por ejemplo mediante una impresora de inyección sobre las caras enfrentadas de ambos sustratos. La distancia existente entre las caras fría y caliente de tal dispositivo es muy pequeña. There are also certain organic prototypes that use nyp-type organic semiconductors, arranged alternately. Such is the case of the device proposed in patent application US20130042899, which includes two substrates that constitute, respectively, the cold and hot faces of the device, and which includes pairs of semiconductor members of different dopings trapped between both substrates, and which apply for example by means of an injection printer on the facing faces of both substrates. The distance between the cold and hot faces of such a device is very small.
Muchos de estos dispositivos presentan serios inconvenientes, como su escasa eficiencia y poca viabilidad en su escalado a grandes superficies.  Many of these devices have serious drawbacks, such as their low efficiency and low viability when scaling large areas.
En la solicitud US20110094556 se describe un dispositivo termoeléctrico con una configuración planar en sus elementos termoeléctricos constituido por pistas termoeléctricas cortas dispuestas sobre un sustrato rígido, alternando elementos de material de tipo n con elementos de material de tipo p, los cuales no son materiales orgánicos. El sustrato se encuentra atrapado, junto con otra serie de elementos y capas de materiales aislantes, entre una capa superior y una inferior que constituyen las caras fría y caliente del dispositivo, o viceversa. La aplicación del dispositivo propuesto en US20110094556 en grandes superficies es inviable (debido al elevado coste que supondría), su configuración planar con pistas termoeléctricas tan cortas impide que el dispositivo se pueda utilizar con diferencias de temperaturas grandes ya que sería muy difícil de mantener una diferencia de temperatura grande. Este tipo de dispositivos necesita disipar el calor de la cara fría, al ser la distancia entre las caras fría y caliente muy pequeña.  In the application US20110094556 a thermoelectric device is described with a planar configuration in its thermoelectric elements constituted by short thermoelectric tracks arranged on a rigid substrate, alternating elements of material of type n with elements of material of type p, which are not organic materials. The substrate is trapped, together with another series of elements and layers of insulating materials, between an upper and a lower layer that constitute the hot and cold faces of the device, or vice versa. The application of the device proposed in US20110094556 in large areas is unfeasible (due to the high cost that it would entail), its planar configuration with such short thermoelectric tracks prevents the device from being used with large temperature differences since it would be very difficult to maintain a difference large temperature Such devices need to dissipate heat from the cold face, as the distance between the cold and hot faces is very small.
En la solicitud Internacional WO2012101312A1 se describe un dispositivo termoeléctrico a escala micrométrica (microgenerador), el cual no es apto para aplicaciones sobre grandes superficies. El dispositivo propuesto en dicha solicitud solamente puede estar constituido por nanohilos de Silicio como elementos termoeléctricos, siendo necesario, en particular, el uso de nanohilos de silicio de tipo n y de tipo p, no contemplándose el uso de materiales orgánicos.  International application WO2012101312A1 describes a micrometric scale thermoelectric device (microgenerator), which is not suitable for applications on large surfaces. The device proposed in said application can only be constituted by silicon nanowires as thermoelectric elements, being necessary, in particular, the use of n-type and p-type silicon nanowires, not considering the use of organic materials.
Aunque el dispositivo descrito en WO2012101312A1 tenga una configuración planar de sus elementos termoeléctricos, la diferencia de temperatura ha de ser desde el centro del dispositivo hacia los extremos, lo cual, teniendo en cuenta el tamaño reducido del dispositivo (de unos 5x5 mm2), hace que sea difícil alcanzar una diferencia de temperatura muy grande. Although the device described in WO2012101312A1 has a planar configuration of its thermoelectric elements, the temperature difference must be from the center of the device to the ends, which, taking into account the reduced size of the device (about 5x5 mm 2 ), It makes it difficult to achieve a very large temperature difference.
El dispositivo propuesto en WO2012101312A1 no es flexible y, obviamente, es inviable para aplicaciones a gran escala.  The device proposed in WO2012101312A1 is not flexible and is obviously not feasible for large-scale applications.
Por otra parte, en la solicitud Internacional WO2013065856A1 se describe un dispositivo de conversión termoeléctrica que sí que utiliza un solo tipo de semiconductor orgánico, tipo p en este caso, utilizando polímeros semiconductores, tales como PEDOT, PAÑI, Polipirrol, etc., con la posibilidad de incorporar un sustrato flexible, y que reúne las características del preámbulo de la reivindicación 1 de la presente invención. En el dispositivo propuesto en WO2013065856A1 , los elementos de polímero semiconductor presentan una conformación vertical, tal y como puede apreciarse en su Figura 1 , estando tales elementos dispuestos sobre el sustrato según una dirección sustancialmente perpendicular, con uno de sus extremos fijado al sustrato y sus extremos opuestos fijados a una capa aislante, adoptando por tanto una estructura tipo sándwich que atrapa, entre el sustrato y la capa aislante, a los elementos de polímero semiconductor, donde el sustrato y la capa aislante constituyen, respectivamente, las caras fría y caliente del dispositivo, o viceversa. Como se aprecia en su Figura 2, la diferencia de temperatura a convertir en voltaje ha de producirse entre dichas caras fría y caliente, las cuales se encuentran separadas entre sí por una corta distancia, lo que hace que siempre sea necesario disipar el calor en la cara fría para poder mantener una diferencia de temperatura aceptable. Tal disipación de calor de la cara fría es aún más necesaria si se tiene en cuenta que los elementos de polímero semiconductor utilizados son de un solo tipo de dopaje, lo que significa que las uniones eléctricas entre los mismos se hacen desde la cara fría a la cara caliente, y como el metal utilizado en tales uniones eléctricas es mucho mejor conductor del calor que el semiconductor termoeléctrico, y tiene una longitud muy pequeña, tal metal rápidamente calienta la parte fría, debido a una mejor transmisión de calor entre la parte fría y caliente, con lo que se pierde mucha eficiencia. On the other hand, in the International application WO2013065856A1 a thermoelectric conversion device is described that does use a single type of organic semiconductor, type p in this case, using semiconductor polymers, such as PEDOT, PAÑI, Polypyrrole, etc., with the possibility of incorporating a flexible substrate, and that meets the characteristics of the preamble of claim 1 of the present invention. In the device proposed in WO2013065856A1, the semiconductor polymer elements have a vertical conformation, as can be seen in Figure 1, such elements being arranged on the substrate in a substantially perpendicular direction, with one of its ends fixed to the substrate and its opposite ends fixed to an insulating layer, thus adopting a sandwich structure that traps, between the substrate and the insulating layer, the semiconductor polymer elements, where the substrate and the insulating layer constitute, respectively, the hot and cold faces of the device, or vice versa. As can be seen in Figure 2, the difference in temperature to be converted into voltage must occur between said hot and cold faces, which are separated from each other by a short distance, which makes it always necessary to dissipate heat in the cold face to maintain an acceptable temperature difference. Such heat dissipation of the cold face is even more necessary if one takes into account that the semiconductor polymer elements used are of a single type of doping, which means that the electrical connections between them are made from the cold face to the hot face, and as the metal used in such electrical joints is much better conductor of heat than the thermoelectric semiconductor, and has a very small length, such metal quickly heats the cold part, due to a better heat transmission between the cold part and hot, so much efficiency is lost.
Los materiales termoeléctricos en el dispositivo propuesto en Thermoelectric materials in the device proposed in
WO2013065856A1 se preparan mediante métodos mecánicos de recubrimiento, y el proceso de fabricación contiene numerosas etapas que lo hacen complicado, con lo que se traduce en un considerable aumento del coste de procesado del dispositivo. Explicación de la invención WO2013065856A1 are prepared by mechanical coating methods, and the manufacturing process contains numerous stages that make it complicated, which translates into a considerable increase in the processing cost of the device. Explanation of the invention.
Resulta necesario ofrecer una alternativa al estado de la técnica que cubra las lagunas halladas en el mismo, aportando un dispositivo termoeléctrico que, entre otros, mejore la eficiencia de los conocidos, permita mantener suficientemente alejadas las partes fría y caliente como para no tener la necesidad de disipar el calor de la parte fría, y sea apto para aplicaciones a gran escala.  It is necessary to offer an alternative to the state of the art that covers the gaps found therein, providing a thermoelectric device that, among others, improves the efficiency of the known, allows keeping cold and hot parts far enough away so as not to have the need of dissipating heat from the cold part, and is suitable for large-scale applications.
Con tal fin, la presente invención concierne a un dispositivo termoeléctrico orgánico, que comprende:  To this end, the present invention concerns an organic thermoelectric device, comprising:
- un sustrato,  - a substrate,
- unos elementos de polímero semiconductor orgánico conductor de un solo tipo de portadores, tipo n o, preferentemente, tipo p, y que están dispuestos sobre dicho sustrato; - unos elementos de conexión, conductores de electricidad, que interconectan en serie a dichos elementos de polímeros semiconductores orgánicos; y - elements of conductive organic semiconductor polymer of a single type of carriers, type not, preferably, type p, and which are arranged on said substrate; - connection elements, electricity conductors, which interconnect in series to said organic semiconductor polymer elements; Y
- un primer y un segundo electrodos conectados, respectivamente, con dos de dichos elementos de polímeros semiconductores orgánicos;  - a first and a second electrode connected, respectively, with two of said organic semiconductor polymer elements;
donde unos primeros y unos segundos extremos de los elementos de polímero semiconductor orgánico constituyen, respectivamente, una parte fría y una parte caliente del dispositivo, o están unidos o dispuestos adyacentes a las mismas.  where first and a few second ends of the organic semiconductor polymer elements constitute, respectively, a cold part and a hot part of the device, or are attached or arranged adjacent thereto.
A diferencia de las propuestas conocidas, en particular a diferencia del dispositivo propuesto WO2013065856A1 , en el dispositivo propuesto por el primer aspecto de la invención los elementos de polímero semiconductor orgánico tienen una conformación planar, son alargados en una dirección y están dispuestos coplanarmente sobre el sustrato, según una disposición en la que los primeros y segundos extremos de los elementos de polímero semiconductor orgánico se encuentran localizados sobre dos respectivos extremos opuestos del sustrato.  Unlike the known proposals, in particular unlike the proposed device WO2013065856A1, in the device proposed by the first aspect of the invention the organic semiconductor polymer elements have a planar conformation, are elongated in one direction and are arranged coplanarly on the substrate , according to an arrangement in which the first and second ends of the organic semiconductor polymer elements are located on two respective opposite ends of the substrate.
En el dispositivo propuesto por el primer aspecto de la presente invención, en general, las partes fría y caliente están constituidas por las porciones del propio sustrato donde se encuentran dispuestos los extremos de los elementos alargados o pistas de polímero semiconductor orgánico.  In the device proposed by the first aspect of the present invention, in general, the hot and cold parts are constituted by the portions of the substrate itself where the ends of the elongate elements or tracks of organic semiconductor polymer are arranged.
Para un ejemplo de realización preferido, el sustrato es flexible, y para otro ejemplo de realización, menos preferido, éste es rígido.  For a preferred embodiment, the substrate is flexible, and for another less preferred embodiment, it is rigid.
Preferentemente, los mencionados dos elementos de polímero semiconductor orgánico con los que el primer y el segundo electrodos están respectivamente conectados son los dos elementos extremos de la serie que constituye dicha conexión en serie de elementos de polímeros semiconductores orgánicos, aunque, obviamente, si se conectan el primer y el segundo electrodos en otros elementos de la serie que no sean los dos elementos extremos el dispositivo también funciona, aunque obteniéndose una menor diferencia de voltaje que la existente entre los dos elementos externos, por lo que esta última conexión menos eficiente también es contemplada como un ejemplo de realización menos preferido del dispositivo propuesto por la presente invención.  Preferably, the aforementioned two organic semiconductor polymer elements with which the first and second electrodes are respectively connected are the two end elements of the series constituting said serial connection of organic semiconductor polymer elements, although obviously if they are connected the first and second electrodes in other elements of the series other than the two extreme elements the device also works, although obtaining a smaller voltage difference than that existing between the two external elements, so this last less efficient connection is also contemplated as a less preferred embodiment of the device proposed by the present invention.
Con aún una mayor preferencia, el primer y el segundo electrodos se encuentran conectados con los extremos libres de dichos elementos extremos de la serie, ya que es donde se producirá una mayor diferencia de voltaje.  With even greater preference, the first and second electrodes are connected to the free ends of said end elements of the series, since this is where a greater voltage difference will occur.
Los mencionados primer y segundo electrodos están constituidos, según un ejemplo de realización, por al menos unas respectivas porciones de dos de los elementos de conexión. Según otro ejemplo de realización, el primer y el segundo electrodos son unos elementos de conexión adicionales a dichos elementos de conexión. The mentioned first and second electrodes are constituted, according to an embodiment example, by at least some respective portions of two of the connecting elements. According to another embodiment, the first and second electrodes are additional connection elements to said connection elements.
De acuerdo con un ejemplo de realización, los elementos de polímero semiconductor orgánico alargados tienen formas rectangulares.  According to an embodiment, the elongated organic semiconductor polymer elements have rectangular shapes.
Según un ejemplo de realización, las direcciones en las que los elementos de polímero semiconductor orgánico son alargados son paralelas entre sí.  According to an embodiment, the directions in which the organic semiconductor polymer elements are elongated are parallel to each other.
De acuerdo con un ejemplo de realización, los elementos de polímero semiconductor orgánico alargados están equiespaciados entre sí, en una dirección transversal.  According to an exemplary embodiment, the elongated organic semiconductor polymer elements are equally spaced apart in a transverse direction.
Según otros ejemplos de realización, dichos elementos de polímero semiconductor orgánico alargados están separados entre sí, transversaimente, unas distancias variables.  According to other exemplary embodiments, said elongated organic semiconductor polymer elements are transverse spaced apart, varying distances.
En general, la anchura de los elementos de polímero semiconductor orgánico está dentro de un rango que va desde uno o varios nanómetros hasta uno o varios centímetros, y por lo que se refiere a los valores de longitud y ancho de tales elementos de polímero, y la relación entre ambas, éstos pueden ser cualquiera considerados apropiados para la aplicación deseada, aunque teniendo en cuenta que la aplicación preferida es la relativa a superficies a gran escala, unas distancias longitudinales de unos o varios metros es preferida.  In general, the width of the organic semiconductor polymer elements is within a range from one or several nanometers to one or several centimeters, and as regards the length and width values of such polymer elements, and the relationship between the two, these may be considered appropriate for the desired application, although taking into account that the preferred application is related to large-scale surfaces, longitudinal distances of one or several meters is preferred.
Debido a que la distancia entre la parte fría y la parte caliente es, en general, considerable (por ejemplo del orden de varios metros), las conexiones eléctricas, es decir los anteriormente mencionados elementos de conexión, que interconectan en serie a los elementos de polímeros semiconductores orgánicos, desde la parte caliente a la fría, son suficientemente largas para disipar el calor por sí mismas durante el camino, no transmitiéndose por tanto el calor a la parte fría. De igual modo, los elementos de polímero también son muy largos, por lo que tampoco transmiten el calor de la parte caliente a la parte fría. Por tanto, no es necesario el uso de un disipador de calor en la parte fría.  Because the distance between the cold part and the hot part is, in general, considerable (for example of the order of several meters), the electrical connections, that is to say the aforementioned connection elements, which interconnect in series the elements of Organic semiconductor polymers, from the hot to the cold part, are long enough to dissipate the heat on their own during the journey, thus heat is not transmitted to the cold part. Similarly, the polymer elements are also very long, so they also do not transmit heat from the hot part to the cold part. Therefore, it is not necessary to use a heat sink in the cold part.
Ventajosamente el dispositivo incluye también una capa protectora y de sellado por encima de al menos los elementos dispuestos sobre el sustrato, para protección y aislamiento frente a condiciones ambientales adversas.  Advantageously, the device also includes a protective and sealing layer above at least the elements arranged on the substrate, for protection and isolation against adverse environmental conditions.
Un segundo aspecto de la invención concierne a un sistema termoeléctrico que incluye dos o más dispositivos como los del primer aspecto, conectados eléctricamente en serie o en paralelo y con sus sustratos montados físicamente uno encima del otro, de manera que se consiga generar un mayor voltaje de salida que con un solo dispositivo. En un tercer aspecto, la presente invención concierne a un método para la fabricación del dispositivo del primer aspecto mediante la realización de las siguientes etapas: A second aspect of the invention concerns a thermoelectric system that includes two or more devices such as those of the first aspect, electrically connected in series or in parallel and with their substrates physically mounted one above the other, so that a higher voltage is generated. output than with a single device. In a third aspect, the present invention concerns a method for manufacturing the device of the first aspect by performing the following steps:
a) depositar sobre el sustrato una capa de metal o compuesto conductor eléctrico (tal como Oro, Acero, ITO o Grafito) que no sea electroquímicamente activo, siguiendo un patrón predeterminado,  a) deposit on the substrate a layer of metal or electrically conductive compound (such as Gold, Steel, ITO or Graphite) that is not electrochemically active, following a predetermined pattern,
b) sintetizar dicho polímero semiconductor orgánico conductor de un solo tipo de portadores, por electropolimeración, sobre dicho metal o compuesto conductor eléctrico constituyendo dichos elementos de polímero semiconductor orgánico, siguiendo dicho patrón predeterminado, y tras ello eliminar la capa de metal o compuesto conductor eléctrico; y  b) synthesizing said conductive organic semiconductor polymer from a single type of carriers, by electropolymerization, on said metal or electrically conductive compound constituting said organic semiconductor polymer elements, following said predetermined pattern, and then eliminating the metal or electrically conductive compound layer ; Y
c) proporcionar dichos elementos de conexión de manera que interconecten en serie a los elementos de polímeros semiconductores orgánicos, mediante un elemento o compuesto buen conductor de electricidad, como es el caso de cualquier metal conductor eléctrico, tal como Cobre, plata, oro, indio, aluminio etc.  c) providing said connection elements in such a way that they interconnect in series the organic semiconductor polymer elements, by means of a good conductor or component, such as any electrical conductor metal, such as Copper, silver, gold, indium , aluminum etc.
Debido a que tales elementos de interconexión conectan los extremos de los elementos de polímeros semiconductores orgánicos dispuestos en la parte fría con los dispuestos en la parte caliente, interesa que el calor de la parte caliente no se propague hasta la parte fría, por lo que, con tal fin, es deseable hacer que tales elementos de conexión, conformados en general en forma de pistas, sean lo más largos posible para que el calor se disipe durante el camino de una parte hacia la otra, de tal modo que no se transmita el calor de la parte caliente a la parte fría y, por tanto, siempre se genere una diferencia de temperatura entre las partes fría y caliente.  Because such interconnecting elements connect the ends of the organic semiconductor polymer elements arranged in the cold part with those arranged in the hot part, it is of interest that the heat of the hot part does not propagate to the cold part, whereby, for this purpose, it is desirable to make such connecting elements, generally formed in the form of tracks, as long as possible so that the heat dissipates during the path from one part to the other, so that the transmission is not transmitted heat from the hot part to the cold part and, therefore, a temperature difference is always generated between the hot and cold parts.
Opcionalmente, el método comprende realizar, tras dicha etapa c), una etapa de optimización del dopado del polímero semiconductor de los elementos de polímero semiconductor orgánico conductor, mediante reducción u oxidación del semiconductor utilizando métodos químicos, es decir mediante tratamiento con una agente oxidante o reductor, o mediante métodos electroquímicos, es decir mediante el uso de una celda electroquímica.  Optionally, the method comprises performing, after said step c), an optimization step of the doped semiconductor polymer of the conductive organic semiconductor polymer elements, by reduction or oxidation of the semiconductor using chemical methods, that is by treatment with an oxidizing agent or reducer, or by electrochemical methods, that is, by using an electrochemical cell.
Según un ejemplo de realización, el método comprende, tras la etapa c) o tras la etapa de optimización del dopado, si es el caso, la realización de una etapa d) de eliminación de material sobrante de semiconductor de polímero semiconductor orgánico, quedando únicamente dispuestos sobre el sustrato los elementos de polímero semiconductor orgánico alargados y los elementos de conexión.  According to an example of embodiment, the method comprises, after stage c) or after the stage of optimization of the doping, if necessary, the realization of a stage d) of elimination of excess material of semiconductor of organic semiconductor polymer, leaving only arranged on the substrate the elongated organic semiconductor polymer elements and the connection elements.
Por lo que se refiere a la aplicación de la anteriormente mencionada capa protectora y de sellado, ésta se lleva a cabo utilizando cualquier disolución polimérica adecuada, como por ejemplo el PMMA (Polimetilmetacrilato), pudiendo aplicarse por ejemplo mediante espray, tal como mediante un spray sellador de aislamiento. As regards the application of the aforementioned protective and sealing layer, this is carried out using any polymer solution. suitable, such as PMMA (Polymethylmethacrylate), which can be applied, for example, by spray, such as by means of an insulation sealant spray.
Por lo que se refiere a la deposición de la etapa a), ésta se lleva a cabo por evaporación térmica o por cualquier otro método que deposite un metal sobre un sustrato.  As regards the deposition of step a), this is carried out by thermal evaporation or by any other method that deposits a metal on a substrate.
Según un ejemplo de realización preferido, el sustrato es flexible, hecho por ejemplo de al menos uno de los siguientes materiales: PoliEtilenTereftalato (PET), poliuretano, polipropileno y polietileno, o de una combinación de los mismos.  According to a preferred embodiment, the substrate is flexible, made for example of at least one of the following materials: Polyethelene Terephthalate (PET), polyurethane, polypropylene and polyethylene, or a combination thereof.
Para otro ejemplo de realización, el sustrato es rígido, hecho por ejemplo de al menos unos de los siguientes materiales: vidrio, cuarzo y resinas poliméricas termoestables, o de una combinación de los mismos.  For another embodiment, the substrate is rigid, made for example of at least one of the following materials: glass, quartz and thermoset polymeric resins, or a combination thereof.
Aunque podría utilizarse este método para fabricar un dispositivo que combinase, de manera alternada, elementos de polímero semiconductor orgánico de tipo n con otros de tipo p, el método de síntesis de las pistas semiconductoras, es decir de los elementos de polímero semiconductor orgánico, y proceso de fabricado del dispositivo resultaría muy complejo, ya que para que se puedan alternar los polímeros de tipo n con los de tipo p habría que sintetizar primero los de un tipo y luego los del otro tipo. Esto a la hora de proceso de fabricado resultaría muy costoso en comparación con utilizar semiconductores de un mismo tipo ya que todas las pistas se sintetizan a la vez. Although this method could be used to manufacture a device that alternately combines elements of organic semiconductor polymer of type n with others of type p, the method of synthesis of the semiconductor tracks, that is of the elements of organic semiconductor polymer, and The manufacturing process of the device would be very complex, since so that the polymers of type n can be alternated with those of type p, those of one type would have to be synthesized first and then those of the other type. This at the time of manufacturing process would be very expensive compared to using semiconductors of the same type since all the tracks are synthesized at the same time.
Tal y como se ha indicado anteriormente, preferentemente los polímeros utilizados son de tipo p, ya que hoy en día los polímeros de tipo n son muy inestables y de muy baja eficiencia con lo que no resultan prácticos a la hora implementarlos en dispositivos. Obviamente, si la estabilidad y eficiencia de los de tipo n aumenta considerablemente en el futuro, su elección será tan preferida como la de los de tipo p.  As indicated above, preferably the polymers used are of type p, since today n-type polymers are very unstable and very low efficiency, so it is not practical to implement them in devices. Obviously, if the stability and efficiency of type n increases considerably in the future, your choice will be as preferred as those of type p.
Un cuarto aspecto de la invención concierne a un revestimiento para cerramiento que comprende el dispositivo del primer aspecto.  A fourth aspect of the invention concerns a cladding covering comprising the device of the first aspect.
Para un ejemplo de realización, el revestimiento comprende dos o más dispositivos termoeléctricos conectados eléctricamente en serie o en paralelo.  For an exemplary embodiment, the coating comprises two or more thermoelectric devices electrically connected in series or in parallel.
En función del ejemplo de realización, dicho revestimiento es: una lámina a superponer a una o más fachadas de un edificio (por ejemplo disponiendo la parte caliente en una fachada donde incida el sol y la parte fría en una fachada a la sombra), una placa, un panel, etc.  Depending on the exemplary embodiment, said cladding is: a sheet to be superimposed on one or more facades of a building (for example, by placing the hot part on a facade where the sun falls and the cold part on a shadow facade), a board, panel, etc.
Un quinto aspecto de la presente invención concierne a un cerramiento que incluye el revestimiento del cuarto aspecto. En función del ejemplo de realización, dicho cerramiento es una pared, un panel, una ventana, una puerta, una cortina, etc. A fifth aspect of the present invention concerns an enclosure that includes the coating of the fourth aspect. Depending on the exemplary embodiment, said enclosure is a wall, a panel, a window, a door, a curtain, etc.
Un sexto aspecto de la presente invención concierne a un sistema híbrido solar termoeléctrico, que comprende un panel solar y, asociado al mismo, el dispositivo del primer aspecto, disponiendo la parte caliente en una zona en contacto con el panel y la parte fría en una posición alejada de las zonas del panel donde inciden los rayos solares, complementándose así, con la energía obtenida mediante el dispositivo termoeléctrico, la producción de energía obtenida mediante el panel solar.  A sixth aspect of the present invention concerns a thermoelectric solar hybrid system, comprising a solar panel and, associated therewith, the device of the first aspect, providing the hot part in an area in contact with the panel and the cold part in a position away from the areas of the panel where the sun's rays affect, thus complementing, with the energy obtained by the thermoelectric device, the production of energy obtained by the solar panel.
Para un ejemplo de realización, el sistema híbrido comprende dos o más dispositivos termoeléctricos conectados eléctricamente en serie o en paralelo.  For an exemplary embodiment, the hybrid system comprises two or more thermoelectric devices electrically connected in series or in parallel.
La presente invención es particularmente aplicable a la producción de energía en aplicaciones termoeléctricas a gran escala, ya que el dispositivo termoeléctrico propuesto, debido a su bajo coste de producción, es ideal para la producción de energía en grandes superficies.  The present invention is particularly applicable to energy production in large-scale thermoelectric applications, since the proposed thermoelectric device, due to its low production cost, is ideal for energy production in large areas.
Breve descripción de los dibujos Brief description of the drawings
Las anteriores y otras ventajas y características se comprenderán más plenamente a partir de la siguiente descripción detallada de unos ejemplos de realización con referencia a los dibujos adjuntos, que deben tomarse a título ilustrativo y no limitativo, en los que:  The foregoing and other advantages and features will be more fully understood from the following detailed description of some embodiments with reference to the attached drawings, which should be taken by way of illustration and not limitation, in which:
la Figura 1 es una representación esquemática, a nivel funcional, del dispositivo propuesto por el primer aspecto de la presente invención;  Figure 1 is a schematic representation, at a functional level, of the device proposed by the first aspect of the present invention;
la Figura 2 ilustra al método de fabricación propuesto por el tercer aspecto de la invención, según un ejemplo de realización, representando los resultados de cada una de las etapas del método hasta conseguir el producto final, es decir el dispositivo del primer aspecto de la presente invención, según se aprecia en la vista (d);  Figure 2 illustrates the manufacturing method proposed by the third aspect of the invention, according to an exemplary embodiment, representing the results of each of the steps of the method until the final product is achieved, that is the device of the first aspect of the present invention, as seen in view (d);
la Figura 3 es una gráfica que muestra las medidas experimentales obtenidas, relacionando voltaje generado en función de diferencia de temperatura entre parte caliente y parte fría de un prototipo construido del dispositivo propuesto por el primer aspecto;  Figure 3 is a graph showing the experimental measurements obtained, relating voltage generated as a function of temperature difference between hot part and cold part of a prototype constructed of the device proposed by the first aspect;
la Figura 4 ¡lustra, en perspectiva y de manera esquemática, al cerramiento propuesto por el quinto aspecto de la presente invención, para un ejemplo de realización; y  Figure 4 illustrates, in perspective and schematically, the enclosure proposed by the fifth aspect of the present invention, for an exemplary embodiment; Y
la Figura 5 ilustra, también en perspectiva y de manera esquemática, al sistema híbrido solar termoeléctrico propuesto por el sexto aspecto de la presente invención, según un ejemplo de realización. Descripción detallada de unos ejemplos de realización Figure 5 illustrates, also in perspective and schematically, the thermoelectric solar hybrid system proposed by the sixth aspect of the present invention, according to an exemplary embodiment. Detailed description of some embodiments
El funcionamiento del dispositivo D propuesto por el primer aspecto de la presente invención se basa en uniones termoeléctricas de un semiconductor orgánico de tipo p o n (como por ejemplo PEDOT, PAÑI, polipirrol, policarbazol, etc.) de los extremos frió F y caliente C de una serie de pistas E de polímero de un espesor de mieras o nanómetros, tal y como muestra la Figura 1 , conectadas eléctricamente en serie por mediación de los elementos de conexión T, de modo que la corriente generada por la diferencia de temperatura fluye a través de los extremos frió F y caliente C del dispositivo, generándose un voltaje V entre los electrodos U1 y U2. En principio cualquier polímero o material con propiedades termoeléctricas que se pueda sintetizar mediante métodos electroquímicos es susceptible de ser utilizado en el dispositivo.  The operation of the device D proposed by the first aspect of the present invention is based on thermoelectric junctions of a pon-type organic semiconductor (such as PEDOT, PAÑI, polypyrrole, polycarbazole, etc.) of the cold and hot C ends of a series of polymer tracks E of a thickness of microns or nanometers, as shown in Figure 1, electrically connected in series by means of the connecting elements T, so that the current generated by the temperature difference flows through of the cold and hot ends C of the device, generating a voltage V between the electrodes U1 and U2. In principle, any polymer or material with thermoelectric properties that can be synthesized by electrochemical methods is likely to be used in the device.
Tal y como se ha escrito en un apartado anterior, un tercer aspecto de la invención concierne a un método de fabricación del dispositivo D. Éste método de fabricación consta de cuatro etapas, según un ejemplo de realización, tal y como muestra la Figura 2, que representa los diferentes productos intermedios (vistas (a), (b) y (c)) y final (vista (d)), obtenidos tras la aplicación de cada una de las respectivas etapas del método.  As written in a previous section, a third aspect of the invention concerns a manufacturing method of the device D. This manufacturing method consists of four stages, according to an embodiment example, as shown in Figure 2, which represents the different intermediate products (views (a), (b) and (c)) and final (view (d)), obtained after the application of each of the respective stages of the method.
La primera etapa, o etapa a), es la de creación sobre un sustrato S del dibujo que se quiera recubrir del polímero conductor. Este dibujo o patrón determinado se ha de hacer de un metal o compuesto conductor que no sea electroquímicamente activo, como por ejemplo acero u oro. En la fabricación de un prototipo experimental se ha utilizado como sustrato PET al que se le han depositado mediante evaporación metálica una capa de oro GL constituida por 16 pistas de oro de un espesor de 2 mm separadas 2 mm entre sí, aunque en la Figura 2(a) se han ¡lustrado únicamente, a modo de representación esquemática, 6 pistas de oro.  The first stage, or stage a), is the creation on a substrate S of the drawing that is to be coated with the conductive polymer. This particular drawing or pattern must be made of a metal or conductive compound that is not electrochemically active, such as steel or gold. In the manufacture of an experimental prototype, a layer of GL gold consisting of 16 gold tracks of a thickness of 2 mm separated 2 mm from each other has been deposited by metallic evaporation, although in Figure 2 (a) 6 gold tracks have been illustrated only as a schematic representation.
En la segunda etapa, o etapa b), se sintetiza el polímero semiconductor orgánico PS conductor de un solo tipo de portadores, por electropolimeración, sobre el metal o compuesto conductor eléctrico GL, siguiendo dicho patrón predeterminado, y tras ello se eliminar la capa de metal o compuesto conductor eléctrico GL, es decir, en este caso, la capa de oro.  In the second stage, or stage b), the organic conductor semiconductor polymer PS of a single type of carriers is synthesized, by electropolymerization, on the metal or electrical conductor compound GL, following said predetermined pattern, and after that the layer of metal or electrical conductor compound GL, that is, in this case, the gold layer.
Para llevar a cabo dicha electropolimeración del polímero semiconductor PS, el sustrato S se utiliza como electrodo de trabajo en la segunda etapa. Para la fabricación del prototipo experimental se ha utilizado una celda de tres electrodos: un electrodo de trabajo, constituido por el sustrato con el dibujo de oro, un electrodo auxiliar de malla de platino, un electrodo de referencia de Ag/AgCI y un potenciostato. La disolución electroquímica estaba compuesta por el monómero del polímero conductor, en este caso etilendioxitiofeno (EDOT) y 1-Butil-3-metilim¡dazol hexafluorofosfato en acetonitrilo. La electropolimerización se lleva a cabo a -3 mA de tal forma que el dibujo de oro es recubierto por el polímero que se está sintetizando, en el caso del prototipo experimental, PEDOT:PF6. Tal y como se ha comentado anteriormente, posteriormente se elimina la capa de oro, en este caso con agua regia, de tal forma que sobre el sustrato S de PET solo queda el polímero conductor PS como muestra la Figura 2 (b). To carry out said electropolymerization of the semiconductor polymer PS, the substrate S is used as the working electrode in the second stage. For the manufacture of the experimental prototype, a three electrode cell has been used: a working electrode, consisting of the substrate with the gold pattern, an auxiliary electrode with a mesh of platinum, an Ag / AgCI reference electrode and a potentiostat. The electrochemical solution was composed of the monomer of the conductive polymer, in this case ethylenedioxythiophene (EDOT) and 1-Butyl-3-methylimdazole hexafluorophosphate in acetonitrile. The electropolymerization is carried out at -3 mA so that the gold pattern is coated by the polymer being synthesized, in the case of the experimental prototype, PEDOT: PF6. As previously mentioned, the gold layer is subsequently removed, in this case with royal water, so that only the conductive polymer PS remains on the PET substrate S as shown in Figure 2 (b).
La tercera etapa, o etapa c) (ver Figura 2(c)), consiste en la realización de los contactos entre las pistas de polímero semiconductor (uniones parte fría y caliente), es decir en proporcionar los elementos de conexión T de manera que ¡nterconecten en serie a los elementos de polímeros semiconductores orgánicos E, mediante un elemento o compuesto buen conductor de electricidad. Para este caso se puede utilizar cualquier compuesto que conduzca la electricidad como un metal, aunque conviene que esté configurado para que no sea muy buen conductor térmico (constituyéndolos en la forma de pistas largas), en el caso del prototipo experimental se ha utilizado oro aunque puede ser perfectamente aluminio.  The third stage, or stage c) (see Figure 2 (c)), consists in making the contacts between the semiconductor polymer tracks (hot and cold part junctions), that is, providing the connecting elements T so that Connect in series the elements of organic semiconductor polymers E, by means of an element or compound that is a good conductor of electricity. For this case you can use any compound that conducts electricity as a metal, although it should be configured so that it is not a very good thermal conductor (constituting them in the form of long tracks), in the case of the experimental prototype gold has been used although It can be perfectly aluminum.
Como etapa opcional, el método comprende realizar, tras la etapa c), una etapa de optimización del dopado del polímero semiconductor PS de los elementos de polímero semiconductor orgánico conductor, mediante reducción u oxidación del semiconductor utilizando métodos químicos o electroquímicos.  As an optional step, the method comprises performing, after step c), an optimization step of the dopedness of the PS semiconductor polymer of the conductive organic semiconductor polymer elements, by reduction or oxidation of the semiconductor using chemical or electrochemical methods.
La última etapa, o etapa d), consiste en la eliminación del material sobrante de polímero semiconductor orgánico PS, quedando únicamente dispuestos sobre el sustrato S los elementos de polímero semiconductor orgánico alargados E y los elementos de conexión T, tal y como se aprecia en la Figura 2(d), quedando así el dispositivo D formado.  The last stage, or stage d), consists in the elimination of the excess material of organic semiconductor polymer PS, only the elongated organic semiconductor polymer elements E and the connection elements T being arranged on the substrate S, as can be seen in Figure 2 (d), thus the device D being formed.
Las partes fría y caliente (indicadas respectivamente como F y C en la Figura 1 ), están constituidas, para el ejemplo de realización de la Figura 2, por las porciones del propio sustrato S donde se encuentran dispuestos los extremos de los elementos o pistas de polímero semiconductor orgánico alargados E.  The hot and cold parts (indicated respectively as F and C in Figure 1), are constituted, for the exemplary embodiment of Figure 2, by the portions of the substrate S itself where the ends of the elements or tracks are arranged. elongated organic semiconductor polymer E.
Puede verse en la Figura 2(d), cómo los primer U1 y segundo U2 electrodos se encuentran dispuestos sobre los extremos libres de los elementos E ubicados en los extremos de la serie de elementos E.  It can be seen in Figure 2 (d), how the first U1 and second U2 electrodes are arranged on the free ends of the elements E located at the ends of the series of elements E.
Aunque en la representación esquemática de la Figura 2(d), se ha ilustrado al dispositivo comprendiendo únicamente seis pistas de polímero E, en el diseño real del prototipo experimental construido, éste consta de 16 pistas E de PEDOT unidas mediante pistas de oro T. Although in the schematic representation of Figure 2 (d), the device has been illustrated comprising only six polymer tracks E, in the actual design of the Experimental prototype built, this consists of 16 PEDOT E tracks linked by T gold tracks.
Dependiendo del proceso de fabricación se pueden adoptar múltiples geometrías y tamaños, además, la anchura y el número de pistas de polímero E puede cambiarse.  Depending on the manufacturing process, multiple geometries and sizes can be adopted, in addition, the width and number of polymer tracks E can be changed.
Mediante técnicas litográficas se puede conseguir realizar un sustrato S con pistas conductoras de una anchura de mieras o incluso nanómetros, lo que conlleva a un incremento del número de pistas de polímero por unidad de superficie. Este aumento del número de pistas por unidad de superficie aumentará la tensión producida por unidad de diferencia de temperatura (voltaje Seebeck). También se pueden montar varios dispositivos en serie, uno encima de otro, de modo que se multiplicará la potencia generada.  By means of lithographic techniques, a substrate S can be made with conductive tracks of a width of microns or even nanometers, which leads to an increase in the number of polymer tracks per unit area. This increase in the number of tracks per unit area will increase the voltage produced per unit temperature difference (Seebeck voltage). Several devices can also be mounted in series, one on top of the other, so that the power generated will be multiplied.
Se ha caracterizado la tensión que genera el dispositivo en función de la temperatura, tal y como se muestra en la Figura 3. Las medidas experimentales se han hecho, sobre el prototipo construido, antes y después de someter al polímero semiconductor a un tratamiento de optimización de los parámetros termoeléctricos mediante reducción química con hidracina, según un estudio que los presentes inventores han realizado, partiendo de un polímero semiconductor con un coeficiente de Seebeck de 413 μν/Κ hasta obtener un polímero semiconductor optimizado con un coeficiente de Seebeck de 91 μν/Κ. Los resultados son esperanzadores ya que, como se aprecia en la Figura 3, se han conseguido (para el caso del polímero optimizado) cerca de 25 mV con una diferencia de temperatura de 60 °C con solo una capa de dispositivo y solo 16 pistas de polímero conductor. The voltage generated by the device as a function of temperature has been characterized, as shown in Figure 3. Experimental measurements have been made on the prototype built before and after subjecting the semiconductor polymer to an optimization treatment. of the thermoelectric parameters by chemical reduction with hydrazine, according to a study that the present inventors have made, starting from a semiconductor polymer with a Seebeck coefficient of 413 μν / ν until obtaining an optimized semiconductor polymer with a Seebeck coefficient of 91 μν / Κ The results are encouraging because, as shown in Figure 3, about 25 mV have been achieved (for the case of the optimized polymer) with a temperature difference of 60 ° C with only one device layer and only 16 tracks of conductive polymer
Se pueden llegar a alcanzar valores de voltios disminuyendo la anchura de las pistas de polímero, para que quepan más por unidad de superficie y superponiendo varias capas de dispositivos, es decir mediante el sistema propuesto por el segundo aspecto de la invención. El revestimiento propuesto por el cuarto aspecto de la invención comprende, según un ejemplo de realización, al dispositivo D según se ilustra en la Figura 2(d) o, ventajosamente, con un mayor número de elementos de pistas E de polímero y con unas dimensiones adecuadas al soporte sobre el que se pretenda disponer.  Volt values can be reached by decreasing the width of the polymer tracks, so that they fit more per unit area and overlapping several layers of devices, that is, by the system proposed by the second aspect of the invention. The coating proposed by the fourth aspect of the invention comprises, according to an exemplary embodiment, the device D as illustrated in Figure 2 (d) or, advantageously, with a greater number of polymer track elements E and with dimensions appropriate to the support on which it is intended to be arranged.
En la Figura 4 se ilustra al cerramiento propuesto por el quinto aspecto de la invención, para un ejemplo de realización para el que éste comprende una pared J sobre la que se encuentra adosado el revestimiento del cuarto aspecto constituido por el dispositivo D. Para mayor claridad, no se han ¡lustrado los diferentes elementos que forman el dispositivo D aunque, obviamente, estos son como los ilustrados en la Figura 2(d), en mayor o menor número y con mayores o menores dimensiones. The enclosure proposed by the fifth aspect of the invention is illustrated in Figure 4, for an exemplary embodiment for which it comprises a wall J on which the lining of the fourth aspect constituted by the device D. For clarity, the different elements that form the device D have not been illustrated although, obviously, these are as illustrated in Figure 2 (d), in greater or lesser number and with greater or lesser dimensions.
Finalmente, en la Figura 5 se ilustra al sistema híbrido solar termoeléctrico propuesto por el sexto aspecto de la presente invención, para el que éste comprende un panel solar K (en general un panel fotovoltaico) sobre el que inciden unos rayos solares R, y, asociado al mismo, el dispositivo termoeléctrico D, para complementar la producción de energía del panel solar K, estando la cara caliente C del dispositivo D dispuesta en contacto con el panel solar K, y la cara fría F en una zona de sombra, en este caso tras el panel K, de manera que entre ambas caras C, F existe una diferencia de temperatura ΔΤ suficiente para que el dispositivo termoeléctrico D genere un voltaje apreciable.  Finally, Figure 5 illustrates the thermoelectric solar hybrid system proposed by the sixth aspect of the present invention, for which it comprises a solar panel K (in general a photovoltaic panel) on which solar rays R, and, associated therewith, the thermoelectric device D, to complement the energy production of the solar panel K, the hot face C of the device D being in contact with the solar panel K, and the cold face F in a shaded area, in this case behind panel K, so that between both sides C, F there is a temperature difference ΔΤ sufficient for the thermoelectric device D to generate an appreciable voltage.
Para otro ejemplo de realización (no ¡lustrado), el sistema híbrido comprende dos o más dispositivos termoeléctricos D conectados eléctricamente en serie o en paralelo.  For another embodiment (not illustrated), the hybrid system comprises two or more thermoelectric devices D electrically connected in series or in parallel.
Un experto en la materia podría introducir cambios y modificaciones en los ejemplos de realización descritos sin salirse del alcance de la invención según está definido en las reivindicaciones adjuntas.  A person skilled in the art could introduce changes and modifications in the described embodiments without departing from the scope of the invention as defined in the appended claims.

Claims

Reivindicaciones Claims
1. - Dispositivo termoeléctrico orgánico, que comprende: 1. - Organic thermoelectric device, comprising:
- un sustrato (S), - a substrate (S),
- unos elementos de polímero semiconductor orgánico (E) conductor de un solo tipo de portadores y que están dispuestos sobre dicho sustrato (S); - conductive organic semiconductor polymer elements (E) with a single type of carriers and which are arranged on said substrate (S);
- unos elementos de conexión (T), conductores de electricidad, que interconectan en serie a dichos elementos de polímeros semiconductores orgánicos (E); y - connection elements (T), electrical conductors, which interconnect in series said organic semiconducting polymer elements (E); and
- un primer (U1 ) y un segundo (U2) electrodos conectados, respectivamente, con dos de dichos elementos de polímeros semiconductores orgánicos (E); - a first (U1) and a second (U2) electrodes connected, respectively, with two of said organic semiconductor polymer elements (E);
donde unos primeros y unos segundos extremos de los elementos de polímero semiconductor orgánico (E) constituyen, respectivamente, una parte fría (F) y una parte caliente (C) del dispositivo, o están unidos o dispuestos adyacentes a las mismas; where first and second ends of the organic semiconductor polymer elements (E) constitute, respectively, a cold part (F) and a hot part (C) of the device, or are attached or arranged adjacent thereto;
estando el dispositivo caracterizado porque dichos elementos de polímero semiconductor orgánico (E) tienen una conformación planar, son alargados en una dirección y están dispuestos coplanarmente sobre dicho sustrato (S), según una disposición en la que dichos primeros y segundos extremos de los elementos de polímero semiconductor orgánico (E) se encuentran localizados sobre dos respectivos extremos opuestos del sustrato (S). the device being characterized in that said organic semiconductor polymer elements (E) have a planar conformation, are elongated in one direction and are arranged coplanarly on said substrate (S), according to an arrangement in which said first and second ends of the elements of organic semiconductor polymer (E) are located on two respective opposite ends of the substrate (S).
2. - Dispositivo según la reivindicación 1 , caracterizado porque dicho sustrato (S) es flexible. 2. - Device according to claim 1, characterized in that said substrate (S) is flexible.
3. - Dispositivo según una cualquiera de las reivindicaciones anteriores, caracterizado porque dichos elementos de polímero semiconductor orgánico alargados (E) tienen formas rectangulares. 3. - Device according to any one of the preceding claims, characterized in that said elongated organic semiconductor polymer elements (E) have rectangular shapes.
4. - Dispositivo según una cualquiera de las reivindicaciones anteriores, caracterizado porque las direcciones en las que los elementos de polímero semiconductor orgánico (E) son alargados son paralelas entre sí. 4. - Device according to any one of the previous claims, characterized in that the directions in which the organic semiconductor polymer elements (E) are elongated are parallel to each other.
5. - Dispositivo según la reivindicación 4, caracterizado porque dichos elementos de polímero semiconductor orgánico alargados (E) están equiespaciados entre sí, en una dirección transversal. 5. - Device according to claim 4, characterized in that said elongated organic semiconductor polymer elements (E) are equally spaced from each other, in a transverse direction.
6. - Dispositivo según la reivindicación 4, caracterizado porque dichos elementos de polímero semiconductor orgánico alargados (E) están separados entre sí, transversalmente, unas distancias variables. 6. - Device according to claim 4, characterized in that said elongated organic semiconductor polymer elements (E) are separated from each other, transversely, by variable distances.
7.- Dispositivo según una cualquiera de las reivindicaciones anteriores, caracterizado porque dichos dos elementos de polímero semiconductor orgánico (E) con los que dichos primer (U1 ) y segundo (U2) electrodos están respectivamente conectados son los dos elementos extremos de la serie que constituye dicha conexión en serie de elementos de polímeros semiconductores orgánicos (E). 7. Device according to any one of the preceding claims, characterized in that said two organic semiconductor polymer elements (E) with which said first (U1) and second (U2) electrodes are respectively connected are the two extreme elements of the series that constitutes said series connection of elements of organic semiconductor polymers (E).
8. - Dispositivo según la reivindicación 7, caracterizado porque los primer (U1 ) y segundo (U2) electrodos se encuentran conectados con los extremos libres de dichos elementos extremos de la serie. 8. - Device according to claim 7, characterized in that the first (U1) and second (U2) electrodes are connected to the free ends of said end elements of the series.
9. - Dispositivo según una cualquiera de las reivindicaciones anteriores, caracterizado porque la anchura de dichos elementos de polímero semiconductor orgánico (E) está dentro de un rango que va desde uno o varios nanómetros hasta uno o varios centímetros. 9. - Device according to any one of the preceding claims, characterized in that the width of said organic semiconductor polymer elements (E) is within a range ranging from one or several nanometers to one or several centimeters.
10. - Dispositivo según una cualquiera de las reivindicaciones anteriores, caracterizado porque dichos primer (U1 ) y segundo (U2) electrodos están constituidos por al menos unas respectivas porciones de dos de dichos elementos de conexión (T). 10. - Device according to any one of the preceding claims, characterized in that said first (U1) and second (U2) electrodes are constituted by at least respective portions of two of said connection elements (T).
1. - Sistema termoeléctrico que comprende al menos dos dispositivos (D) según una cualquiera de las reivindicaciones anteriores conectados eléctricamente en serie o en paralelo y con sus sustratos montados físicamente uno encima del otro. 1. - Thermoelectric system comprising at least two devices (D) according to any one of the previous claims electrically connected in series or in parallel and with their substrates physically mounted on top of each other.
12. - Método para la fabricación de un dispositivo termoeléctrico orgánico y, que comprende fabricar el dispositivo según una cualquiera de las reivindicaciones 1 a 10 mediante la realización de las siguientes etapas: 12. - Method for the manufacture of an organic thermoelectric device, which comprises manufacturing the device according to any one of claims 1 to 10 by carrying out the following steps:
a) depositar sobre dicho sustrato (S) una capa de metal o compuesto conductor eléctrico (GL) que no sea electroquímicamente activo, siguiendo un patrón predeterminado, a) deposit on said substrate (S) a layer of metal or electrically conductive compound (GL) that is not electrochemically active, following a predetermined pattern,
b) sintetizar dicho polímero semiconductor orgánico (PS) conductor de un solo tipo de portadores, por electropolimeración, sobre dicho metal o compuesto conductor eléctrico (GL) constituyendo dichos elementos de polímero semiconductor orgánico (E), siguiendo dicho patrón predeterminado, y tras ello eliminar la capa de metal o compuesto conductor eléctrico (GL); y b) synthesizing said conductive organic semiconductor polymer (PS) of a single type of carriers, by electropolymeration, on said metal or electrically conductive compound (GL) constituting said organic semiconductor polymer elements (E), following said predetermined pattern, and thereafter remove the layer of metal or electrically conductive compound (GL); and
c) proporcionar dichos elementos de conexión (T) de manera que interconecten en serie a los elementos de polímeros semiconductores orgánicos (E), mediante un elemento o compuesto buen conductor de electricidad. c) providing said connection elements (T) so that they interconnect in series the organic semiconducting polymer elements (E), using a good electrically conductive element or compound.
13. - Método según la reivindicación 12, caracterizado porque comprende realizar, tras dicha etapa c), una etapa de optimización del dopado del polímero semiconductor de los elementos de polímero semiconductor orgánico conductor, mediante reducción u oxidación del semiconductor utilizando métodos químicos o electroquímicos. 13. - Method according to claim 12, characterized in that it comprises carrying out, after said step c), a step of optimizing the doping of the semiconductor polymer of the conductive organic semiconductor polymer elements, by reduction or oxidation of the semiconductor using chemical or electrochemical methods.
14. - Método según la reivindicación 12 ó 13, caracterizado porque comprende, tras dicha etapa c) o tras dicha etapa de optimización del dopado, la realización de una etapa d) de eliminación de material sobrante de polímero semiconductor orgánico (PS), quedando únicamente dispuestos sobre el sustrato (S) los elementos de polímero semiconductor orgánico alargados (E) y los elementos de conexión (T). 14. - Method according to claim 12 or 13, characterized in that it comprises, after said stage c) or after said doping optimization stage, carrying out a stage d) of elimination of excess organic semiconductor polymer (PS) material, leaving Only the elongated organic semiconductor polymer elements (E) and the connection elements (T) are arranged on the substrate (S).
15. - Método según la reivindicación 12, 13 ó 14, caracterizado porque dicha deposición de dicha etapa a) se lleva a cabo por evaporación térmica. 15. - Method according to claim 12, 13 or 14, characterized in that said deposition of said step a) is carried out by thermal evaporation.
16. - Método según una cualquiera de las reivindicaciones 12 a 15, caracterizado porque dicho sustrato (S) es flexible. 16. - Method according to any one of claims 12 to 15, characterized in that said substrate (S) is flexible.
17.- Método según la reivindicación 16, caracterizado porque dicho sustrato (S) flexible está hecho de al menos uno de los siguientes materiales: PoliEtilenTereftalato (PET), poliuretano, polipropileno y polietileno, o de una combinación de los mismos. 17.- Method according to claim 16, characterized in that said flexible substrate (S) is made of at least one of the following materials: Polyethylene Terephthalate (PET), polyurethane, polypropylene and polyethylene, or a combination thereof.
18.- Método según una cualquiera de las reivindicaciones 12 a 15, caracterizado porque dicho sustrato (S) es rígido. 18.- Method according to any one of claims 12 to 15, characterized in that said substrate (S) is rigid.
19.- Método según la reivindicación 18, caracterizado porque dicho sustrato rígido (S) está hecho de al menos unos de los siguientes materiales: vidrio, cuarzo y resinas poliméricas termoestables, o de una combinación de los mismos. 19.- Method according to claim 18, characterized in that said rigid substrate (S) is made of at least one of the following materials: glass, quartz and thermostable polymer resins, or a combination thereof.
20.- Revestimiento para cerramiento que comprende al menos un dispositivo termoeléctrico (D) según una cualquiera de las reivindicaciones 1 a 10. 20.- Enclosure covering comprising at least one thermoelectric device (D) according to any one of claims 1 to 10.
21.- Revestimiento según la reivindicación 20, caracterizado porque comprende al menos dos dispositivos termoeléctricos (D) según una cualquiera de las reivindicaciones 1 a 10 conectados eléctricamente en serie o en paralelo. 21.- Coating according to claim 20, characterized in that it comprises at least two thermoelectric devices (D) according to any one of claims 1 to 10 electrically connected in series or parallel.
22. - Cerramiento que incluye el revestimiento de la reivindicación 20 ó 21. 22. - Enclosure that includes the covering of claim 20 or 21.
23. - Sistema híbrido solar termoeléctrico, que comprende un panel solar y, asociado al mismo, al menos un dispositivo termoeléctrico (D) según una cualquiera de las reivindicaciones 1 a 10. 23. - Solar thermoelectric hybrid system, comprising a solar panel and, associated therewith, at least one thermoelectric device (D) according to any one of claims 1 to 10.
24. - Sistema híbrido según la reivindicación 23, caracterizado porque comprende al menos dos dispositivos termoeléctricos (D) según una cualquiera de las reivindicaciones 1 a 10 conectados eléctricamente en serie o en paralelo. 24. - Hybrid system according to claim 23, characterized in that it comprises at least two thermoelectric devices (D) according to any one of claims 1 to 10 electrically connected in series or parallel.
PCT/ES2015/000059 2014-04-30 2015-04-30 Organic thermoelectric device, thermoelectric system, method for producing the device, coating for enclosure, enclosure and hybrid solar thermoelectric system WO2015166120A1 (en)

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