ES2352407B1 - DECONTAMINANT ENERGY COATING. - Google Patents

Abstract

Coating, both energetic and decontaminating, of the electrochemical photovoltaic type, usable as a translucent photovoltaic cell, essentially characterized by being a first nanocrystalline layer of broadband semiconductor (1), preferably made of TiO {sub, 2}, deposited on a generating unit through a transparent conductive intermediate layer (18) of the type made of chemical compounds such as FTO, ITO or AZO. The generating unit is composed of a basic set of three elements: an electrode (2, 3, 4, 5 and 6), an electrolyte (7) and a translucent counter electrode (8, 9 and 10).

Description

Electric power consumer site, a

Decontaminating energy coating.

Technical field

The object of the present invention, as expressed in the statement of this specification, refers to a decontaminating energy coating, of electrochemical photovoltaic type, usable as a translucent photovoltaic cell or as a coating of opaque architectural and / or ornamental elements, for the cogeneration of alternative electric energy and for the purification of the environment. Background of the invention

The conversion of light energy into electricity has its background in semiconductors; When they began to be manufactured, it was observed that if they were exposed to light, a small electric current was generated.

The generation of electrical energy in a photovoltaic cell occurs, in summary, as follows: A photon of energy light similar to that which connects electrons to the nucleus of an atom may be able, when absorbed, to separate the electron from the nucleus, to which it is attached, enough distance for this electron to wander through the crystalline network through an area of space between atoms in a random direction. The place occupied by the electron, being empty represents a positive charge, which also moves randomly through the network. Both charges are directed from the semiconductor surface to less illuminated areas, where mutual attraction can recombine them, keeping the system in general in the form of equilibrium. The materials where this phenomenon occurs are called intrinsic semiconductors and the classic example is Silicon (Si). For an electric current to exist, an electric field is required that attracts the charges generated by the light and forces it to go in opposite directions. This is achieved by joining a semiconductor with excess of e-electrons in its network (this semiconductor is called extrinsic and is doped with impurity atoms with 5 electrons in its valence band, so that when joining the semiconductor network of If in this case, with 4 links, there would be a decompensated electron that is easy to separate from the links and make it move through the glass) with another semiconductor with electron deficits or excess holes h + (this semiconductor is also called extrinsic and it is doped with atoms such as impurities with 3 electrons in its valence band, so that when incorporated into the Si semiconductor network, with 4 links, there would be a decompensated gap that is easy to separate from the bonds and move it through the glass ). At the junction of these semiconductors n (for the doped with electrons) and p (for the doped with holes) an electrostatic attraction arises between the charges in the opposite direction that will direct the charges towards that region until the forces are compensated and stabilized with those of the remaining network in the volume of the material. In this way, at the junction, an electrostatic electric field zone is formed, which will attract the opposite direction charges and repel the same direction. Those photons coming from the light source with adequate energy, and that affect the surface p, will start electrons that will cross the area of electrical potential and will not be able to return. At that time layer n acquires an overpotential on p. If you connect some direct current electric conductors.

Although these materials are normally used for the transformation of light energy into electricity, they have the disadvantage that the processing cost for obtaining pure silicon is very high and even polluting. There is another process of separation of charge carriers in a specific type of solar cell, where it occurs by diffusion of these from the areas of greatest concentration of carriers to those of lower concentration, following a gradient of electrical potential. This principle is used in third generation photovoltaic cells, which are cheaper and cleaner manufacturing method.

In the early 1990s, Michael Grätzel invented a new type of photovoltaic cell that, unlike those based on PN semiconductor junctions, the new one is based on electrochemical reactions. What the “Grätzel” cell, named in honor of its creator, does is partially simulate the process of photosynthesis, using some organic dye or pigment (“chromophore”), either of a natural type (such as chlorine juice) or blackberry dye) or be of an arti fi cial type, such as, for example, a transition metal complex.

The cell basically consists in that, on a glass substrate covered with a conductive layer, a semiconductor is deposited which, in turn coated with a layer of the aforementioned organic dye (or chromophore) and aided by a suitable electrolyte, has purpose to absorb the photons of light to generate electron-hollow pairs and thus produce electrical energy.

In the current state of the art, Grätzel photoelectrochemical cells are regenerating, of the semiconductor-electrolyte oxide interface type. A regenerative cell is understood as an electrochemical device in which the reactions of the electrodes are reversible and the reactive chemical species are conserved.

Patent WO 91/16719 of a regenerating photoelectrochemical cell is known, which includes a glass electrode coated with a conductive layer, transparent to light. This electrode also has a layer of TiO2 titanium dioxide which is made in the form of a porous nanostructure with a structure formed by colloidal particles "fried" ("anatase") and coated with a monomolecular layer of chromophores. This device includes a second crystal with a transparent conductive layer, which is coated, in turn, with a thin layer of transparent Platinum (Pt) that acts as a catalyst, to form the cell's electrode. Both crystals are packaged and sealed tightly, so that between them there is a space that in turn is filled with an electrolyte, which acts as a “redox” agent, as well as the electron exchanger and hole conveyor. These reference cells are known by the name of solar cells sensitized with dyes, or simply by their acronym in English DSSC (Dye Sensitized Solar Cell).

Given the low manufacturing costs of these photovoltaic cells, numerous feasibility studies have been carried out with the aim of introducing them into the market.

However, there are a number of deficiencies that characterize this type of cells and that have limited their massive introduction; Currently, many jobs are being carried out to solve these problems.

One of the drawbacks of these current devices is the low consistency of the active TiO2 layer and the limited adhesion of said layer with respect to the surface of the substrate on which it is deposited.

Another drawback is the limitation of the size of these devices when it is intended to extend their scope not only to solar panels, but also to large parts, construction, structural and / or ornamental elements.

Another drawback, which concerns sensitized cells, is that the ultraviolet component of sunlight can penetrate the active layer of TiO2 through the light-exposed face of the electrode and the first transparent conductive layer; this can cause a problem that is the direct excitation of the electrons of the valence band of the TiO2 semiconductor, thus generating very oxidizing (h +) holes, which influence the degradation of organic compounds (such as dyes) and very markedly in electrolyte photodegradation, as demonstrated in numerous studies; together with this, the generation of holes and direct electronic excitation of the semiconductor, as is known, favors the undesirable phenomenon of recombination. The presence of electrons in the semiconductor conduction band by direct excitation of the valence band, can turn off the sensitizer, inhibiting the act of electronic transfer, with the consequent conversion of the energy of the absorbed photons in the dye, and the consequent electronic transfer to the semiconductor conduction band, in a photonic act; This phenomenon then favors cell heating and reduces the efficiency of the device.

It would also be advisable to be able to take advantage of the intrinsic conversion capacity (which the semiconductor has) of converting UV radiation from light into energy, which in today's cells is normally wasted; This would be possible if a design of the device other than the current ones is used, as described later in this report,

Another drawback is that the intricate surface of colloidal TiO2, such as that described in current cells, has negative aspects, such as its consistency over time due to the weakness of the links between colloidal particles, which can disable them for future reconstruction and replacement of the constituent elements (such as dyes and electrolyte) by methods that guarantee their prolonged use over time; such is the case proposed in WO 2006/122114 A2 of "Solar Cell Sensitized with Rechargeable Dyes". With the regeneration mechanism proposed in said patent, the nanostructured layer undergoes a rinse or wash that is eroding and can wear it over time until it is disabled.

It is also worth mentioning the disadvantage that when the cells are outdoors, they must have surfaces exposed to the outside environment that are kept clean of dirt and external organic elements that could impede the passage of light into said cells. This would require a constant and periodic cleaning of these surfaces; otherwise we would limit its photovoltaic performance. A surface that lacks self-cleaning properties, or that is not expressly cleaned periodically, can be quickly disabled in its photovoltaic function, especially if it is horizontal surfaces such as roofs

or similar, on which the dirt settles by gravity itself.

In addition, there is the disadvantage that current cells are normally semi-transparent or translucent, and therefore, do not have adequate efficiency for installation on a matt opaque surface, such as a wall, tiles, posts, etc., since each photon of light that passes through the cell, ends up being absorbed by said matt surface, wasting its energy. In the proposed invention this phenomenon is eliminated by depositing on the substrate a shiny metallic layer that reflects the light, again passing the reflected photons through the photoactive layers.

Finally, current photoelectrochemical cells lack decontaminating, bactericidal and / or purifying properties of the environment in which they are found, because the semiconductor is encapsulated and not exposed to the external environment. Description of the invention

In order to overcome these drawbacks, the innovative energy decontamination coating has been designed, object of the present technical report.

In general terms, the present invention refers to a novel type of photoelectrochemical cell, realizable in both small and medium formats, and configurable, either as a transparent solar panel, or as a coating for parts and / or other opaque structural or ornamental elements of a building, such as tiles, tiles or similar.

Both the panels and the coverings are capable of performing four functions: a first electric current generating function with adequate efficiency, a second function of self-protection from ultraviolet light while de fi lting it, a third function of behaving as a decontaminant (and / or bactericidal) of the environment and, finally, a fourth function of presenting self-cleaning properties of the surface exposed to light.

With respect to the latter property, the constructive elements, such as window panes, tiles and tiles for walls and pavements, tiles, bricks, blocks and others, if implemented as sensitized solar cells, a matter that is feasible and arises as one of the objectives of this invention, they must have surfaces exposed to the external environment that are always kept clean of dirt and external organic elements that impede the passage of light into the cell.

With respect to the above, it is worth noting that one of the priority objectives pursued with the present invention is the integration, in a single device, of the photovoltaic generation functions with the self-cleaning and decontaminating properties of the environment surrounding the constructive elements on which said device is installed; on the other hand, the self-cleaning, decontaminating and bactericidal properties of the device must be executed on the outer surface exposed to the environment. As the external environment is an erosive and hostile environment for coatings that are implemented on exposed surfaces, it is necessary that the deposited functional semiconductor has characteristics especially suitable to resist the inclemency of the exterior, property that also presents the coating object of the present invention .

The novel invention is made so that the different layers that make up the generating structure have a strong anchoring of these to the substrate surface, an essential reason to ensure a solid communication between layers, high adhesion and an increase in the interface surface.

The new coating is designed in such a way that, on the one hand, the zones of electronic conduction of the ionic are very isolated, while on the other hand, it has also been designed to unlock as much as possible the conduction of electrons through the semiconductor , decreasing in both cases the recombination process and therefore increasing the energy efficiency of the device.

The coating object of this report presents an active layer of TiO2, of a novel nature, with a high adhesion to the substrate surface and a high consistency, both properties corresponding to the requirements established for the construction and / or architectural elements; It also has an area of exposure greater than that which can be obtained with colloidal particles “fries”, which solves by its own structure some of the most limiting problems of this technology. With the novel coating, there is an increase in efficiency per unit area, given the smaller dimensions that are achieved in an embodiment at the molecular level, as compared to an embodiment from aggregated colloidal particles.

The new energy coating, as already mentioned, presents two different structuring options; The first, designed to be used as a transparent element, is suitable for use both in independent photovoltaic cells, integrated in solar panels, as well as for use as windows, doors and other elements. This structuring option can be illuminated on both sides. The second structuring option, designed to be applied to opaque surfaces, is suitable for implementation as a monofacial cladding of opaque construction or architectural elements such as tiles, tiles or similar (that is, those used to cover walls, floors and / or roofs). This second option of monofacial structuring is designed to be illuminated by a single face.

The first structuring option, designed to be used as a transparent element, can be used in the manufacture of photovoltaic cells to implement semi-transparent structural units of solar panels. This configuration is also applicable as a substitute for window panes for all types of building; even the interior glass of a housing window or other type of room, if it is coated with the decontaminating and bactericidal layer (described below) and the transparent conductive layer (also described below), could be used as a purifying element of the interior environment of such housing or premises and, especially, in hospitals, kindergartens, geriatrics centers and other collective and social centers, which would not be necessary to enable additional interior sources of germicidal UV radiation generation.

It is also known that DSSCs work very well and stably in low light conditions; This characteristic makes them ideal for indoor use. As stated in the previous paragraph, the ability to convert these cells into decontaminating, self-cleaning and bactericidal elements adds a very attractive feature to be introduced as constituent components of windows and other interior elements.

The second structuring option, designed to be applied to opaque surfaces, allows energy cells and at the same time decontaminants, self-cleaning and bactericides (hereinafter referred to as FDAB), given the potential possibilities they possess, to be incorporated into many aspects of the construction, joining a single integrated system called “Self-sustaining System of Decontaminating Energy Construction” (SACED), occupying the surfaces of the spaces, both exterior and interior, that form ceilings, walls, pavements of terraces, facades of houses and / or buildings, ships industrial, warehouses, schools, hospitals, sports centers and, in general, all types of architectural construction that use units such as tiles, tiles, bricks, blocks, and / or any other element, structural or ornamental, capable of being reconverted or redesigned with the additional surface properties of the FDAB type.

The first configuration option of the novel energy coating proposed to constitute FDAB cells, that is, the transparent configuration, is constituted by a first nanocrystalline layer (that is, at the same time thin and transparent) of broadband semiconductor, preferably made of TiO2 , which has self-cleaning, decontaminating and bactericidal characteristics, which acts as a fi lter of ultraviolet radiation from sunlight or any other external source while allowing visible light to pass, so that said ultraviolet radiation does not penetrate inside the generating unit and deteriorate the chromophore or electrolyte layers explained below; The TiO2 layer is deposited on said generating unit through a transparent conductive intermediate layer of the type already used in current techniques, based on chemical compounds such as FTO (Fluorine dopped Tin Oxide), ITO or AZO. A basic set of three elements is called a generating unit, with a nominative but not limiting nature: an electrode, an electrolyte and a transparent counter electrode. The electrode is composed of a crystal transparent to visible light, which is coated on its inner face with a transparent conductive layer of those known in the current art (such as FTO, ITO or AZO), a compact TiO2 layer transparent that, according to the current state of the art, acts as a barrier or insulation between the electrolytic liquid and the conductive transparent layer, a nanophotovoltaic layer of TiO2 with an irregular “anatase” structure, and finally, a chromophore monolayer that is it deposits on the extensive and irregular surface of the nanophotovoltaic layer of TiO2. The counter electrode is composed, in turn, of a transparent crystal in visible light, which is coated on the inside with a transparent conductive layer of those known in the market (such as FTO, ITO or AZO) and with a transparent layer of a catalyst, among which one can cite Pt platinum, graphite, spongy Ti, Gold, Ni or any other suitable catalyst. Externally, this crystal is also coated with a conductive transparent layer, which in turn is coated with a broadband semiconductor nanocrystalline layer, preferably made of TiO2, which has self-cleaning, environmental decontaminating and bactericidal characteristics, while It also acts as a fi lter of the ultraviolet component from sunlight or any other external source, so that this component does not penetrate inside the generating unit. The novel cell, as in the classic variant, is sealed tightly by joining the two crystals and it is injected into the space between electrode and counter electrode, a suitable electrolytic liquid that performs “redox” functions between electrode and counter electrode. The ends of the transparent conductive layers of the electrode and the counter electrode are joined through an external electrical work circuit to feed some electrical or electronic component by means of the circulation of the generated electrons (e-).

The application of a transparent conductive intermediate layer deposited on the outer face of the electrode glass, composed of FTO, ITO or AZO and, as an innovative element with respect to the state of the art, is proposed as an innovative element with regard to the state of the art. in turn on this, a transparent nanocrystalline semiconductor layer based on TiO2, which performs the functions already described as a fi lter element of UV radiation, in addition to being self-cleaning, decontaminant and bactericidal, when its valence band is excited by the energy waves of the UV component of light and release, in the act, very oxidizing (h +) holes that are capable of decomposing volatile organic elements in contact with the surface to its simplest components, such as CO2, H2O and salts, as well as hydroxyl radicals very strong and superoxides, reacting with the water of the atmosphere. The latter free radicals also break down the organic elements with high effectiveness, such that TiO2 is currently considered one of the most effective and stable decontaminants that exist in nature, successfully used in water decontamination.

One of the most important mechanisms of innovation is the possibility of giving utility to the electrons that are released in the act of direct excitation of the valence band of the semiconductor towards its conduction band at the moment when the decontamination mechanism is activated described, while the holes released (h +) are used in the oxidation of organic compounds. At that moment, the electrons are decompensated in the structure, the recombination mechanism is difficult and these decompensated electrons can be freely evacuated from the semiconductor conduction band through the transparent conductive intermediate layer to a polarized circuit and, from this , to the external electrical circuit of work, passing through a semiconductor diode of low impedance, which in turn prevents the leakage of electrons (e-) that circulate through said external electrical circuit. This mechanism is of the utmost importance in the novel invention, because in the act the energy efficiency of the cell is increased, by giving an energy generating utility to the UV component of light. On the other hand, it is necessary to highlight the function of UV filter that is assigned to the design presented, regardless of the functions that the mechanism is performing, in that it is dedicated to a decontaminant function or not, and that at the moment in which there is no reaction of the holes (h +) generated with external elements of the medium, the electrons in the conduction band are eventually forced by electrostatic mechanisms to recombination, which prevents the passage of the component UV from the light inside the cell, which, as already explained, is not favorable for the stability of the cell's work and its durability.

Likewise, it is proposed, as an innovation, to add the transparent conductive layer on the external face of the counter electrode crystal, composed of FTO, ITO or AZO, and on this, a nanocrystalline layer of TiO2 based broadband semiconductor; in this way, the electrons are freely evacuated from the conduction band of the semiconductor, through the transparent conductive layer to a second polarized circuit, and from this, to the external electrical circuit, passing first through a second semiconductor low diode impedance, which in turn prevents the leakage of electrons that circulate through the external electrical work circuit.

In this way, according to the configuration of the novel energy coating in the semi-transparent cell mode described, said cell plays a role of UV filter from both sides thereof, preventing from the electrode side that they reach the TiO2 semiconductor layer transparent compact and the nanophotovoltaic layer of TiO2 "anatase" and directly excites the valence band electrons, generating gaps (h +) that can affect the chromophore monolayer and the electrolytic liquid for the reasons explained above. For the same reason, the outer face of the counter electrode also prevents the passage of UV radiation.

The two outer layers of broadband semiconductor, composed of TiO2, are nanocrystalline, that is, they are both thin and transparent in structure, to allow the free passage of visible light; these layers absorb the ultraviolet component of the light, thereby guaranteeing the assigned functions of fi lter, decontaminant, self-cleaning and bactericide, described above.

The transparent compact TiO2 layer of the electrode, acts as a barrier layer that serves, on the one hand, to offer a solid contact between the transparent conductive layer and the nanophotovoltaic layer of TiO2 anatase, thereby facilitating electronic transfer and, on the another, to prevent short circuits between the electrolyte liquid that bathes the TiO2 anatase layer and the transparent conductive layer, thereby inhibiting the recombination phenomenon.

The second configuration option of the novel energy coating proposed to constitute FDAB cells, that is, the monofacial configuration applicable to opaque surfaces, is constituted by a first transparent broadband semiconductor layer, preferably made of TiO2, which has self-cleaning characteristics, environmental decontaminants and bactericides, which acts as a fi lter of ultraviolet radiation from sunlight or any other external source while allowing visible light to pass, so that said ultraviolet radiation does not penetrate inside the unit Generate and deteriorate the chromophore or electrolyte. The TiO2 layer is deposited on said generating unit through a transparent conductive intermediate layer of the type already used in current techniques, based on compounds such as FTO, ITO or AZO. A generating unit, with a nominative but not limiting nature, is understood as a basic set of three elements: an electrode, an electrolyte and a counter electrode. This counter electrode is opaque and reflective so that the visible visible radiation that would pass through the interior of the cell and be wasted, be re fl ected and return to the interior of the cell to be reused. The electrode is composed of a crystal transparent to visible light, which is coated on its inner face with a transparent conductive layer made of materials that are already known in the current art (such as FTO, ITO or AZO), a transparent compact TiO2 layer which, according to the state of the art, acts as a barrier or insulation between the electrolytic liquid and the conductive transparent layer, a nanophotovoltaic layer of TiO2 with an irregular “anatase” structure, and finally, a monolayer of chromophore that is deposited on the extensive and irregular surface of the nanophotovoltaic layer; The electro-electrode is in turn composed, on the one hand, of the opaque body of the constructive element itself, that is to say tile, tile or similar, on whose surface a coating in the form of a spongy titanium metal layer is applied, which would execute at the same time the functions of conductive layer and catalyst. This layer of Ti can be deposited directly on the raw and rough surface of ceramic or other material, or on this previously polished and / or enameled surface, or with any degree of roughness. The opaque cell, as in the translucent variant explained above, is hermetically sealed by joining the glass with the body of the tile and a suitable electrolyte is injected that executes the redox functions between the electrodes; the ends of the transparent conductive layer of the electrode and the metallic Ti layer of the counter electrode, are joined through an external electrical working circuit.

The decompensated electrons that are produced in the first broadband nanocrystalline layer when the openings (h +) released are used in the oxidation of environmental pollutants, can be freely evacuated from the semiconductor conduction band through the intermediate layer transparent conductor towards a polarized circuit and, from this, to the external electrical circuit of work, passing before through a semiconductor diode of low impedance, which in turn prevents the leakage of electrons (e-) that circulate through said electrical circuit external.

In this variant of the novel energy coating for opaque surfaces, where the conductive and catalytic metal layer of Ti is deposited directly on an enameled, polished or rough but shiny surface, this Ti layer, being metallic, acts as a mirror in the which reflects the visible light that passes through the previous photoactive layers of the cell and has not been absorbed by them. After reflection, this light is processed again by the photoactive layers and can be reused in the photovoltaic conversion process, which unquestionably increases the efficiency of the cell. The conductive and catalytic metal layer of Ti ensures, on the other hand, an electronic conduction better than the transparent conductive layers existing in the current state of the art (such as those mentioned FTO, ITO or AZO) by having a lower resistance, which improves the efficiency of the photovoltaic cell by lowering the ohmic or resistive loss rate and / or the recombination rate of electron-electron pairs.

The outer layer of broadband semiconductor composed of TiO2 is, at the same time, of a fine and transparent structure, to allow the free passage of visible light; This layer absorbs the ultraviolet component of the light, thereby guaranteeing the assigned functions of fi lter, decontaminant, self-cleaning and bactericide, described above.

Optionally, in this variant of the novel energy coating for opaque surfaces, the conductive and catalytic metal layer of spongy Ti can be coated, in turn, by another transparent Pt catalyst layer (not shown in the drawings), which could increase the catalytic properties of the whole and thereby facilitate the electronic transfer of regeneration to the electrolyte.

Optionally also, any opaque architectural element of the aforementioned, such as tiles, bricks, blocks or others, of which they can be used as monofacial FDAB cells, can also be structured as bifacial FDAB cells, that is, they can carry the novel energy coating on both sides; this possibility doubles the power generation capacity of said architectural elements; An example of such a design could be used, for example, in bricks for gates and / or walls that receive lighting on both sides. Description of the drawings

In order to illustrate how much we have exposed so far, this descriptive report is attached and, as an integral part thereof, of a set of drawings in which it has been represented in a simplified and schematic way, two examples of practical explanations only explanatory although not limiting, of the characteristics of the novel invention.

Figure 1 shows a diagram, in cross-section, of the novel energy coating in transparent configuration.

Figure 2 shows a diagram, also in cross-section, of the novel energy coating in reflective opaque con fi guration. Description of a practical example

The two practical examples of embodiment of the invention are described below; The first (Figure 1), designed to be used as an independent transparent element, is suitable for use both in independent photovoltaic cells incorporated into solar panels and for use as windows, doors and other related window panes. This structuring option can be illuminated on both sides. The second structuring option (Figure 2), designed to be applied to opaque surfaces, is suitable for implementation as a monofacial cladding of constructive or architectural elements, also opaque, such as tiles, tiles or similar ones (that is, those used to cover walls, floors and / or ceilings); This second option of monofacial structuring is designed to be illuminated by a single face.

The first configuration option of the novel energy coating proposed to constitute FDAB cells, that is, the transparent configuration, is constituted by a first nanocrystalline layer (that is, at the same time thin and transparent) of broadband semiconductor (1) made of TiO2, which has self-cleaning, decontaminating and bactericidal characteristics, which acts as a fi lter of ultraviolet radiation (19) from sunlight or any other external source while allowing visible light (20) to pass through, with the so that said ultraviolet radiation (19) does not penetrate inside the generating unit and deteriorates the chromophore (6) or electrolyte (7) layers explained below. The TiO2 layer (1) is deposited on said generating unit through a transparent conductive intermediate layer (18) of the type already used in current techniques, based on chemical compounds such as FTO, ITO or AZO. A generating unit is understood as a basic set of three elements: an electrode (2, 3, 4, 5 and 6), an electrolyte (7) and a transparent counter electrode (8,9 and 10). The electrode is composed of a crystal (2) transparent to visible light (20), which is coated on its inner face with a transparent conductive layer (3) of which are known in the current art (such as FTO, ITO or AZO), a transparent compact TiO2 layer (4) which, according to the current state of the art, acts as a barrier or insulation between the electrolytic liquid (7) and the conductive transparent layer (3), a nanophotovoltaic layer of TiO2

(5)

with an irregular “anatase” structure, and finally, a chromophore monolayer (6) that is deposited on the extensive and irregular surface of the nanophotovoltaic layer (5) of TiO2. The counter electrode is composed, in turn, of a crystal (10) transparent to visible light (20), which is coated on the inside with a transparent conductive layer (9) of those known in the market (such as FTO, ITO or AZO) and with a transparent layer of a catalyst (8) such as Pt platinum. Externally this crystal is also coated with a conductive transparent layer (17), which in turn is coated with a nanocrystalline layer of broadband semiconductor

(eleven)

made of TiO2, which has self-cleaning, environmental decontaminating and bactericidal characteristics, while also acting as a fi lter of the ultraviolet component (19) from sunlight or any other external source, so that this component does not penetrate the interior of the generating unit. The novel cell is hermetically sealed by joining the two crystals (2 and 10) and a suitable electrolytic liquid (7) that executes "redox" functions between said electrode and counter electrode is injected into the space between electrode and counter electrode. The ends of the transparent conductive layers (3 and 9) of the electrode and the counter electrode, are joined through an external electrical work circuit (16) to power any electrical or electronic component by means of the circulation of the generated electrons (e-) .

The application of a transparent conductive intermediate layer (18) deposited on the outer face of the glass (2), composed of FTO, ITO, is proposed as an innovative element with regard to the state of the art. or AZO and, in turn on this, a transparent nanocrystalline semiconductor layer (1) based on TiO2, which performs the functions already described as a fi lter element of UV radiation (19), in addition to being self-cleaning, decontaminant and bactericidal , when its valence band is excited by the energy waves of the UV component (19) of the light and, in the act, release very oxidizing holes (h +) that are capable of decomposing volatile organic elements in contact with the surface until their simpler components, such as CO2, H2O and salts, as well as very strong and superoxid hydroxyl radicals, when reacting with the water in the atmosphere. The latter free radicals also break down the organic elements with high effectiveness, such that TiO2 is currently considered one of the most effective and stable decontaminants that exist in nature.

In the novel coating object of this report, electrons that are released in the act of direct excitation of the valence band of the semiconductor towards its conduction band at the moment when the decontamination mechanism described is activated, is given time that the released holes (h +) are used in the oxidation of the environmental polluting organic compounds. At that moment, when the electrons are decompensated in the structure, the recombination mechanism is difficult and these electrons are freely evacuated from the semiconductor conduction band through the transparent conductive intermediate layer

(18) towards a polarized circuit (15) and, from this, to the external electrical work circuit (16), passing before through a semiconductor diode of low impedance (14), which in turn prevents the leakage of electrons (e-) circulating in the external electrical circuit (16); This mechanism is of the utmost importance in the novel invention, since in the act the energy efficiency of the cell is increased, by giving an energy generating utility to the UV component (19) of the light. On the other hand, it is necessary to highlight the UV filter function (19) that is assigned to the design presented, regardless of the functions that the mechanism is carrying out, in so far as it is dedicated to a decontaminant function or no, since at the moment in which there is no reaction of the holes (h +) generated with external elements of the medium, the electrons in the conduction band are eventually forced by electrostatic mechanisms to recombination, which prevents the passage of the UV component (19) of the light inside the cell, which, as already explained, is not favorable for the stability of the work of the cell and its durability.

It is also innovation, to add the transparent conductive layer (17) on the outer face of the glass (10), composed of FTO, ITO or AZO, and on this, a broadband semiconductor nanocrystalline layer (11) based on TiO2 . In this way, electrons are freely evacuated from the semiconductor conduction band, through the transparent conductive layer (17) to a second polarized circuit (12), and from this, to the external electrical circuit (16), passing before through a second low impedance semiconductor diode (13), which in turn prevents the leakage of electrons that circulate through the external electrical work circuit (16).

In this way, according to the configuration of the novel energy coating in the semitransparent cell mode described, said cell plays a role of UV fi lter (19) from both sides thereof, preventing the electrode from reaching the layer. of a transparent compact TiO2 semiconductor (4) and the nanophotovoltaic layer of TiO2 “anatase” (5) and directly excites the electrons of the valence band, generating holes (h +) that can affect the chromophore monolayer (6) and to the electrolytic liquid (7) for the reasons explained above; for the same reason, the outer face of the counter electrode also prevents the passage of UV radiation (19).

The two outer layers of broadband semiconductor (1 and 11), composed of TiO2, are nanocrystalline, that is, they are both thin and transparent in structure, to allow the free passage of visible light. These layers are those that absorb the ultraviolet component (19) of the light, thereby guaranteeing the assigned functions of fi lter, decontaminant, self-cleaning and bactericide, described above.

The transparent compact TiO2 layer (4) of the electrode, acts as a barrier layer that serves, on the one hand, to offer a solid contact between the transparent conductive layer (3) and the nanophotovoltaic layer of TiO2 anatase (5), facilitating with it the electronic transfer and, on the other, to prevent short circuits between the electrolyte liquid (7) that bathes the TiO2 anatase layer (5) and the transparent conductive layer (3), thereby inhibiting the recombination phenomenon.

The second configuration option of the novel energy coating proposed to constitute FDAB cells, that is, the monofacial configuration applicable to opaque surfaces, is constituted by a first transparent broadband semiconductor layer (1) made of TiO2, which has self-cleaning characteristics , environmental decontaminants and bactericides, which acts as a fi lter of ultraviolet radiation (19) from sunlight or any other external source while allowing visible light (20) to pass through, so that said ultraviolet radiation ( 19) Do not penetrate inside the generating unit and damage the chromophore (6) or electrolyte (7). The TiO2 layer (1) is deposited on said generating unit through a transparent conductive intermediate layer (18) of the type already used in current techniques, based on compounds such as FTO, ITO or AZO. The generating unit is composed of a basic set of three elements: an electrode (2, 3, 4,5 and 6), an electrolyte (7) and a counter electrode (21 and 22). This counter electrode is opaque and re fl ective, so that the visible visible radiation that would pass through the interior of the cell and be wasted, be re fl ected (23) and return to the interior of the cell to be reused. The electrode is composed of a crystal (2) transparent to visible light (20), which is coated on its inner face with a transparent conductive layer (3) made of materials that are already known in the current art (such such as FTO, ITO or AZO), a transparent compact TiO2 layer (4) that, according to the state of the art, acts as a barrier or insulation between the electrolytic liquid (7) and the conductive transparent layer (3), a layer TiO2 nanophotovoltaic (5) with an irregular “anatase” structure, and finally, a chromophore monolayer (6) that is deposited on the large and irregular surface of the nanophotovoltaic layer (5). The counter electrode is in turn composed, on the one hand, of the opaque body of the construction element itself (22), that is, tile, tile or the like, on whose surface the energy coating is applied and, on the other hand, of a metallic layer (21) of spongy Titanium, which would perform the functions of conductive layer and catalyst at the same time. This layer of Ti can be deposited directly on the raw and rough surface of ceramic or other material, or on this previously polished and / or enameled surface, or with any degree of roughness. The opaque cell, as in the transparent variant explained above, is sealed tightly by joining the glass (2) with the body of the tile (22) and a suitable electrolyte (7) is injected which executes the redox functions between the electrodes. The ends of the transparent conductive layer (3) of the electrode and the metallic layer of spongy Ti

(twenty-one)

of the counter electrode, they are connected through an external electrical work circuit (16). The decompensated electrons that are produced in the first broadband nanocrystalline layer (1) when the holes (h +) released are used in the oxidation of environmental pollutants, are freely evacuated from the conductive band of the semiconductor through the transparent conductive intermediate layer (18) towards a polarized circuit (15) and, from there, to the external electrical work circuit (16), passing first through a semiconductor diode of low impedance (14), which in turn prevents the leakage of electrons (e-) circulating through said external electrical circuit (16).

In this variant of the novel energy coating for opaque surfaces, where the conductive and catalytic metal layer of Ti (21) is deposited directly on a polished enameled surface

or rough (but bright), this layer of Ti (21), being metallic, acts as a mirror in which the visible light (23) that passes through the previous photoactive layers of the cell is reflected and has not been absorbed by these . After reflection, this light (23) is processed again by the photoactive layers and can be reused in the photovoltaic conversion process, which unquestionably increases the efficiency of the cell. The conductive and catalytic metal layer of Ti (21) ensures, on the other hand, an electronic conduction better than the transparent conductive layers existing in the current state of the art (such as those mentioned FTO, ITO or AZO) for having a lower resistance , which improves the efficiency of the photovoltaic cell by lowering the index of ohmic or resistive losses and / or the rate of recombination of electron-hollow pairs.

The outer layer of broadband semiconductor (1) composed of TiO2 is, at the same time, of a fine and transparent structure, to allow the free passage of visible light; this layer absorbs the ultraviolet component (20) of the light, thereby guaranteeing the assigned functions of fi lter, decontaminant, self-cleaning and bactericide, described above.

Optionally, in this variant of the novel energy coating for opaque surfaces, the conductive and catalytic metallic layer of spongy Ti

(21) can, in turn, be coated by another transparent Pt catalyst layer (not shown in the drawings), which increases the catalytic properties of the assembly and thereby facilitates the electronic transfer of regeneration to the electrolyte.

Optionally also, any opaque architectural element (22) of the aforementioned, such as tiles, bricks, blocks or others, of which they can be used as monofacial FDAB cells, can also be structured as bifacial FDAB cells, that is, they can carry the new energy coating on both sides; This possibility doubles the power generation capacity of these architectural elements. An example of such a design could be used for example in bricks for gates and / or walls that receive lighting on both sides.

The materials used in the manufacture of the different elements that compose it, as well as the shapes, dimensions and accessories that it may present, will be independent of the object of the present invention, being able to be replaced by other technically equivalent ones, provided they do not affect the Essentiality thereof or depart from the scope defined in the claims section.

Once the concept expressed has been established, the claims note is written below, thus summarizing the novelties that are to be claimed.

Claims (7)

1. Coating, both energetic and decontaminating, of the electrochemical photovoltaic type, usable as a translucent photovoltaic cell, essentially characterized by being a first nanocrystalline layer of broadband semiconductor (1), preferably made of TiO2, deposited on a unit generator through a transparent conductive intermediate layer (18) of the type made of chemical compounds such as FTO, ITO or AZO. The generating unit is composed of a basic set of three elements: an electrode (2, 3, 4, 5 and 6), an electrolyte (7) and a translucent counter electrode (8, 9 and 10). The electrode is composed of a crystal (2) transparent to visible light (20), which is coated on its inner face with a transparent conductive layer (3) based on compounds such as FTO, ITO or AZO, a layer of TiO2 transparent compact (4), a nanophotovoltaic layer of TiO2

(5)

with an irregular “anatase” structure, and finally, a chromophore monolayer (6) that is deposited on the surface of the nanophotovoltaic layer (5) of TiO2. The counter electrode is composed, in turn, of a crystal (10) transparent to visible light (20), which is coated on the inside with a transparent conductive layer (9) of those known in the market (such as FTO, ITO or AZO) and with a transparent layer of a catalyst (8), such as platinum Pt, graphite, spongy Ti, Gold, Ni or any other suitable catalyst. Externally this crystal is also coated with a transparent conductive layer (17), which in turn is coated with a nanocrystalline layer of broadband semiconductor (11), preferably made of TiO2; The cell is hermetically sealed by joining the two crystals (2 and 10) and a suitable electrolytic liquid (7) is injected into the space between electrode and counter electrode. The ends of the transparent conductive layers (3 and 9) of the electrode and the counter electrode are joined through an external electrical work circuit (16). The decompensated electrons generated in the first transparent nanocrystalline layer (1) of the cell, are evacuated to a polarized circuit (15) and, from this, to the external electrical work circuit (16), passing through a semiconductor diode of low impedance (14). For the same purpose, a second polarized circuit is added for the transparent nanocrystalline layer (11) of the opposite face of the cell

(12)

and a second low impedance semiconductor diode (13).

2. Decontamination energy coating, usable as a coating of opaque architectural and / or ornamental elements, essentially characterized by being a first nanocrystalline layer of broadband semiconductor (1), preferably made of TiO2, deposited on a generating unit through a transparent conductive intermediate layer (18) of the type made of chemical compounds such as FTO, ITO or AZO. The generating unit is composed of a basic set of three elements: an electrode (2, 3, 4, 5 and 6), an electrolyte (7) and an opaque and reflective counter electrode (21 and 22). The electrode is composed of a crystal (2) transparent to visible light (20), which is coated on its inner face with a transparent conductive layer (3) based on compounds such as FTO, ITO or AZO, a layer of Transparent compact TiO2 (4), a nanophotovoltaic layer of TiO2 (5) with an irregular “anatase” structure, and finally, a chromophore monolayer (6) that is deposited on the surface of the nanophotovoltaic layer (5) of TiO2 . The opaque and reflective counter electrode (21 and 22) is composed on the one hand of the opaque body of the construction element (22) and, on the other hand, of a metallic layer (21) of spongy titanium; The opaque cell is sealed tightly joining the glass (2) with the body of the construction element (22) and a suitable electrolyte is injected (7); the ends of the transparent conductive layer (3) of the electrode and the metallic spongy Ti layer (21) of the counter electrode, are joined through an external electrical working circuit (16); The decompensated electrons are evacuated through the transparent conductive intermediate layer (18) to a polarized circuit (15) and, from this, to the external electrical work circuit (16), passing first through a semiconductor diode of low impedance ( 14).

3.

Energetic and decontaminating coating, according to claim two, characterized in that the conductive and catalytic metal layer of spongy Ti (21) can be coated, in turn, by another transparent Pt catalyst layer.

Four.

Decontaminating energy coating, according to second and third claims, characterized in that, optionally, to any opaque architectural element (22) the coatings described on the other side are deposited, making the photovoltaic cell bifacial.

5.

Energy and decontaminant coating, according to previous claims, where the coating is used in building interiors, which saves the energy consumption of homes, because it reuses part of the energy consumed in interior lighting. Also, indoors this coating cleanses and decontaminates the environment.

6.

Energy and decontaminant coating according to any of the preceding claims, characterized in that, in parallel to the fulfillment of the functions as a decontaminant, bactericidal and self-cleaning the semiconductor, by absorbing the ultraviolet component of light, it releases in the act excitons (electron-hollow pairs). The released electrons, during the performance of these functions, are decompensated and free of the mutual electric field that attract them to the generated holes, at which time they are used, by evacuation through circuits 12 and 15, to increase cellular generating efficiency , by joining the current of the work circuit 16.

SPANISH OFFICE OF THE PATENTS AND BRAND Application no .: 200930186 SPAIN Date of submission of the application: 05.20.2009 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: See Additional Sheet RELEVANT DOCUMENTS

Category

Documents cited Claims Affected

TO

US 2005236038 A1 (MIYOSHI KOZO) 27.10.2005, summary; paragraphs [31-49]; Figure 1. 1.2

TO

OKADA, M. et al. Fabrication of multifunctional coating which combines low-e property and visiblelight-responsive photocatalytic activity. Thin solid films, Vol. 442, No. 1-2, 2003, pages 217-221 <DOI: 10.1016 / S0040-6090 (03) 00985-4> 1.2

TO

US 2003 150485 A1 (KOYANAGI et al.) 08.08.2003, summary; paragraphs [52-122], [177-186]; Figure 1. 1.2

TO

US 5525440 A (KAY et al.) 11.06.1996, summary; column 1, line 10 - column 2, line 54; Figure 1. 1.2

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims • for claims no:

Date of realization of the report 01.02.2011

Examiner A. Figuera González Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 200930186 CLASSIFICATION OBJECT OF THE APPLICATION H01G9 / 20 (01.01.2006) H01L31 / 04 (01.01.2006) H01M14 / 00 (01.01.2006) C03C17 / 23 (01.01.2006) Minimum documentation sought (classification system followed by classification symbols) H01G, H01L, H01M, C03C, B01J Electronic databases consulted during the search (name of the database and, if possible, search terms used) INVENES, EPODOC, WPI, TXTEN, COMPENDEX, INSPEC, XPAIP, XPESP, XPIEE, XPI3E, Internet State of the Art Report Page 2/4  WRITTEN OPINION Application number: 200930186 Date of Written Opinion: 01.02.2011 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims Claims 1 -6 IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims Claims 1 -6 IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 200930186 1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

US 2005236038 A1 (MIYOSHI KOZO) 10/27/2005

D02

OKADA, M. et al. Fabrication of multifunctional coating which combines low-e property and visible-light-responsive photocatalytic activity. Thin solid films, Vol. 442, No. 1-2, 2003, pages 217-221 <DOI: 10.1016 / S0040-6090 (03) 00985-4> 2003

D03

US 2003 150485 A1 (KOYANAGI et al.) 08/14/2003

D04

US 5525440 A (KAY et al.) 11.06.1996

2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement  CLAIMS 1 and 2. Document D01 describes a photovoltaic cell of a structure similar to the generating unit that is part of the object of claim 1. Document D02 describes a multifunctional coating with antibacteriological, self-cleaning and anti-fogging activity formed by a layer of FTO and one of TiO2 that are deposited on a glass and that is similar to layers 1 and 18 and to layers 17 and 11 that are part of the object of claim 1. It would have been obvious to the person skilled in the art to make a combination of these two devices to obtain a photovoltaic cell such as that of document D01 with the advantages of having a multifunctional coating such as that described in document D02. However, the invention object of claim 1 goes beyond a simple superposition of these elements since a common circuit is arranged in which not only the energy generated by the photovoltaic cell is used but also the decompensated electrons generated by the coating by using circuits with low impedance polarized diodes. There is no indication in the state of the recovered art to carry out this recovery of the decompensated electrons of the coating layers. Similar reasoning can be applied to independent claim 2. It is therefore considered that independent claims 1 and 2 meet the requirements of novelty and inventive activity in accordance with articles 6 and 8 of the Patent Law.  CLAIMS 3 TO 6 Claims 3 to 6, depending on claims that have novelty and inventive activity, meet in turn the requirements of novelty and inventive activity. State of the Art Report Page 4/4