Thermal energy recovery cover panels for zero-emission electricity generation

Abstract

[Solution] The present invention relates to a modular metal panel for thermal energy recovery, with or without chamber, that can be used on a building, or on a self-propelled mobile structure, or on another type of prefabricated or non-prefabricated structure, having a metal structure (11) that serves as a support for at least one layer (12) of thermally conductive carbonaceous material coupled to a thermoelectric converter that can generate electrical energy based on a thermal difference between a first surface and a second surface of the at least one layer (12). The present invention also relates to a method for manufacturing said panel.

Description

[Technical Field]

[0001] The present invention relates to the field of metal roof panels, and in particular to roof panels with thermal energy recovery (hot or cold) for generating electricity with zero emissions. [Background technology]

[0002] Many buildings are known to be covered, both in the walls and on the roof, with panels of different types of material, which panels are typically made to improve the thermal insulation of the interior of the building.

[0003] Known types of panels cannot recover any energy, but they can be used inside a "building" because their exterior surface is exposed to thermal energy from the sun or from the air (hot or cold).

[0004] Furthermore, known types of panels are sensitive to the action of one or more atmospheric phenomena, in particular the action of erosive forces such as sand found in desert regions but also in coastal areas, which can also cause significant wear of the surface of the panel itself. Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is therefore to describe a thermal energy recovery panel that overcomes the above-mentioned drawbacks and at the same time makes it possible to generate zero-emission electricity. [Means for solving the problem]

[0006] <Summary of the Invention> According to the present invention, modular metal panels with thermal energy recovery, both chambered and non-chambered, that can be used on buildings or self-propelled mobile structures, or any other type of prefabricated or non-prefabricated structure, are made to generate electricity with zero emissions.

[0007] The metal panel for thermal energy recovery to generate zero-emission electrical energy with a chamber includes a metal structure serving as a support substrate and at least one metal plate or other material on which one or more of the metal structures serving as a support substrate are disposed, the metal structure serving as a support substrate includes a first layer of thermally conductive carbonaceous material having an oriented geometric molecular structure superimposed on the surface of the metal structure serving as a substrate, and a thermoelectric converter in contact with the layer of thermally conductive carbonaceous material.

[0008] The metal panel with thermal energy recovery for generating zero-emission electrical energy, without chambers and for forming ventilated wall or roof coverings, particularly suitable for buildings, comprises a metal structure acting as a support substrate, a first layer of a material carbonaceous heat conductor (or thermally conductive carbonaceous material) having an oriented geometric molecular structure superimposed on the surface of the metal structure acting as a substrate, and a thermoelectric converter in contact with the layer of thermally conductive carbonaceous material.

[0009] Advantageously, said surface of said metal panel comprises at least a second layer of thermally conductive carbonaceous material superimposed on said first layer of thermally conductive carbonaceous material.

[0010] In particular, the thermoelectric converter is placed on the metal structure which acts as a substrate.

[0011] In particular, in said transducer, at least the first layer of carbonaceous material is thermally conductive.

[0012] In particular, in the converter, the first and second layers of the thermally conductive carbonaceous material each have sp .sigma. between carbon atoms constituting the layers of the carbonaceous material. 2 Type bonds and sp 3 and the first layer has a percentage of each of the sp 2 Bonds of type sp 3 The percentage of bonds of type sp in the second layer of carbonaceous material 2 Bonds of type sp 3 The percentage of binding of the type is different.

[0013] Advantageously, said thermoelectric converter comprises at least one similar Peltier cell.

[0014] More specifically, the thermoelectric converter comprises a pair of similarly stacked Peltier cells.

[0015] According to the invention, a method for manufacturing said metal panel with thermal energy recovery is carried out for generating electricity with zero emissions, said method comprising a deposition step of at least one layer of a carbonaceous material having an ordered geometric structure on a substrate made of a metallic material in the environment of a deposition machine, said environment being under vacuum and isolated from the external environment under controlled temperature and pressure conditions, said deposition being carried out orthogonally or locally radially with respect to a plane or shape substantially defined by said substrate made of a metallic material.

[0016] Advantageously, said depositing step includes the step of obtaining at least one set of pressure and temperature values ​​within said vacuum and isolated environment.

[0017] Advantageously, the deposition step comprises the generation of an electromagnetic field that is at least partially invested in the substrate, and automatic control of the intensity of the electromagnetic field by a data processing unit of the deposition machine.

[0018] Advantageously, there is also a step of varying the strength of the electromagnetic field during the deposition of a plurality of superimposed layers of carbonaceous material, in which the strength of the electromagnetic field is varied with respect to the previously or subsequently deposited layers, with respect to the variation in the strength of the electromagnetic field. 2 Type and sp 3 A change in the concentration of type bonds occurs.

[0019] Advantageously, the method also includes the step of mounting a thermoelectric converter on the panel itself, said thermoelectric converter having at least one surface placed in contact with said at least one layer. [Brief explanation of the drawings]

[0020] <Explanation of the attached drawings> The invention will now be described with reference to the accompanying non-limiting drawings in which: [Figure 1] Figure 1 shows a cross section of a metal chamber panel; [Figure 2] Figure 2 shows a cross section of a metal panel without a chamber; [Figure 3] Figure 3 illustrates a detail of a portion of a metal panel with thermal energy recovery, including a device for the transfer of thermal energy; [Figure 4] Figure 4 shows a second alternative embodiment of the metal panel; [Figure 5] FIG. 5 shows a schematic diagram of a machine for manufacturing the metal panels of FIGS. 3 and 4; [Figure 6-7]Figures 6 and 7 respectively show graphs detailing the processing steps to obtain a panel according to the invention, in particular graphs of density as a function of the thickness of the coating layer in the material carbonaceous and percentage of sp3 type bonds depending on the supply voltage of the metal substrate; [Figure 8] FIG. 8 shows a table of thickness values ​​for layers of carbonaceous material. DETAILED DESCRIPTION OF THE INVENTION

[0021] With reference to the accompanying drawings, reference numeral 10 generally indicates a portion of a metal panel with thermal energy recovery, the metal panel having at least one metal structure acting as a support substrate 11, including a layer of carbonaceous material (more details of which will be explained herein below), and configured to transport thermal energy in one or more substantially predetermined directions to enable conversion into electrical energy.

[0022] In particular, as shown in the cross-sectional view of Figure 1, the panel has a metal plate or other material or fixed profile 11' in addition to a metal substrate 11, thus creating a metal panel for thermal energy recovery with or without chamber (with natural ventilation), which can also reduce heat dispersion and noise transmission.

[0023] In particular, panel 10 comprises a substrate 11 lying in a plane identified by a first pair of axes X, Y, on which is superimposed at least one layer 12 of carbonaceous material, which ideally has a uniform thickness across its entire surface, thus identifying first and second surfaces 13 and 14 facing one another and, in particular, substrate 11 and outwardly facing surfaces, respectively. The superposition of substrate 11 and layer 12 of carbonaceous material occurs on a Z-axis substantially orthogonal to the pair of axes X, Y. For clarity of representation, thermal energy impinging on the panel is indicated schematically in FIG. 3 by arrows 1000.

[0024] The layer 12 makes it possible to create a guide for at least one preferred direction of the thermal energy received at the second face 14 of the layer 12 .

[0025] In an alternative embodiment shown in FIG. 4, the metal panel object of the invention comprises several layers 12a, 12b, 12c, each layer superimposed on the previous layer.

[0026] Ideally sp 2 Each of the bond layers is connected to other sp 2 It has the same thickness as the bonding layer and is sp 3 Each of the bond layers is connected to other sp 3 It has the same thickness as the tie layer.

[0027] The metal panel 10 according to the present invention is manufactured by a process which includes a first pre-washing step, in which the substrate 11 is carefully cleaned to allow the correct growth of a first layer 12 of nanometer-sized carbonaceous material.

[0028] In particular, the first pre-cleaning step is designed to promote the removal of all micrometer impurities and most of the nanometer-sized impurities.

[0029] Since temperatures in excess of 65° C. can be reached during the pre-cleaning step, it is also important that the substrate 11 be able to be exposed to these temperatures without being damaged.

[0030] Specifically, the pre-cleaning step is, in the first alternative solution: - preventive coating of the substrate surface with acetone; - a subsequent rubbing step with a pad; - a subsequent rinsing step, preferably carried out with isopropyl alcohol (propan-2-ol); - A subsequent drying step of the substrate with a nitrogen gun (N2).

[0031] Alternatively, the cleaning phase may be in addition to or instead of one or more of the previous phases: - oxygen plasma etching stage to remove residual organic films (etching process); - the RCA Clean technology step of removing metal, oxide and organic contaminants, which is carried out in two stages: a first organic cleaning stage, which advantageously removes organic insoluble contaminants with a 5:1:1 solution of H2O:H2O2:NH4OH, and a second stage called "Oxide Strip", which removes the thin layer of SiO2 on which metal contaminants may have accumulated; - the stage called "piranha clean" or "piranha etch", which removes organic substances (photoresist, oils, etc.), obtained by mixing 98% H2SO4 and 30% H2O4 in a volume ratio of 2-4:1, followed by heating the substrate thus cleaned to 100 ° C; - an ultrasonic cleaning step, in which the substrate is placed in an ultrasonic cleaner and these ultrasonic waves remove contaminants.

[0032] It has been observed during the course of experiments that the optimum solution for cleaning the substrate 11 involves immersion in piranha solution (H2SO2:H2O2, 7:3, 10') followed by ultrasonic cleaning.

[0033] Finally, the end of the cleaning step is always followed by a deposition step on the substrate 11 in an HV or UHV chamber, in which it is cleaned with a low-energy etch to avoid amorphization, at which point the substrate is ready to be processed.

[0034] Processing then continues in the vacuum chamber 111 (FIG. 5) of the deposition machine 110 (FIG. 5), where a threshold pressure is reached (preferably 10 -1 Pa), followed by a deposition step of one or more layers 12 of carbonaceous material.

[0035] In particular, the deposition machine 110 comprises at least one movable magnetron sputtering 120, a system for gripping and moving the substrate, arranged inside a vacuum chamber 111, and a gas inlet 150 having an end arranged inside said vacuum chamber. The vacuum chamber 111 creates a clean environment isolated from the outside, in which the following deposition steps take place under optimal conditions of temperature and pressure, which are managed and controlled according to the process.

[0036] During the deposition phase, the magnetron 120 is activated and generates an electromagnetic field that impinges on the substrate 11 in a precise manner during translation along a plane substantially parallel to the X, Y plane identified by the substrate 11.

[0037] Thus, in effect, there is relative movement between the magnetron 120 and the substrate 11 in the X, Y plane, which allows for the deposition of carbonaceous materials in a much more precise manner than conventional sputtering techniques.

[0038] Also inside the vacuum chamber 111 is an electron gun 130 that sends an electron beam to a target in carbon 140, preferably (but not limited to) a planar type, positioned in contact with the electrode. Carbon atoms branch off from the carbon target 140 and are directed towards the substrate 11.

[0039] In particular, the target 140 was chosen to be 99.99% pure graphite in order to obtain a coating with a crystalline structure with properties similar to those of diamond.

[0040] The purity of the graphite, with a value of 99.99%, facilitates obtaining a highly efficient deposition of the carbonaceous material layer 12 and avoids the diffusion of impurities within the vacuum chamber 111, which may significantly reduce the overall efficiency of the device.

[0041] The magnetron 120 is operated with simultaneous entry into the chamber of gases for deposition, which preferably and without limitation include argon gas (argon) with a small percentage of H2 (hydrogen).

[0042] The deposition stage may include one or more deposition steps of layers 12 of carbonaceous material, depending on the desired thickness to result in the set of layers 12 that may be present overall (or the deposition stage may include one or more deposition steps of layers 12, depending on how thick the set of layers 12 of carbonaceous material is desired to be overall).

[0043] In particular, in a single deposition step, the deposition machine 110 allows for the deposition of a layer 12 of carbonaceous material having a thickness measured along the Z axis equal to 100 nm. However, through multiple deposition steps, further uniform layers are superimposed on each layer 12 of carbonaceous material until a maximum thickness of 6 μm is reached.

[0044] The number of layers 12 of carbonaceous material makes it possible to predetermine the amount of thermal energy that the device 10 according to the invention (metal panel for thermal energy recovery) is able to transfer.

[0045] Preferably, a cooling interval is placed between one deposition step and the next, which allows the temperature to be kept below a value that could cause a degradation of the performance of the device 10 (metal panel with thermal energy recovery).

[0046] During the deposition process, the substrate 11 may be subjected to a voltage greater than or less than zero, which may even reach several hundred volts, as will be described below. This voltage is technically called a "bias voltage." This favors the deposition process of the carbonaceous material on the substrate 11 and, by varying the potential to which the substrate is subjected, reduces the sp 3 sp in relation to the percentage of bonds (typical of diamonds) 2The percentage of bonds (typical of graphite) varies.

[0047] According to the present invention, sp 2 or sp 3 By type bonds we mean bonds that are created by a hybridization process that takes place on a certain number of orbitals (s, p, d orbitals) with slightly different energy contents, which allows one or more central atoms of a molecule to obtain new equivalent hybrid orbitals (equal energy) with lobes oriented along the possible bond directions that they can form with other atoms. In particular, sp 2 A type orbital involves three orbitals, one s-type and two p-type. Vice versa, sp 3 The bond of type s has four hybridized orbitals, one of which is s-type and three of which are p-type.

[0048] In particular, during the deposition phase, the carbonaceous material assumes a substantially crystalline shape with a regular geometric structure similar to that of diamond, and in particular, the use of magnetron 120 recreates a geometric structure that is oriented in the same direction in a first, simpler embodiment of the deposition process.

[0049] This means that the bias voltage on the substrate 11 can be varied during the various deposition steps of the carbonaceous material, thereby changing the crystalline morphology of the carbonaceous material from layer to layer, and therefore changing the strength, density, and quantitative thermal transport capacity characteristics of each layer.

[0050] In particular, in the crystalline form desired for application in the device of the present invention, carbon is typically sp 2 Instead of the typical sp bond in diamonds, 3In particular, the crystal structure is tetrahedral (or, more particularly, in the crystal form desired for application in the device of the present invention, the carbon has the sp 2 Instead of the typical sp bond in diamonds, 3 In particular, the crystal structure is tetrahedral.

[0051] Rather than having a single layer of tall carbonaceous material, it is preferable to deposit several layers of carbonaceous material with a thin Z-axis height;

[0052] Indeed, by reducing the height of each layer of carbonaceous material deposited on the substrate 11, and in particular by keeping it below 100 nm per layer, it is possible to reduce both the temperature and the mechanical stresses in the layer itself, advantageously avoiding the sp 30 typical of graphite, in the interest of mechanical resistance and higher thermal conductivity. 2 It has been found that the percentage of type binding can be reduced.

[0053] Finally, sp 3 A continuous superposition of at least two, and preferably more, layers 12 of carbonaceous material predominantly of type bond is 2 Further experiments have shown that the absolute highest thermal transfer efficiency is found when the carbonaceous material is separated by at least one layer 12 of predominantly bonded carbonaceous material.

[0054] The described deposition process can advantageously leave the physical properties of the support substrate unchanged, and can advantageously add high thermal conductivity properties, such as to ensure fast transfer of thermal energy.

[0055] Indeed, the density properties of the material vary depending on whether a single layer of carbonaceous material is used or several layers superimposed on the substrate 11 in separate deposition passages, as shown in Figure 6. The diagram in Figure 6 details a structure in which the substrate 11 has been subjected to a bias voltage of -20V during both a single deposition phase (solid line) and several deposition phases (dashed line).

[0056] From this graph in FIG. 6, it can be seen that the rapid increase in density with decreasing thickness along the Z axis is due to the presence of a small number of microvoids, i.e., sp 3 It can be seen how it shows the index of the generation of type bonds.

[0057] Once you reach approximately 70 Å, the concentration changes with increasing thickness depending on whether there is a single layer or more of carbonaceous material, reaching approximately 2.44 g / cm for a single layer. 3 The value tends to decrease to 2.6 g / cm for several layers. 3 It remains on the order of more than .

[0058] This is because continuous exposure of the substrate 11 and the layer 12 of carbonaceous material to the action of ion bombardment increases the temperature within the layer 12, resulting in the formation of sp 2 This is because the percentage of binding increases.

[0059] Instead, FIG. 7 shows that the bias voltage fluctuation on the substrate 12 2 or sp 3 The graph in question shows in detail how the potential favors the formation of sp type bonds between -20V and 0V. 3 The percentage of binding shows that it almost stabilizes around 30%, increases sharply in the interval from 0 to 20 V, stabilizes around 45%, and then substantially decays between about 40 and 38% in the range from 30 V to 100 V.

[0060] Above this bias voltage, the sp decreases linearly to less than 20% at a bias voltage equal to 200 V, except for short-term inflections. 3 A more rapid decay in the percentage of binding is observed.

[0061] Therefore, the graph of FIG. 7 can be divided into three zones: a first zone (I) at a bias voltage between −20 V and 0 V, where there is no ion bombardment by carbon, which is deposited gently on the substrate 11 only under the action of the technical gas introduced into the vacuum chamber 111, and therefore carbon deposition occurs in a state of approximately equilibrium; a second zone (II) [0 to 100] V, where an ion sub-implantation mechanism is activated in the substrate; and a third zone (III) [100 to 200] V, where a thermalization process is activated.

[0062] It should be noted that the voltages shown in the graph are actually negative, ie the first zone actually corresponds to a positive substrate voltage.

[0063] sp 2 or sp 3 Layers of mold material are stacked one on top of the other, and the first layer 12 (said layer A) is subjected to a bias voltage (V b =-10V) and the second layer 12 (said layer B) is deposited by applying a bias voltage equal to -20V to the substrate 11, and each layer is deposited by d a and d b Experiments were performed in which the films were deposited on one, two, or three substrates with total thicknesses between 1000 and 10 ...

[0064] The total product thickness is equal to 900-1000-2600 Angstroms (90-100-260 nm).

[0065] The first deposition consists of a bilayer with dA1 ~ 150 Å and dB1 ~ 230 Å. The second through ninth depositions have dA1 ~ 50 Å. The total thickness is equal to 2620 Å (262 nm).

[0066] sp 3The content of V b The first deposited layer A1 exhibits low stress (1.35 GPa) and ensures good adhesion to the substrate 11. The first layer B1 deposited on A1 exhibits an increase in tension up to 4.5 GPa. The subsequent deposition of layer 12 has little effect on both A and B. Above a thickness of 1800 Å, the stress saturates at 5.2 GPa.

[0067] To evaluate the effect of layer A on the mean stress of the coating, the following group of layers 12a-C of carbonaceous material were deposited: * a (~900Å) and * b (~1000 Å). Thickness data are shown in the table in Figure 8.

[0068] Several deposition "recipes" are reported below which, in the course of the experiments carried out, have been shown to allow the realization of particularly effective devices according to the invention.

[0069] The first recipe, implemented by sputtering with a magnetron in the machine described above, is: - Target 140: 99.9999% pure graphite, 10 mm thick (indicated) and 75 / 90 mm diameter (indicated). - Gases introduced into the vacuum chamber 111: CH4; - Pressure inside the vacuum chamber: 5 * 10 -3 Torr; - Total gas flow rate = 70 SCCM, SCCM: standard cubic centimeters per minute (cm 3 / min). - Magnetron parameter settings: f=13.56MHz; power=150W.

[0070] The first recipe identified above made it possible to produce devices whose overall coating, consisting of multiple layers, had thicknesses of, for example, 300 nm, 600 nm, 1 μm, 3 μm, 6 μm, 10 μm, 20 μm.

[0071] The second recipe, implemented with pulsed bipolar asymmetric sputtering type, is: - Target 140: 99.9999% pure graphite, 10 mm thick (indicated) and 75 / 90 mm diameter (indicated). - Gases introduced into the vacuum chamber 111: Ar+7.5% CH4; - Pressure inside the vacuum chamber: 9.75 * 10 -3 Torr; - Magnetron parameter setting: power density = 4.4W / cm 2 ; - Characteristics of the pulsed DC signal on the magnetron 120: positive pulse +37.5V; negative impulse -(600÷700)V; source used = ENI RPG-50 (as shown); duty cycle = 70% (obtained from a frequency of 150kHz, positive pulse 2016ns); substrate bias voltage (-300÷0)V.

[0072] The second recipe identified above made it possible to produce devices whose overall coating, consisting of multiple layers, had thicknesses of, for example, 300 nm, 600 nm, 1 μm, 3 μm, 6 μm, 10 μm, and 20 μm.

[0073] The third recipe, implemented by magnetron sputtering, is instead characterized by the following parameters: - Target 140: 99.9999% pure graphite with a thickness of 10 mm (indicated) and a diameter of 75 / 90 mm (indicated); - Gases introduced into the vacuum chamber 111: Ar+H2 (0.7%); - Pressure inside the vacuum chamber 110: 30 * 10 -3 Torr; - Total flow rate inside the vacuum chamber: 40 standard cubic centimeters per minute (cm 3 / min); - Magnetron set power: 200W

[0074] The third recipe identified above made it possible to produce devices whose overall coating, consisting of multiple layers, had thicknesses of, for example, 300 nm, 600 nm, 1 μm, 3 μm, 6 μm, 10 μm, and 20 μm.

[0075] Further recipes have been developed that use carbon nanotubes to create layers of carbonaceous materials.

[0076] In particular, the first further recipe involves the use of magnetron sputtering: - 140 targets of a mixture of graphite (powder size 20 ÷ 80 nm) and 0.5% Ni powder with dimensions 60 ÷ 100 nm; - Gas introduced into the vacuum chamber 111: N2 with a purity of 99.999%; - Vacuum chamber pressure: 0.075 Torr; - Total gas flow rate: 30 SCCM standard cubic centimeters per minute (cm 3 / min); - Magnetron parameter setting: power 80W.

[0077] A second recipe was further modified using nanotubes through a technique called RF-DC bias sputtering: - Target 140 is bombarded with 99.9999% pure graphite + Ni. - Catalytic agent: a coating layer or coating of 10 nm Ni pre-deposited on the substrate. - Gas introduced into the vacuum chamber 111: N2 with a purity of 99.999%; - Vacuum chamber pressure: 0.020 Torr; - Total gas flow rate: 30 SCCM standard cubic centimeters per minute (cm 3 / min). - Magnetron parameter settings: power 100W, substrate bias supply voltage: -20V.

[0078] The deposition process can advantageously leave unchanged the physical properties of the substrate that produces the support (modular metal panel with thermal energy recovery). This is particularly important because the support substrate that produces the modular metal panel with thermal energy recovery must fulfill all the functions for which it is designed. Specifically, the panel, in addition to recovering thermal energy, also serves as an insulating cover for the walls or roofs or coverings of buildings for mobile, self-propelled structures or other types of prefabricated or non-prefabricated structures, and therefore must meet the physical, dimensional, and mechanical resistance properties predicted and defined for the specific application.

[0079] Through the described process, the carbonaceous material coating and therefore the modular metal panel with thermal energy recovery is given high resistance to chemical and abrasive agents, so that the functionality and efficiency of the nanocoating remains unchanged over time.

[0080] Advantageously, therefore, the transport of thermal energy provided by the device 10 according to the invention is of anisotropic type and therefore has a preferred direction, however, this should not be understood in a limiting manner, since it is possible to obtain a different preferred direction for each layer 12 of carbonaceous material deposited on the previous layer.

[0081] The machine 110 comprises a data processing unit and a number of sensors arranged inside the vacuum chamber 111 and electrically connected to said data processing unit, which directly or through a servo system drive at least the amount and frequency of energy emitted by the magnetron(s), the flow and pressure of the gas(es) inside the vacuum chamber 111, wherein the inside of the processing chamber and the panel metal T to be coated sub It is also possible to dynamically change the temperature T inside both the

[0082] In particular, the amount E and frequency of energy emitted by the magnetron(s) and the flow F of the gas(es) depend on at least two parameters: the substrate T sub and the residual pressure P inside the vacuum chamber c The data processing unit therefore determines, at each instant, the values ​​of the amount of energy E and the flow F of gas(es), the thickness of the deposition of the layer 12 of carbonaceous material, and the type, sp 2 or sp 3 In order to maintain this, a retro-activated control is implemented which is corrected according to the above parameters.

[0083] In particular, the at least one capacitive pressure sensor is preferably part of a plurality of sensors electrically connected to a data processing unit.

[0084] For each type of substrate 11, the data processing unit calculates a set of predetermined parameters (E, Hz, F, T, T sub ) to initiate the deposition phase, which is then adapted according to data collected by an assembly of sensors located inside the vacuum chamber 111 during the deposition process itself.

[0085] This ensures greater qualitative repeatability of the process, which is particularly useful when many more devices 10 are manufactured in series and have the same operating characteristics.

[0086] In use, the layer of carbonaceous material is capable of transporting thermal energy in the presence of a thermal differential between its substrate 11 and the second surface of the upper carbonaceous material layer. In particular, the structure of the layer of carbonaceous material is such that it has a thermal transmittance higher than that of the surrounding environment, creating a type of thermal superconductor.

[0087] In this way, heat dissipation, for example by radiation into the environment surrounding the device itself, or even by contact of the device with foreign objects, is minimized.

[0088] Using a thermal imaging device, several experiments were performed on a sample with a 200 nm carbonaceous material layer, a 50°C temperature difference between the substrate 11 side and the exposed side of the carbonaceous material layer, and an area effective for transporting thermal energy of approximately 10 × 10 mm. The average measured thermal conductivity was 1570 W / (m·K), with the maximum peak recorded being 1750 W / (m·K).

[0089] The thermoelectric converter 20 is placed in contact with a portion of the surface of the panel 10 and can convert thermal energy into electrical energy. Advantageously, the thermoelectric converter 20 can be applied to a portion of one side of the panel 10, thus realizing a system for converting thermal energy into electrical energy.

[0090] The thermoelectric converter 20 is preferably made up of multiple microcells, as well as multiple Peltiers, through which the overall efficiency achieved by the system in thermoelectric conversion can reach a peak of 55%, with an average of 40%.

[0091] The thermoelectric converter 20 has its first surface 20f in particular in direct contact with a portion of the surface of the coated panel and is configured to generate an electric current initiated by a heat difference established between an inner portion of the panel and an outer portion of the panel. The layer or layers 12 must, in use, be applied to the outer surface of the panel or to the surface facing the thermal energy of the external environment of the building or mobile structure or other prefabricated or non-prefabricated structure.

[0092] Considering a panel according to the invention, it has been observed that a particularly efficient thermoelectric converter can produce as much as 4000 W of power for a 1 sqm exposed area at a temperature difference of 50°C, which reduces to 2700 W at a temperature difference of 40°C, 1150 W at a temperature difference of 30°C, 550 W at a temperature difference of 10°C, or 300 W at a temperature difference of 5°C.

[0093] If the panel is not exposed to a sufficient thermal difference to generate energy, at least a temporary thermal imbalance can be induced by an electrical energy source using the following procedure: by supplying an electric current to the thermoelectric converter, the converter itself undergoes temperature fluctuations that can cause a transfer of thermal energy between the layers of carbonaceous material present on the substrate. This energy injection can be used as an initiation condition for the imbalance to initiate the transfer of thermal energy from the top surface of the carbonaceous material layer towards the thermoelectric converter 20. A particularly efficient solution for constructing a Peltier-like cell is achieved by stacking a pair of thermoelectric converters 20, each having a first or upper surface (technically definable as the "hot" surface) and a second or lower surface (technically definable as the "cold" surface), with the second lower surface of the first thermoelectric converter of the pair resting on the first upper surface of the second thermoelectric converter of the pair, or in either case facing the first upper surface of the second thermoelectric converter of the pair.

[0094] Advantageously, this makes it possible to recover on the second thermoelectric converter part of the dissipated thermal energy coming from the first thermoelectric converter. It should also be noted that the panel treated by adding a carbonaceous material as described above is much less susceptible to soiling, since the part of layer 12 facing outward (not facing other layers or the substrate) is very smooth (has very few microvoids) and is virtually impervious to the action of external substances such as sand, which is common not only in desert environments but also in coastal areas and which can even cause significant wear on the surface of the panel itself.

[0095] Advantageously, therefore, the panels, objects of the present invention can be used in applications in desert or coastal environments to contribute to the regulation (or regularization) of the internal temperature of buildings without being damaged by sandstorms, which are known to be able to scratch conventional surfaces (by sandblasting) due to the abrasive action of sand lifted by the wind.

[0096] Advantageously, the panel object of the present invention can be used for applications in extreme arctic and antarctic environments where extreme cold prevails, to contribute to the regulation of the internal temperature of buildings, without any damage caused by low temperatures and without interrupting the supply of light and electricity in the absence of direct sunlight.

[0097] Advantageously, the thermoelectric converter has at least one surface in contact with said layer of carbonaceous material to maximize the thermal energy recovery effect and is advantageously mounted on at least one side of the panel so as to be protected.

[0098] Finally, it will be apparent that modifications, additions and variations obvious to those skilled in the art may be applied to the panels, articles and the like of the present invention without departing from the scope of protection provided by the appended claims.

[0099] The following is the invention as originally described in the present application. <Claim 1> A metal panel with thermal energy recovery comprising a metal structure serving as a support substrate (11), at least a first layer (12; 12a-12c) of a thermally conductive carbonaceous material having an oriented geometric molecular structure, and a thermoelectric converter in contact with said layer of thermally conductive carbonaceous material. <Claim 2> 10. The panel of claim 1, comprising at least a second layer of thermally conductive carbonaceous material superimposed on said first layer of thermally conductive carbonaceous material. <Claim 3> 3. A panel according to claim 1 or 2, comprising at least one plate of metal or other material separated from the first support substrate by an insulating chamber. <Claim 4> 4. The panel according to claim 1, wherein the thermoelectric converter is disposed on at least one side of the panel. <Claim 5> 5. A panel according to any one of claims 1 to 4, wherein said at least one first layer of thermally conductive carbonaceous material provides anti-fouling, abrasion resistant and corrosion resistant properties. <Claim 6> 3. The panel of claim 2, wherein the first and second layers (12a-12c) of thermally conductive carbonaceous material each have a percentage of sp2 bonds and sp3 bonds between carbon atoms comprising the layers of carbonaceous material, and the first layer has a percentage of sp2 bonds and sp3 bonds that is different from the percentage of sp2 bonds and sp3 bonds of the second layer of carbonaceous material. <Claim 7> 7. The panel according to any one of claims 1 to 6, wherein the thermoelectric converter comprises at least one cell of a type similar to a Peltier-type cell. <Claim 8> 8. The panel according to claim 1, wherein the thermoelectric converter comprises a pair of stacked Peltier-like cells. <Claim 9> 7. A method for producing a thermal energy recovery panel according to any one of claims 1 to 6, comprising a step of depositing at least one layer (12; 12a-12c) of a carbonaceous material having an ordered geometric structure on a substrate (11) made of a metallic material in an environment (111) of a deposition machine (110), said environment being vacuum sealed and isolated from the external environment under controlled temperature and pressure conditions, said deposition occurring perpendicularly or locally along a radial direction relative to a plane or shape substantially defined by said substrate (11) made of a metallic material. <Claim 10> 8. The method of claim 7, wherein the depositing step includes obtaining at least one set of pressure and temperature values ​​within the isolated environment (111). <Claim 11> 8. The method according to claim 7, wherein the deposition step at least partly comprises the generation of an electromagnetic field applied to the substrate (11) and automatic control of the intensity of the electromagnetic field by a data processing unit of the deposition machine (110). <Claim 12> 10. The method of claim 8 or 9, further comprising the step of providing a thermoelectric converter on at least one side of the panel, the thermoelectric converter having at least one surface arranged in contact with the at least one layer (12). <Claim 13> 11. The method of any one of claims 7 to 10, further comprising varying the strength of the electromagnetic field during the deposition of a plurality of superimposed layers (12a-12c) of carbonaceous material, wherein said change in strength of the electromagnetic field produces a change in the concentration of sp2 and sp3 bonds in the deposited layer relative to a previously or subsequently deposited layer.

Claims

1. A metal panel with thermal energy recovery, comprising a metal structure serving as a support substrate (11), at least a first layer (12; 12a-12c) of a thermally conductive carbonaceous material having an oriented geometric molecular structure, at least a second layer (12; 12a-12c) of a thermally conductive carbonaceous material superimposed on the first layer of the thermally conductive carbonaceous material, and a thermoelectric converter in contact with the layer of the thermally conductive carbonaceous material, wherein the first and second layers (12a-12c) of the thermally conductive carbonaceous material each have sp junctions between the carbon atoms constituting the layer of the carbonaceous material. ２ Type bonds and sp ３ and the first layer has a respective percentage of sp type bonds of the second layer of carbonaceous material. ２ type bond and the sp ３ The sp different from the percentage of type bonds ２ type bond and the sp ３ A metal panel characterized by having a percentage of mold bond.

2. 10. The metal panel of claim 1, comprising at least one plate of metal or other material separated from the first support substrate by an insulating chamber.

3. 2. The panel of claim 1, wherein the thermoelectric converter is disposed on at least one side of the panel.

4. Metal panel according to any one of claims 1 to 4, characterized in that the thermoelectric converter comprises at least one cell of the Peltier type or similar.

5. A metal panel according to any one of claims 1 to 4, characterized in that the thermoelectric converter comprises a pair of superimposed Peltier or similar cells.

6. 6. A method for producing a metal panel with thermal energy recovery according to any one of claims 1 to 5, characterized in that it comprises a deposition stage of at least one layer (12; 12a-12c) of a carbonaceous material with a structurally ordered geometry on a substrate (11) made of a metallic material in an environment (111) of a deposition machine (110), said environment being vacuum sealed and isolated from the external environment under controlled temperature and pressure conditions, said deposition occurring orthogonally or locally along a radial direction relative to a plane or shape substantially defined by said substrate (11) made of a metallic material.

7. 7. The method of claim 6, wherein the deposition stage includes obtaining at least one set of pressure and temperature values ​​within the isolated environment (111).

8. 7. The method according to claim 6, characterized in that the deposition stage comprises at least in part the generation of an electromagnetic field applied to the substrate (11) and automatic control of the intensity of the electromagnetic field by a data processing unit of the deposition machine (110).

9. 7. The method of claim 6, further comprising the step of installing a thermoelectric converter on at least one side of the panel, the thermoelectric converter having at least one surface positioned in contact with the at least one layer (12).

10. The method further comprises the step of varying the strength of the electromagnetic field during the deposition of the plurality of superimposed layers (12a-12c) of carbonaceous material, wherein the change in strength of the electromagnetic field results in a change in the sp of the deposited layer relative to a previously or subsequently deposited layer. ２ and sp ３ The method of any one of claims 8 to 9, wherein a change in concentration of binding is produced.

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