Thermal energy recovery cover plate for generating electrical energy

Abstract

The invention relates to a modular metal sheet for thermal energy recovery, with and without cavities, usable for buildings, self-propelled mobile structures or other types of prefabricated or non-prefabricated structures, with a metal structure (11) as a support, for at least one layer (12) of thermally conductive carbonaceous material coupled to a thermoelectric converter, electrical energy can be generated on the basis of a temperature difference between the first face and the second face of the at least one layer (12). The invention also relates to a method for manufacturing said sheet.

Description

Technical Field

[0001] The present invention relates to the field of metal roof panels, and in particular to a roof panel with a heat recovery (heat or cold) function, which is used for generating electric energy with zero emission. Background Art

[0002] It is known that the walls and roofs of many buildings are covered with panels of different types of materials. These panels are usually used to improve the thermal insulation of the interior of the building.

[0003] Existing types of panels are unable to recover any energy, although their outer surfaces are subjected to thermal energy from the sun or thermal energy (heat or cold) from the air, which could have been used inside the building.

[0004] Furthermore, panels of known type are sensitive to the effects of one or more atmospheric phenomena, in particular to the effects of corrosive agents (such as sand in desert or coastal areas), which may lead to considerable wear of the panel surface.

[0005] The object of the present invention is therefore to describe a heat recovery panel that solves the above-mentioned drawbacks and at the same time produces zero-emission electrical energy. Summary of the invention

[0006] According to the present invention, modular metal panels with and without cavities with heat recovery are manufactured for zero emission generation of electrical energy, which can be used in buildings, self-propelled mobile structures or any other type of prefabricated or non-prefabricated structures.

[0007] The metal plate with a cavity for heat recovery to generate zero-emission electricity includes a metal structure as a supporting substrate, at least one metal plate or other material, on which one or more metal structures are provided as a supporting substrate. The metal structure as a supporting substrate includes a first thermally conductive carbonaceous material layer; the layer is superimposed on the surface of the metal structure as a substrate and has a directional geometric molecular structure, and a thermoelectric converter in contact with the thermally conductive carbonaceous material layer.

[0008] The cavity-free metal plate for heat recovery to generate zero-emission electricity is particularly suitable for buildings for creating wall or roof ventilation coverings, comprising a metal structure as a supporting substrate, a first layer of heat-conducting carbonaceous material; the layer is superimposed on the surface of the metal structure as a substrate and has a directional geometric molecular structure, and a thermoelectric converter in contact with the heat-conducting carbonaceous material layer.

[0009] Preferably, the surface of the metal plate comprises at least a second thermally conductive carbonaceous material layer superimposed on the first thermally conductive carbonaceous material layer.

[0010] Specifically, the thermoelectric converter is located on the metal structure as a substrate.

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

[0012] Specifically, in the converter, the first and second heat-conductive carbonaceous material layers each have a sp between carbon atoms forming the carbonaceous material layers. 2 Type bond and sp 3 The percentage of type bonds, the sp 2 Type bond and the sp 3 The percentage of type bonds is related to the sp 2 Type bond and the sp 3 The percentage of type bonds is different.

[0013] Preferably, the thermoelectric converter comprises at least one Peltier-like unit.

[0014] More specifically, the thermoelectric converter comprises a pair of superimposed Peltier-like cells.

[0015] According to the present invention, a method for manufacturing the metal plate for thermal energy recovery is implemented to generate electrical energy with zero emissions, and the method includes the steps of depositing at least one layer of carbonaceous material with an ordered geometric structure on a substrate made of metal material in a vacuum and isolated environment under controlled temperature and pressure conditions; the deposition is carried out along a direction orthogonal or locally radial to a plane or shape basically determined by the substrate made of metal material.

[0016] Preferably, the depositing step comprises the step of acquiring at least one set of pressure and temperature values ​​in the vacuum and isolation environment.

[0017] Preferably, said depositing step comprises the step of generating an electromagnetic field at least partially acting on said substrate and automatically controlling said strength of said electromagnetic field by means of a data processing unit of said deposition machine.

[0018] Preferably, the method further comprises a step of changing the intensity of the electromagnetic field during the stage of depositing a plurality of superimposed carbonaceous material layers, wherein the sp 2 Type bond and sp 3 The change in the concentration of bonds relative to the previously or subsequently deposited layers.

[0019] Preferably, the method further comprises the step of mounting a thermoelectric converter on the board; the thermoelectric converter having at least one surface in contact with the at least one layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The present invention will now be described with reference to the accompanying non-limiting drawings, in which:

[0021] Figure 1 A cross-sectional view of a metal plate with a cavity is shown;

[0022] Figure 2 A cross-sectional view of a metal plate without a cavity is shown;

[0023] Figure 3 A partial detail view of a metal plate for heat recovery including a heat transfer device is shown;

[0024] Figure 4 A second alternative embodiment of the metal plate is shown;

[0025] Figure 5 Shows the manufacturing Figure 3 and Figure 4 Schematic diagram of the machine for producing metal sheets;

[0026] Figure 6 and Figure 7 Graphs showing details of the process for obtaining a plate according to the invention, in particular they relate to a density versus carbonaceous material coating thickness graph, and sp 3 The relationship between the percentage of type bond and the voltage supplied to the metal substrate;

[0027] Figure 8 A table of carbonaceous material layer thickness values ​​is shown. DETAILED DESCRIPTION

[0028] Referring to the accompanying drawings, figure numeral 10 generally represents a portion of a metal plate for heat recovery; the metal plate has at least one metal structure as a supporting substrate 11, and the metal plate includes a carbonaceous material layer, the details of which will be better described below, and the carbonaceous material layer is configured to conduct heat energy along one or more basically predetermined directions to convert it into electrical energy.

[0029] Specifically, Figure 1 As shown in the cross-sectional view, the plate includes, in addition to the metal substrate 11, a metal plate or other material or a fixed profile 11', thereby forming a metal plate for heat recovery with or without a cavity (natural ventilation), which can also reduce heat loss and noise transfer.

[0030] Specifically, the plate 10 includes a substrate 11, located on a plane defined by a first pair of axes X and Y, on which is superimposed at least one carbonaceous material layer 12, the carbonaceous material layer having a desired uniform thickness over its entire surface, thereby defining a first face 13 and a second face 14 opposite to each other, and specifically facing the substrate 11 and the outside, respectively. The superposition of the substrate 11 and the carbonaceous material layer 12 occurs on a Z axis that is substantially orthogonal to the pair of X and Y axes. For clarity, Figure 3 The heat energy acting on the plate is schematically shown by arrows 1000 in FIG.

[0031] The layer 12 allows directing the thermal energy received on the second face 14 of the layer 12 in at least one preferred direction.

[0032] exist Figure 4 In the alternative embodiment shown, the metal sheet of the invention comprises a plurality of layers 12a, 12b, 12c, each layer being superimposed on the previous layer.

[0033] Ideally, each sp 2 The thickness of the bonding layer and other sp 2 The bonding layer is the same, each sp 3 The thickness of the bonding layer and other sp 3 The bonding layer is the same.

[0034] According to the present invention, the metal plate 10 is manufactured by a process including a first pre-cleaning step, in which the substrate 11 is carefully cleaned on a nanoscale scale to ensure the correct growth of the first carbonaceous material layer 12 .

[0035] Specifically, the first pre-cleaning step aims to eliminate all micron-sized impurities and most nano-sized impurities.

[0036] Since the temperatures during the pre-cleaning step may exceed 65°C, it is important that the substrate 11 can withstand these temperatures without damage.

[0037] Specifically, the pre-cleaning step can be performed by the following first alternative:

[0038] -Pre-cover the substrate surface with acetone;

[0039] -Subsequent wiping step with pad;

[0040] - a subsequent rinsing step, preferably with isopropanol (propan-2-ol);

[0041] - Then use a nitrogen gun (N 2 ) Step of drying the substrate.

[0042] Alternatively, the cleaning stage may also, in addition to or in addition to one or more of the previous stages, include:

[0043] - Oxygen plasma etching stage (etching treatment) to remove the remaining organic film;

[0044] -RCA cleaning technology stage, to remove metals, oxides and organic pollutants, is divided into two stages: the first organic cleaning stage, using 5:1:1 H 2 O:H 2 O 2 :NH 4OH solution removes insoluble organic contaminants; the second stage, called “oxide stripping,” removes thin layers of SiO that may have accumulated metal contaminants 2 .

[0045] - "Piranha Cleanse" or "Piranha Etch" by mixing 98% H 2 SO 4 and 30% H 2 O 4 (volume ratio of 2-4:1) to remove organic materials (photoresist, oil, etc.), and then heat the cleaned substrate to 100°C;

[0046] -Ultrasonic cleaning stage: the substrate is placed in an ultrasonic cleaning machine to remove contaminants through ultrasound.

[0047] Experiments have shown that the best solution for cleaning the substrate 11 is to immerse it in a piranha solution (H 2 SO 2 :H 2 O 2 , 7:3, 10 minutes), and then ultrasonic cleaning was performed.

[0048] Finally, after the cleaning phase, the substrate 11 always undergoes a deposition phase in a HV or UHV chamber, cleaned by low-energy etching to avoid amorphization. At this point, the substrate is ready for processing.

[0049] Subsequently, the process is performed in the vacuum chamber 111 ( Figure 5 ) in the vacuum chamber; in the vacuum chamber, the internal air is evacuated by a molecular vacuum pump to reach a threshold pressure (preferably less than 10 -1 Pa), followed by a deposition phase of one or more layers 12 of carbonaceous material.

[0050] In particular, the deposition machine 110 comprises at least one mobile magnetron sputtering 120, a system for holding and moving the substrate, located in a vacuum chamber 111, and a gas inlet 150, the end of which is also located in the vacuum chamber. The vacuum chamber 111 creates a clean, isolated environment in which the deposition phase is carried out under controlled and managed temperature and pressure optimal conditions according to the process.

[0051] During the deposition phase, the magnetron 120 is activated and generates an electromagnetic field that precisely acts on the substrate 11 as the substrate 11 translates along an X, Y plane defined by planes parallel to the substrate 11 .

[0052] Therefore, relative motion occurs between the magnetron 120 and the substrate 11 in the X, Y plane, which enables the deposition of the carbonaceous material to be more precise than conventional sputtering techniques.

[0053] Also located within the vacuum chamber 111 is an electron gun 130 that emits an electron beam toward a carbon target 140, which is preferably, but not limitedly, a planar type and is positioned in contact with the electrode. Carbon atoms are stripped from the carbon target 140 and directed toward the substrate 11.

[0054] Specifically, the carbon target 140 is selected to be 99.99% pure graphite to obtain a coating having a diamond-like crystal structure.

[0055] The purity of graphite is 99.99%, which facilitates the deposition of the efficient carbonaceous material layer 12 and avoids the diffusion of impurities in the vacuum chamber 111, which may significantly reduce the overall efficiency of the device.

[0056] While the magnetron 120 is activated, a deposition gas enters the chamber, preferably but not limited to Ar (argon) and a small amount of H 2 (hydrogen).

[0057] The deposition phase may include one or more deposition steps of a layer 12 of carbonaceous material, depending on the desired total thickness of the set of layers 12 .

[0058] In particular, in fact, with a single deposition step, the deposition machine 110 can deposit a carbonaceous material layer 12 with a thickness - measured along the Z axis - of 100 nm. However, with multiple deposition steps, more uniform layers can be superimposed on each carbonaceous material layer 12 until a maximum thickness of 6 μm is reached.

[0059] According to the present invention, the number of carbonaceous material layers 12 may predetermine the amount of heat energy that the device 10 (heat recovery metal plate) can transfer.

[0060] Preferably, a cooling interval is left between one deposition step and the next; this keeps the temperature below a value that could cause the performance of the device 10 (heat recovery metal plate) to degrade.

[0061] During the deposition step, the substrate 11 can selectively be subjected to a voltage greater than or less than zero, which, as described below, can in some cases reach several hundred volts. This voltage is referred to as a "bias voltage" in the technical field. This specifically helps the deposition process of the carbonaceous material on the substrate 11, and by changing the voltage applied to the substrate 11, the deposition in the carbonaceous material layer can be controlled. 2 The percentage of bonds (graphitic) can be expressed relative to sp 3 The percentage change of the bond (diamond type).

[0062] According to the present invention, sp 2 or sp 3A sp type bond is a bond generated by a hybridization process that occurs on a predetermined number of orbitals (s, p, d orbitals) with slightly different energy contents; this type of bond allows the acquisition of new equivalent hybrid orbitals (isoenergetic orbitals) whose lobes are oriented in the direction of possible bonds that the central atom in one or more molecules may form with other atoms. Specifically, sp 2 The type orbital involves three orbitals, one of which is s-type and two of which are p-type; on the contrary, in sp 3 In the case of a type bond, four orbitals are hybridized, one of which is s-type and three are p-type.

[0063] In particular, during the deposition step, the carbonaceous material assumes an essentially crystalline shape with an ordered geometric structure similar to that of diamond; in particular, by using the magnetron 120 , a geometric structure is recreated which, in a first and simpler implementation of the deposition process, is oriented in the same direction.

[0064] This means that in each deposition step of the carbonaceous material, the bias voltage on the substrate 11 can be changed, thereby changing the crystal form of the carbonaceous material layer by layer, thereby changing the strength, density and quantitative heat transfer capacity characteristics of each layer.

[0065] Specifically, in the crystalline form desired for use in the apparatus of the present invention, carbon has sp 3 Advantages of type bonds (diamond type) rather than sp 2 Type bond (graphite type). In particular, the crystal structure is tetrahedral.

[0066] Preferably, multiple layers of carbonaceous material are deposited, each layer having a lower height along the Z axis, rather than a single layer of carbonaceous material having a higher height;

[0067] In fact, by reducing the height of each layer of carbonaceous material deposited on the substrate 11, and in particular keeping it below 100 nm per layer, it is possible to reduce the mechanical stresses and the temperature of the layer itself, thus advantageously reducing the sp 2 The percentage of graphite-type bonds is favorable for mechanical strength and higher thermal conductivity.

[0068] Finally, further experiments showed that when at least two, preferably more, sp 3 The carbonaceous material layer 12 having the advantage of type bond is formed by sp 2 The absolute highest heat transfer efficiency is achieved when at least one carbonaceous material layer 12 is separated by a type bond advantage.

[0069] The described deposition process advantageously enables the physical properties of the supporting substrate to remain unchanged while adding properties of high thermal conductivity, for example ensuring a rapid transfer of thermal energy.

[0070] like Figure 6As shown, in fact, depending on whether a single layer of carbonaceous material is used or multiple layers are superimposed on the substrate 11 during different deposition processes, the density characteristics of the material will vary. Figure 6 The diagram shows in detail the structure of the substrate 11 when a bias voltage of -20 V is applied, whether it is a single deposition stage (solid line) or a multiple deposition stage (dashed line).

[0071] Now, from Figure 6 As can be seen from the graph, the rapid increase in density at lower thickness along the Z axis indicates the presence of a small number of microvoids, which is sp 3 Type key generated indicators.

[0072] At about 70 angstroms, the density varies with thickness, depending on whether it is a single or multiple carbonaceous material layers, and in the case of a single layer the density drops to about 2.44 g / cm 3 , while the density of the multilayer case remains at about 2.6 g / cm 3 above.

[0073] This is because the substrate 11 and the carbonaceous material layer 12 are continuously exposed to ion bombardment, which causes the temperature inside the layer 12 to increase, thereby increasing the sp 2 The percentage of type keys.

[0074] Figure 7 Instead, it is shown in detail how the change of bias voltage on substrate 12 promotes sp 2 Type or sp 3 The graph shows that between -20V and 0V, sp 3 The percentage of type bonds remains stable at about 30%, then increases sharply in the 0 to 20V interval, stabilizes at about 45%, and then decays to between about 40% and 38% in the range of approximately 30V to 100V.

[0075] Beyond this bias voltage value, sp 3 The percentage of type bonds decays more rapidly, decreasing linearly except for a brief inflection point to just below 20% at a bias voltage of 200 V.

[0076] Figure 7 The diagram of can thus be divided into three regions, a first region (I) where, at a bias voltage between -20 V and 0 V, carbon is not bombarded by ions but is gently deposited on the substrate 11, which is only acted upon by the technical gas introduced into the vacuum chamber 111; carbon deposition thus occurs under conditions close to equilibrium. This is followed by a second region (II) [0-100] V, where the ion secondary implantation mechanism in the substrate is activated, and a third region (III) [100-200] V, where the thermalization process is activated.

[0077] It should be noted that the voltages indicated in the diagram are actually negative, ie the first region actually corresponds to a positive voltage of the substrate.

[0078] An experiment was conducted in which sp 2 Type or sp 3 The first layer 12 (referred to as layer A) is deposited at a bias voltage of 10V (V b =-10V) substrate 11; the second layer 12 (referred to as layer B) is deposited on the substrate 11 with a bias voltage of -20V, each layer is deposited on one, two or three substrates, with a total thickness of d a and d b between.

[0079] The total product thickness is 900-1000-2600 angstroms (90-100-260nm).

[0080] The first deposition consisted of a double layer, From the second to the ninth deposition, The total thickness is

[0081] sp 3 The content depends on V b The first deposited layer A1 shows low stress (1.35 GPa) and ensures good adhesion to the substrate 11. The first layer B1 deposited on A1 shows an increase in stress to 4.5 GPa. The subsequent deposition of layer 12, whether A or B, has little effect. When the thickness is , the stress saturates at 5.2 GPa.

[0082] In order to evaluate the effect of layer A on the average stress of the coating, the following carbonaceous material layers 12 groups aC were deposited: and Thickness data such as Figure 8 As shown in the table.

[0083] Some deposition "recipes" are reported below which, during experiments, have been shown to enable particularly effective devices according to the invention to be achieved.

[0084] The first recipe, performed by magnetron sputtering on the above machine, consists of:

[0085] - Target 140: 99.9999% pure graphite, thickness 10 mm (indicative), diameter 75÷90 mm (indicative).

[0086] -Gas introduced into the vacuum chamber 111: CH 4 ;

[0087] -Pressure in vacuum chamber: 5*10 -3Torr;

[0088] -Total gas flow = 70 SCCM, standard cubic centimeters per minute (cm 3 / min).

[0089] -Magnetron parameter settings: f = 13.56 MHz; power = 150 W.

[0090] The first formulation described above is capable of producing multi-layer devices with overall coating thicknesses of, for example, 300 nm; 600 nm; 1 μm; 3 μm; 6 μm; 10 μm; 20 μm.

[0091] The second recipe, performed by pulsed bipolar asymmetric sputtering type, includes:

[0092] - Target 140: 99.9999% pure graphite, thickness 10 mm (indicative), diameter 75÷90 mm (indicative).

[0093] - Gas introduced into the vacuum chamber 111: Ar + 7.5% CH4;

[0094] -Pressure in vacuum chamber: 9.75*10 -3 Torr;

[0095] -Magnetron parameter setting: power density = 4.4W / cm 2 ;

[0096] - Characteristics of the pulsed DC signal on the magnetron 120: positive pulse +37.5V; negative pulse -(600÷700)V; source used = ENI RPG-50 (indicative); duty cycle = 70%, obtained by a frequency of 150kHz, positive pulse 2016ns; substrate bias voltage (-300÷0)V.

[0097] The second formulation described above is capable of producing multi-layer devices with overall coating thicknesses of, for example, 300 nm; 600 nm; 1 μm; 3 μm; 6 μm; 10 μm; 20 μm.

[0098] The third recipe, carried out by magnetron sputtering, is characterized by, in contrast, the following parameters:

[0099] - Target 140: 99.9999% pure graphite, thickness 10 mm (indicative), diameter 75÷90 mm (indicative).

[0100] -Gas introduced into the vacuum chamber 111: Ar+H 2 (0.7%);

[0101] -Pressure in vacuum chamber 110: 30*10 -3 Torr;

[0102] -Total gas flow in the vacuum chamber: 40 SCCM, standard cubic centimeters per minute (cm 3 / min).

[0103] -Magnetron power setting: 200W

[0104] The third formulation described above is capable of producing multi-layer devices with overall coating thicknesses of, for example, 300 nm; 600 nm; 1 μm; 3 μm; 6 μm; 10 μm; 20 μm.

[0105] Other formulations have also been developed that use carbon nanotubes to make one or more layers of carbonaceous materials.

[0106] In particular, the first further formulation involves the use of magnetron sputtering:

[0107] - Target 140 is a mixture of graphite (powder size 20÷80 nm) and 0.5% Ni powder (size 60÷100 nm).

[0108] -Gas introduced into vacuum chamber 111: 99.999% pure N 2 ;

[0109] -Vacuum chamber pressure: 0.075 Torr;

[0110] -Total gas flow: 30 SCCM, standard cubic centimeters per minute (cm 3 / min).

[0111] -Magnetron parameter setting: power 80W.

[0112] Another recipe using nanotubes, performed via a technique called RF-DC bias sputtering:

[0113] - Bombarding target 140 which is 99.9999% pure graphite + Ni.

[0114] - Catalyst: 10nm Ni layer or coating previously deposited on the substrate.

[0115] -Gas introduced into vacuum chamber 111: 99.999% pure N 2 ;

[0116] -Vacuum chamber pressure: 0.020Torr;

[0117] -Total gas flow: 30 SCCM, standard cubic centimeters per minute (cm 3 / min).

[0118] -Magnetron parameter settings: power 100W; substrate bias voltage: -20V.

[0119] The deposition process advantageously allows to keep unchanged the physical characteristics of the supporting substrate (thermal energy recovery modular metal panel). This is particularly important since the supporting substrate as a thermal energy recovery modular metal panel must satisfy all the functions for which it is designed. In particular, the panels, in addition to recovering thermal energy, are also used as thermal insulation coverings for walls or roofs of buildings, or coverings for self-propelled mobile structures or other types of prefabricated or non-prefabricated structures, and therefore must comply with the physical, dimensional and mechanical strength characteristics required for the specific application.

[0120] Through the described process, the carbonaceous material coating and the thermal energy recovery modular metal plate have a high resistance to chemical and anti-wear agents, so that the functionality and efficiency of the nano coating remain unchanged over time.

[0121] Preferably, therefore, the heat transfer provided by the device 10 according to the invention is anisotropic and thus has a preferred direction. However, this should not be understood as limiting, as a different preferred direction may be obtained for each layer of carbonaceous material 12 deposited on the previous layer.

[0122] The machine 110 is equipped with a data processing unit and a plurality of sensors located in a vacuum chamber 111, electrically connected to the data processing unit, which directly or through a servo system drives at least: the energy and frequency emitted by the magnetron(s), the flow rate and pressure of the gas(s) in the vacuum chamber 111, wherein the vacuum chamber 111 can also dynamically change the temperature T in the processing chamber and of the metal sheet Tsub to be coated.

[0123] Specifically, the amount E and frequency of energy emitted by the magnetron(s) and the flow rate F of the gas(s) vary according to at least two parameters: the temperature of the substrate Tsub and the vacuum chamber P c The residual pressure in the carbonaceous material layer 12 is thus controlled by the data processing unit, and a feedback control is implemented in which the value of the amount of energy E and the gas (s) flow rate F is corrected according to the above parameters at each time point to maintain the deposition thickness uniformity and type (sp 2 or sp 3 ).

[0124] In particular, the at least one capacitive pressure sensor is preferably part of a plurality of sensors which are electrically connected to the data processing unit.

[0125] For each type of substrate 11 , the data processing unit is configured to start the deposition phase with a predefined set of parameters (E, Hz, F, T, Tsub) and then make adjustments based on the data collected by the sensor assembly located in the vacuum chamber 111 during the deposition step.

[0126] This ensures a higher quality repeatability of the process, which is particularly useful when more devices 10 having the same operating characteristics need to be mass-produced.

[0127] In use, the one or more carbonaceous material layers allow thermal energy to be transferred when there is a temperature difference between the substrate 11 and the second side of the carbonaceous material layer thereon. In particular, the structure of the one or more carbonaceous material layers has a higher heat transfer rate than the surrounding environment, forming a thermal superconductor.

[0128] In this way, heat losses, for example by radiation to the environment surrounding the device or by contact of the device with external objects, are minimized.

[0129] Through experiments conducted on some samples, the area of ​​the effective part for transferring heat energy is about 10x10mm, the thickness of the carbonaceous material layer is 200nm, and the temperature difference between one side of the substrate 11 and the exposed side of the carbonaceous material layer is 50°C, which is displayed by a thermal imaging camera, and the average thermal conductivity is detected to be 1570W / (m·K), and the maximum peak is recorded as 1750W / (m·K).

[0130] Thermoelectric converter 20 is installed on a part of the surface of board 10, and can convert thermal energy into electrical energy. Preferably, thermoelectric converter 20 can be installed on a part of one side of board 10, so as to realize the conversion system of thermal energy and electrical energy.

[0131] Thermoelectric converter 20 is preferably composed of a plurality of Peltier-like micro-cells, through which the overall efficiency of the system in thermoelectric conversion can reach a peak of 55% and an average efficiency of 40%.

[0132] The thermoelectric converter 20, whose first face 20f is in direct contact with a portion of the surface of the coated plate, is configured to generate an electric current based on the temperature difference between the inside and the outside of the plate. One or more layers 12 must be applied to the outer surface of the plate, i.e. the side facing the thermal energy of the external environment of the building or self-propelled mobile structure or other prefabricated or non-prefabricated structure.

[0133] Taking into account the panels according to the invention, it has been observed that, using particularly efficient thermoelectric converters, it is possible to obtain an electrical power of up to 4000 W for an exposed area of ​​1 m2 at a temperature difference of 50°C, falling to 2700 W if the temperature difference is 40°C, to 1150 W if the temperature difference is 30°C, to 550 W if the temperature difference is 10°C and to 300 W if the temperature difference is 5°C.

[0134] If the plates are not subject to temperature differences sufficient to generate energy, a thermal imbalance can be triggered at least temporarily by a power supply by the following steps: By supplying power to the thermoelectric converter, the converter itself will be subject to a temperature change, possibly resulting in a heat transfer between the layers of carbonaceous material on the substrate. This energy injection can be used as an initial condition to initiate an imbalance in the heat transfer, transferring thermal energy from the outermost surface of the carbonaceous material layer to the thermoelectric converter 20. A particularly efficient way to configure a Peltier-like unit is accomplished by superimposing a pair of thermoelectric converters 20, each of which has a first face or upper surface (technically defined as a "hot" face) and a second face or lower surface (technically defined as a "cold face"), and the second lower surface of the first thermoelectric converter of the pair or in any case the first upper surface of the second thermoelectric converter of the pair is facing the first thermoelectric converter of the pair.

[0135] Preferably, this allows to recover part of the dissipated heat energy from the first thermoelectric converter to the second thermoelectric converter. It is also noted that the plates treated with the above-mentioned addition of carbonaceous material are less affected by dust, since the part of layer 12 facing the outside (not facing other layers or substrate) is very smooth (almost free of micropores) and is hardly affected by external agents, such as sand often found in desert environments or coastal areas, where such sand may significantly wear the surface of the plates.

[0136] Preferably, therefore, the panels of the invention may be used in applications in desert or coastal environments to help regulate the temperature inside buildings without being damaged by sandstorms which can often scratch conventional surfaces through the sanding (grinding) action of the wind.

[0137] Preferably, the panels of the present invention may be used in extreme Arctic and Antarctic environments governed by extremely low temperatures to help regulate the temperature inside buildings without being damaged by the low temperatures and without interrupting the power supply in the absence of light and direct solar radiation.

[0138] Preferably, the thermoelectric converter has at least one surface in contact with the carbonaceous material layer to maximize the heat energy recovery effect, and is preferably mounted on at least one side of the plate so as to be protected.

[0139] Finally, it is clear that modifications, additions and variations may be made to the panel of the present invention, as will be apparent to a person skilled in the art, without departing from the scope of protection offered by the appended claims.

Claims

1. A metal plate for heat recovery, comprising a metal structure as a supporting substrate (11), at least a first heat-conducting carbonaceous material layer (12; 12a-12c) having a directional geometric molecular structure, and a thermoelectric converter in contact with the heat-conducting carbonaceous material layer.

2. The plate according to claim 1, comprising at least a second layer of thermally conductive carbonaceous material superimposed on the first layer of thermally conductive carbonaceous material.

3. The board according to claim 1 or 2, comprising at least one metal plate or plate of other material separated from the first supporting substrate by an insulating cavity.

4. A plate according to any one of claims 1 to 3, characterized in that The thermoelectric converter is located on at least one side of the plate.

5. The plate according to any one of claims 1 to 4, characterized in that The at least first layer of thermally conductive carbonaceous material has anti-fouling and anti-wear properties, imparting anti-corrosion characteristics.

6. The plate according to claim 2, characterized in that The first thermally conductive carbonaceous material layer and the second thermally conductive carbonaceous material layer (12a-12c) each have sp between carbon atoms constituting the carbonaceous material layer. 2 Type bond and sp 3 The percentage of type bonds, the sp 2 Type bond and the sp 3 The percentage of type bonds is related to the sp 2 Type bond and the sp 3 The percentage of type bonds is different.

7. A plate according to any one of claims 1 to 6, characterized in that The thermoelectric converter comprises at least one cell similar to a Peltier type cell.

8. A plate according to any one of claims 1 to 7, characterised in that The thermoelectric converter comprises a pair of superimposed Peltier-like cells.

9. A method for manufacturing a heat recovery plate according to any one of claims 1 to 6, the method comprising: A step of depositing at least one carbonaceous material layer (12; 12a-12c) having an ordered geometric structure on a substrate (11) made of a metal material under controlled temperature and pressure conditions in an environment that is vacuum and isolated from the external environment, wherein the deposition is carried out in a direction orthogonal or locally radial to a plane or shape substantially determined by the substrate (11) made of the metal material.

10. The method according to claim 7, characterized in that The deposition phase comprises the step of acquiring at least one set of pressure and temperature values ​​within the isolated environment (111).

11. The method according to claim 7, characterized in that The deposition phase comprises the steps of generating an electromagnetic field at least partially acting on the substrate (11), and automatically controlling the intensity of the electromagnetic field by means of a data processing unit of the deposition machine (110).

12. The method according to claim 8 or 9, further comprising the step of mounting a thermoelectric converter on at least one side of the plate; the thermoelectric converter having at least one surface in contact with the at least one layer (12).

13. The method according to any one of claims 7 to 10, further comprising: When depositing a plurality of superimposed carbonaceous material layers (12a-12c), a step of changing the electromagnetic field strength is performed, wherein the sp of the deposited layers is generated by the change in the electromagnetic field strength. 2 Key and sp 3 The change in the concentration of a bond relative to the concentration of a previously or subsequently deposited layer.

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