A process for making a metal plate to be used as an electrode in an electrochemical process for producing energy and the electrode

Abstract

A process for making an electrode to be used to produce energy, comprising the preparation of an industrial product (100), the at least partial melting of the industrial product (100) at a temperature above 2500°C, a first doping of the industrial product (100) during said melting by adding a first doping substance in a quantity ranging between 25 and 2500 ppm, a second doping of the industrial product (100) during said melting by adding a second doping substance selected from either aluminium or aluminium oxide in a quantity ranging between 25 and 2500 ppm and / or a third doping substance containing silicon, the rolling of said doped industrial product (101) until achieving a first thickness ranging between 20 and 2000 μm and a first annealing of the doped industrial product (101) at a temperature ranging between 500 and 1500°C and following said rolling, preferably between 800 and 1000°C.

Description

[0001] A PROCESS FOR MAKING A METAL PLATE TO BE USED AS AN ELECTRODE IN AN ELECTROCHEMICAL PROCESS FOR PRODUCING ENERGY AND THE ELECTRODE

[0002] This invention relates to a process for making a metal plate to be used as an electrode in an electrochemical process for producing energy, as well as an electrode.

[0003] This invention therefore finds application in the field of energy production, preferably in the production of “clean” energy using an electrochemical process.

[0004] Over the past 20 years, research in the field of clean energy production has accelerated considerably, with research and industrial groups that have invested, and are still investing, considerable resources in identifying processes that allow energy to be generated without producing, or producing fewer, pollutants.

[0005] Among the various alternatives pursued over the years, progress is being made, in an increasingly organised way, in the production of energy using so-called Low Energy Nuclear Reactions. Via such reactions, it would be possible to produce excess power, exploiting an electrochemical process started within an electrochemical cell in which the various components (cell, cathode, anode, electrolyte) have special conditions.

[0006] As is well known, however, one of the main critical issues related to these events is their poor reproducibility, due not so much to the randomness inherent in the process as to the technological difficulty in producing components and materials with constant and repeatable chemical and metallurgical characteristics, even at the micrometric and sub-micrometric levels.

[0007] In this regard, studies are known concerning the preparation of electrodes with special metallurgical and chemical-surface characteristics suitable to favour the absorption / loading capacity of hydrogen or its isotopes (particularly deuterium), so as to achieve very high loading levels. In fact, it has been observed in numerous experiments that a condition necessary to generating excess power in the cell is the presence of a loading level of hydrogen isotopes (e.g. deuterium - D) in the cathode, typically made of palladium (Pd), in excess of 80% (D / Pd ratio > 0.8 atomic fraction).

[0008] More specifically, the Applicant found experimentally that the greatest effects are obtained with palladium deuteride and that the phenomenon is a threshold phenomenon, that is it only occurs when the atomic deuterium / palladium ratio reaches a value above 0.8, preferably close to or above 0.9.

[0009] But not only that, the scientific literature concerning the phenomena of power generation at low temperatures (that is, a temperature not far from ambient temperature) identifies numerous other characteristics that are necessary on the electrodes in order for spontaneous excess power to be observed in the cell. These characteristics are partly illustrated in the Italian patent IT102008901652846 of 2008, in which parameters such as the diameter of the crystalline grains (between 50 and 100 pm), the morphology and orientation of the grains (equal to 100 in most grains), the presence of a limited amount of impurities (<0.05%) and, generally, a high excess voltage are identified.

[0010] This patent also attempts to describe a metallurgical-manufacturing process that make it possible to obtain these characteristics; however, it in fact proved to be unreliable, leading to samples that only partly actually resulted in excess power.

[0011] The Applicant therefore realised that the characteristics identified in the past, together with the process steps described and claimed in IT102008901652846, while increasing the probability of obtaining a so- called “active” electrode, did not guarantee its activation with sufficient reliability.

[0012] Thus, the Applicant intensified their efforts in both the electro-chemical and metallurgical fields in order to identify which other parameters influenced the behaviour of electrodes and how to produce industrial products that met the necessary conditions for generating excess power.

[0013] It is therefore the purpose of this invention to provide a process for making a metal plate to be used as an electrode in an electrochemical process for producing energy, as well as an electrode, capable of overcoming the above-mentioned limitations of the prior art.

[0014] In particular, it is the purpose of this invention to provide a process for making a metal plate to be used as an electrode within an electrochemical process for producing energy that allows a product with defined and repeatable metallurgical and compositional characteristics to be obtained.

[0015] It is, preferably, also the purpose of this invention to provide a process for making a metal plate to be used as an electrode within an electrochemical process for producing energy by which electrodes with a high probability of exhibiting active behaviour in the generation of excess power within electrochemical processes can be obtained.

[0016] These purposes are achieved with a process for producing a metal plate to be used as an electrode within an electrochemical process having the characteristics of one or more of the claims below.

[0017] In particular, these goals are achieved with a process comprising a succession of steps.

[0018] These preferably preparing an industrial product made using one of the following materials is provided: palladium, nickel, vanadium, titanium, uranium, magnesium, yttrium, niobium, or their alloys.

[0019] The industrial product is preferably (at least partially) melted at a temperature above 2000°C, more preferably above 2500°C, even more preferably by means of an oxy-acetylene torch and / or within a melting furnace.

[0020] This melting takes place at least in the surface area of the industrial product and is preferably carried out for an interval of less than 10 seconds, more preferably less than 5 seconds.

[0021] A first doping of the industrial product during said melting is preferably carried out by adding a first doping substance selected from the following: platinum, rhodium, silver, gold and iridium, chromium, manganese, iron, nickel, cobalt, copper, and zinc.

[0022] This doping preferably involves adding an amount of this first doping substance between 350 and 3500 ppm by weight.

[0023] A second doping of the industrial product is preferably involved by means of the addition of:

[0024] - a second doping substance selected from the following: aluminium or aluminium oxide, preferably in a quantity ranging between 25 and 2500 ppm by weight, preferably between 50 and 1200 by weight;

[0025] - a third doping substance, comprising silicon or silicon oxide.

[0026] The method preferably involves rapid cooling of the industrial product immediately after melting.

[0027] The first and / or said second doping are performed in between said melting step and said cooling step.

[0028] Advantageously, this allows the (low-boiling) doping substance molecules to diffuse within the industrial product by migrating in a gaseous state to the surface of the industrial product in a distillation process, which, thanks to rapid cooling, is interrupted by trapping the doping substances with high concentrations in the surface area (interphase) of the industrial product. The doped industrial product is then, preferably, rolled (with the first and / or second and / or third doping substance) to an initial thickness of between 20 and 2000 pm.

[0029] The laminate is then first annealed at temperatures between 500 and 1500°C, preferably between 800 and 900°C, thus obtaining a metal plate suitable for use as an electrode within an electrochemical process.

[0030] Advantageously, this makes it possible to obtain a metal plate with a controlled and repeatable composition and metallurgy, exhibiting surface characteristics capable of increasing the amplitude of the interphase electric field and contributing to the creation of a heterojunction that can function, following an electrolysis process in a suitable electrolyte, as a diode with a negative differential impedance region, for example tunnel diodes with current-voltage curves characterised by a negative differential impedance region. It should be noted that this region can also be created by the electrolytic process itself.

[0031] In addition, the above-mentioned purposes are achieved by means of an electrode having these characteristics and to be used for energy production.

[0032] The electrode thus comprises a metal plate with a first and second exposed face facing each other and separated by a predetermined thickness.

[0033] The plate is preferably made using one of the following materials: palladium, nickel, vanadium, titanium, uranium, magnesium, yttrium, niobium, or their alloys.

[0034] The plate preferably has a grain structure, with each grain having a larger diameter, a predetermined edge thickness and an area, where the largest diameter ranges between 10 and 150 pm, more preferably between 50 and 150 pm.

[0035] In addition, the ratio between said larger diameter and said area is preferably greater than or equal to 0.01 pm1;

[0036] In addition, the orientation of the crystalline planes is preferably (100) in at least 30% of the grains, plus preferably in at least 50% of the grains.

[0037] According to one aspect of the invention, moreover, the metal plate material preferably has a platinum concentration that is substantially constant throughout the thickness of the plate and an aluminium concentration that, in a first and second surface area, reaches a value of at least twice, preferably three times, the aluminium concentration in a central area of the plate between said first and second surface areas.

[0038] The surface areas are preferably close to said first and second faces respectively and their thickness is less than 10% of the plate thickness.

[0039] Advantageously, the Applicant has found that an electrode exhibiting such characteristics, preferably but not necessarily obtained by means of the process described above, contributes to the production of a heterojunction that can function, following an electrolysis process in a suitable electrolyte, as a diode in a region of negative differential impedance, thereby significantly increasing the possibility that the electrode, following electrolysis and possibly suitably excited, generates excess power.

[0040] These and other features, together with their relative advantages, will be clearer from the following exemplary, and therefore non-limiting, description of a preferred, and therefore not exclusive, embodiment of a process for making a metal plate to be used as an electrode within an electrochemical process, potentially also in the solid state, as well as an electrode thus produced as illustrated in the attached figures wherein:

[0041] - Figure 1 schematically outlines the steps in a process for making an electrode to be used for producing energy according to this invention;

[0042] - Figure 2 schematically shows an electrode to be used for producing energy according to this invention;

[0043] - Figure 3 shows a diagram representing the development of the doping substance concentration within the electrode of Figure 2;

[0044] - Figure 4 to 6 schematically show the steps in a process for making an electrode to be used for producing energy according to this invention, in different embodiments.

[0045] With reference to the appended figures, the reference number 1 indicates an electrode to be used for producing power according to this invention.

[0046] The electrode 1 is, as mentioned above, to be used within an electrochemical process for producing clean, low-temperature energy, where the term “low temperature” is used to define a temperature close to or around ambient temperature at atmospheric pressure.

[0047] In particular, this electrode 1 is used within an electrochemical cell, preferably within an electrolytic cell.

[0048] The characteristics of the electrode that this invention relates to are the result of a long period of scientific research, initially based on theoretical work (V. Violante et AL, Fusion Technologies Vol. 39, Mar 2001 , p. 266), that allowed the excess power in deuterated metals to be interpreted on the basis of electrodynamic effects generated on the sample surface at the electrode-electrolyte interphase.

[0049] Starting with this study, research then continued for many years, but it was only recently that the Applicant obtained, both experimentally and on the basis of theoretical considerations, the definition of the characteristics of the electrode that this invention concerns and its production process.

[0050] The electrode 1 is preferably defined by a metal plate or panel with reduced thickness and a surface width that varies with the size of the cell.

[0051] The electrolytic cell (not illustrated) preferably comprises a vessel containing an electrolyte, in which two electrodes are immersed.

[0052] The two electrodes are connected to a power supply that can operate in galvanostatic (current control) or potentiostatic (voltage control) mode, and arranged within the cell so that one end is in electrical conduction with the power supply.

[0053] A first electrode 1 , cathode, is preferably the electrode that this invention concerns.

[0054] A second electrode 20, anode, is defined by a metal plate preferably made of platinum or a platinum-plated metal, for example steel.

[0055] The electrode 1 , or first electrode, thus comprises a metal plate 1a with a first 2 and second 3 exposed face that face each other and are separated by a predetermined thickness.

[0056] The two exposed faces 2, 3 are preferably parallel to each other.

[0057] The thickness of the plate 1 a preferably ranges between 30 and 100 pm, more preferably between 40 and 80 pm. This thickness, however, could also vary considerably depending on the size of the cell and the production requirements.

[0058] In this respect, the plate 1 a preferably has a first surface area 4 close to the first exposed face 2, that is defined by multiple layers extending from the first exposed face for a limited depth.

[0059] In the embodiment shown, the first 4 and second 5 surface area are between 2 and 8 pm thick, more preferably between 3 and 6 pm.

[0060] This limited depth is a few microns, preferably fewer than 10 pm or alternatively less than 10% of the plate 1 a thickness.

[0061] Similarly, the plate 1 a comprises a second surface area 5 close to the second face 3 and with compositional and dimensional characteristics similar to the first surface area 4.

[0062] A central area 6 lies between said first 4 and second 5 surface area.

[0063] The plate 1a is preferably made using one of the following materials: palladium, nickel, vanadium, titanium, uranium, magnesium, yttrium, niobium, or their alloys.

[0064] In the preferred embodiment, the plate 1 a was made of palladium as the most suitable material according to the literature for the application in question.

[0065] This plate 1 has a grain structure, with each grain having a larger diameter, a predetermined edge thickness and an area.

[0066] These grains preferably have specific metallurgical characteristics.

[0067] This is especially important to allow the control of the stress field due to the loading of hydrogen (or its isotopes, such as deuterium) during the electrochemical process, thereby favouring the establishment of excess power.

[0068] This is because, in the presence of stress, the constitutive equation for diffusive flow J = - D grad (C) changes as follows: with:

[0069] D = diffusion coefficient

[0070] C = concentration of the diffusing species (solute)

[0071] V = molar specific volume of the solute o = stress

[0072] R = universal gas constant T = temperature

[0073] That is, an additional term appears that contains the stress gradient.

[0074] It follows that, when a stress field is present, if the condition occurs: you can have zero flux even with a strong concentration gradient. Therefore, to maximise the flux and thus the dissolution of hydrogen (or deuterium), that is the loading of the electrode, the stress field produced by the concentration gradient must be minimised, that is the concentration gradient must be minimised by optimising the metallurgical structure of the electrode 1 .

[0075] The plate 1a actually has an optimised metallurgical structure, with each crystalline grain having a larger diameter, a predetermined edge thickness and an area.

[0076] The largest diameter of each grain is preferably between 10 and 150 pm, more preferably between 50 and 120 pm, while the ratio of this largest diameter to the area is greater than or equal to 0.01 pm’1.

[0077] Another significant characteristic concerns the orientation of the crystalline planes of the electrode.

[0078] In this regard, experimental observations have revealed that the optimal orientation for the application in question is (100), with at least 30% of the crystalline planes oriented in this way.

[0079] More preferably, the proportion of crystalline planes with the orientation (100) is over 30%.

[0080] Advantageously, this makes it possible to optimise the charge density and overvoltage at the chemical interphase.

[0081] It should also be noted that, in accordance with this invention, the plate 1 a preferably has a composition that varies depending on the level of depth with respect to said exposed first and second faces 2, 3.

[0082] According to a first aspect of the invention, in fact, the plate 1 a has a concentration of a first doping substance D1 selected from the following: platinum, rhodium, silver, gold and iridium, chromium, manganese, iron, nickel, cobalt, copper and zinc, which is essentially constant throughout the thickness of the plate 1a.

[0083] More preferably, the concentration of said first doping substance D1 has a maximum variability equal to ±15% of an average value defined as the average between a peak value and a minimum value of said concentration through the whole thickness of the plate 1 a.

[0084] In the preferred embodiment, the first doping substance D1 is platinum.

[0085] More preferably, as illustrated in Figure 3, the concentration of platinum ranges, at every point of the electrode, between 2500 and 4500 ppm by weight, preferably between 3500 and 4000 ppm by weight.

[0086] According to another aspect of the invention, moreover, the plate 1 a has a concentration of a second doping substance D2 and / or a third doping substance D3 that exhibit significant variability between the surface areas and the central area.

[0087] The plate 1 a preferably contains both the second D2 and the third D3 doping substance.

[0088] The second doping substance D2 contains aluminium; more preferably, the second doping substance D2 is aluminium and / or aluminium oxide.

[0089] In the preferred embodiment, the plate 1 a has a concentration of the second doping substance D2 that, in the first and second surface area 4, 5, reaches a value of at least three times the concentration value in the central area 6.

[0090] It should be noted that, preferably, the concentration of the second doping substance D2 (preferably aluminium or aluminium oxide) within the electrode (that is, the plate 1a) has a peak value at a first intermediate plane “R1 ” of each first or second surface area 4, 5.

[0091] In other words, preferably the second doping substance D2 has an increasing concentration starting from the exposed face 2, 3 until it reaches the intermediate plane “P1”, then decreasing between the intermediate plane “P1” and the interface plane.

[0092] The intermediate plane “P1” is preferably defined by a plane, parallel to the exposed faces 2, 3 and basically equidistant between the respective exposed face 2, 3 and an interface plane 7, 8 between the respective surface area 4, 5 and the central area 6.

[0093] In other words, the first surface area 4 has an intermediate plane “P1” basically equidistant between the first exposed face 2 and a first interface plane 7 between the first surface area 4 itself and the central area 6.

[0094] Similarly, the second surface area 5 has an intermediate plane “P1” basically equidistant between the second exposed face 3 and a second interface plane 8 between the second surface area 5 itself and the central area 6.

[0095] In the preferred embodiment, the peak value of the concentration of the second doping substance D2 is between 300 and 1200 ppm by weight.

[0096] In addition, the concentration of the second doping substance D2 in the central area 6 of the plate 1a is always, preferably, less than 200 ppm, more preferably less than 150 ppm.

[0097] The third doping substance D3 preferably comprises silicon and / or a silicon oxide.

[0098] It should be noted that this third doping substance D3 can preferably only be detected in the surface areas 4, 5 and is basically absent in the central area 6.

[0099] The third doping substance D3 preferably has a concentration that reaches a peak value at a second intermediate plane “P2” of each surface area 4, 5.

[0100] The second intermediate plane “P2” may coincide with the first intermediate plane “P1” or be different, as in the embodiment shown.

[0101] The peak concentration value of the third doping substance is between 100 and 300 ppm, preferably between 150 and 250 ppm.

[0102] This invention also concerns a process for producing an electrode to be used for energy production, preferably but not exclusively the electrode 1 according to this invention and described herein.

[0103] That said, all the features mentioned and described in relation to the electrode, where not expressly identified or if incompatible, are to be considered applicable mutatis mutandis to the following description of the process that is the subject of this invention.

[0104] This process involves preparing a metal industrial product 100 made using one of the following materials: palladium, nickel, vanadium, titanium, uranium, magnesium, yttrium, niobium, or their alloys.

[0105] The industrial product 100 is preferably made of palladium, more preferably at least 95% pure palladium.

[0106] In the preferred embodiment, an industrial product 100 is prepared made of palladium with a degree of purity above 99%, preferably above than 99.5%, more preferably above 99.95%.

[0107] In other words, the industrial product 100 preferably has an impurity concentration of less than 1%, more preferably less than 0.5%, even more preferably less than or equal to 0.05%.

[0108] In some embodiments, the industrial product 100 already has a plate-like shape at the beginning of the process, but its initial shape is of no particular significance (it can also comprise three-dimensional, cylindrical, or elliptical elements), with the industrial product assuming a plate-like shape at the end of the process.

[0109] It should be noted that the industrial product 100 is preferably made of palladium as the most suitable material according to the literature for the application in question, but it could equally be made of other materials among those listed above.

[0110] The process preferably involves a melting step, at least a partial one, of the industrial product 100.

[0111] This melting preferably takes place at temperatures above 2500°C.

[0112] In the preferred embodiment, melting is performed by means of an oxyacetylene torch and / or within a melting furnace.

[0113] In the first case (oxy-acetylene torch), energy is supplied by the combustion of acetylene in a strongly oxidising environment.

[0114] The oxy-acetylene torch preferably has a flame temperature of 2,000 / 3,500 °C, preferably between 2,500°C and 3,000°C.

[0115] In the second case (melting furnace), a controlled atmosphere furnace with argon or another inert gas (e.g. nitrogen) is preferably used.

[0116] Advantageously, the use of argon allows the oven temperature to be raised above 1 ,800°C without the risk of the gas's reacting.

[0117] It preferably has an operating pressure between 0.5 and 2 bar, more preferably between 1 and 1 .5 bar.

[0118] The flame temperature is preferably between 2,500 and 3,500°C, more preferably around 3,000-3,100°C.

[0119] It should be noted that, preferably, the melting comprises successively or alternatively:

[0120] - a first melting F1 done using an oxy-acetylene torch at a temperature above 2500°C;

[0121] - a second melting F2, following the first, done inside a melting furnace at a temperature ranging between 1500 and 3500°C.

[0122] In the preferred embodiment, the process involves both the first F1 and the second F2 melting, carried out in succession. According to one aspect of the invention, there is an initial doping of the industrial product 100 during said melting.

[0123] This first doping involves the addition of the first doping substance D1 described above with reference to the electrode 1 .

[0124] This first doping substance D1 , therefore, is selected from the following: platinum, rhodium, silver, gold and iridium, chromium, manganese, iron, nickel, cobalt, copper, and zinc, preferably platinum.

[0125] This first doping substance D1 is added in a quantity ranging between 350 and 3500 ppm by weight, preferably between 500 and 2500 by weight.

[0126] It should preferably be noted that said first doping is carried out during said first melting (that is, during the oxy-acetylene torch melting).

[0127] A second doping of the industrial product 100 is also envisaged; the second doping is carried out during the melting, or during an additional melting step if, as envisaged by some variants of the invention, the process involves two separate melting steps.

[0128] It should be noted that during the melting process, precisely in light of the fact that low-boiling doping substances (aluminium and / or silicon) are present, they tend to be distilled and migrate towards the surface of the industrial product.

[0129] The methodology this invention concerns is based on this principle.

[0130] Indeed, by performing a very rapid cooling (less than 10 seconds, preferably less than 5 seconds), it is possible to trap some of the doping substance particles on the surface (see Figure 3) without migration taking place.

[0131] The second doping preferably involves the addition of a second doping substance D2 and / or a third doping substance D3.

[0132] The second doping substance D2 is the one discussed above and is preferably selected from either aluminium and / or aluminium oxide.

[0133] In this respect, it should be noted that when the second doping substance D2 consists of aluminium, the introduction of air into the melting furnace after extraction of the inert gas leads to the formation of aluminium oxide on the surface.

[0134] A similar process of oxidising the doping substances on the surface also occurs downstream of the subsequent rolling and annealing steps.

[0135] This second doping substance D2 is added in a quantity ranging between 25 and 2500 ppm by weight, preferably between 50 and 1200 by weight.

[0136] The third doping substance D3 instead comprises silicon, as described above with reference to the electrode 1 .

[0137] The third doping substance D3 can be added in the second doping step or, alternatively, in a third doping step.

[0138] It should be noted that, in a first embodiment, the second doping (and, if applicable, the third) is carried out during the first melting, that is during the oxy-acetylene torch melting. In this alternative, the second doping preferably involves adding aluminium oxide to the material of the industrial product 100 in an amount ranging between 25 and 2500 ppm by weight, preferably between 50 and 1200 ppm.

[0139] Alternatively, the second doping (and, if applicable, the third) can be carried out during the second melting (melting furnace), that is at a melting step subsequent to the first oxy-acetylene torch melting.

[0140] The melting is preferably followed by the rapid cooling described above (less than 10 seconds, preferably less than 5 seconds) so as to trap some of the doping substance particles on the surface (see Figure 3) without the distillation being completed.

[0141] In the preferred embodiment, melting is carried out by means of a melting furnace.

[0142] The melting (arc) furnace is preferably equipped with a copper stand, cooled with a fluid whose flow rate and temperature are controlled.

[0143] The control of the cooling fluid is preferably carried out by means of a cooling unit configured to perform a cooling step as soon as the metal plate material changes to a liquid state at least in the melting zone.

[0144] The cooling unit is preferably of the Hyfra type, model eCilly, with:

[0145] - Cooling temperature between 13.5 - 25°C,

[0146] - Refrigerant flow rate = 0.14 mA3 / hr

[0147] - Differential pressure = 4 bar.

[0148] More precisely, the method involves switching off the arc as soon as the metal plate material reaches the melting point, while keeping the cooling unit active to achieve rapid cooling.

[0149] However, the arc is preferably switched off when the melting temperature of the substance with the highest melting point between that of the metal plate itself and that of the doping substances is reached.

[0150] In the preferred embodiment, this temperature corresponds to that of platinum, which is approximately 1768°C.

[0151] This advantageously ensures that the migration of the doping substance particles occurs in a controlled manner and their distillation is limited to a migration towards the surface of the industrial product.

[0152] In the preferred embodiment (palladium metal plate), this melting control allows a maximum temperature of less than 1 ,800°C to be achieved.

[0153] From experimental tests, 87% of the aluminium introduced remains within the liquid metal under these conditions, as confirmed by the ICP-AES analyses performed:

[0154] In this alternative, the second doping preferably involves adding aluminium to the plate-shaped industrial product in an amount ranging between 25 and 2500 ppm, preferably between 50 and 1200 ppm.

[0155] Advantageously, dopings performed thus ensure the presence of elements such as aluminium, silicon and their oxides on the surface.

[0156] The oxides on the surface perform some important functions during the electrochemical process to which the electrode is then subjected.

[0157] For example, they allow the amplitude of the interphase electric field to be increased and contribute to the creation of a heterojunction that can have the behaviour of a diode with a negative differential impedance region in its characteristic l-V curve. At the end of the first and / or second doping, the process provides a doped plate-shaped industrial product 101 .

[0158] The doped plate-shaped industrial product 101 is preferably to be considered the industrial product following both dopings (as well as the third, if applicable) but, in certain alternatives, the industrial product 100 may also be considered a doped plate-shaped industrial product 101 for the purposes of this text following only the first doping.

[0159] At this point, the process involves a rolling of the doped plate-shaped industrial product 101 achieving a first thickness ranging between 20 and 2000 pm. The rolling is preferably a cold rolling.

[0160] In this step, the industrial product begins to take on a plate-like shape.

[0161] In the preferred embodiment, the rolling step comprises a first L1 and a second L2 rolling performed in succession.

[0162] The first (cold) rolling L1 is performed in a rolling mill configured to bring the doped plate-shaped industrial product 101 to an initial thickness of between 500 and 2000, preferably between 800 and 1200 pm.

[0163] The second (cold) rolling L2 is performed in a rolling mill configured to bring the doped plate-shaped industrial product 101 to a second thickness of between 30 and 100 pm, preferably between 40 and 80 pm.

[0164] The process also preferably comprises an initial annealing R1 of the doped plate-shaped industrial product 101 at temperatures between 500 and 1500°C; the first annealing R1 occurs downstream of the rolling.

[0165] This first annealing R1 is preferably performed at a temperature ranging between 700 and 1100°C, more preferably between 800 and 900°C.

[0166] In the preferred embodiment, the first annealing is carried out between the first L1 and second L2 rolling.

[0167] In this respect, a second annealing R2 is preferably carried out after the second rolling L2 at a temperature between 700°C and 1000°C, but preferably carried out in two steps, a first step in which the temperature reaches 400-450°C for a first time interval (20-50 minutes, preferably 30 min) and a second step in which the temperature reaches 800-900°C for a second time interval (50-150 minutes, preferably about 60-120 min).

[0168] Annealing is preferably carried out in a classic tube furnace.

[0169] In some embodiments, a surface layer treatment of the doped and laminated plate-shaped industrial product is also involved using chemical etching.

[0170] This chemical etching preferably comprises the following steps: - etching with a mixture containing nitric acid for an interval of time ranging between 5 seconds and 10 minutes;

[0171] - etching with a mixture of nitric and hydrochloric acid, with hydrochloric acid from 10 ppm to 50%, as is or in a 50% solution with water for an interval of time ranging between 5 seconds and 10 minutes.

[0172] In addition, for certain applications, a step of depositing a surface layer of chromium, preferably by sputtering, is also involved.

[0173] At the end of the process, it is therefore possible to obtain a metal plate 1a for defining the electrode 1 , in particular the cathode, within an electrochemical cell for the production of low-temperature nuclear energy.

[0174] Therefore, the following are some examples illustrating, for descriptive but clearly non-limiting purposes, different embodiments of the process according to this invention.

[0175] EXAMPLE 1

[0176] In a first embodiment according to this invention, the method comprises the following steps:

[0177] - melting in an oxy-acetylene torch with a flame temperature of 2,000°C and a duration of between 10 and 20 seconds;

[0178] - simultaneous doping with the first doping substance (platinum) and the second doping substance (Al or AI2O3);

[0179] - first heat treatment by annealing at approx. 900°C for a time interval of approx. 2 hours;

[0180] - first metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 1 mm;

[0181] - second heat treatment by annealing at approx. 900°C for a time interval of approx. 2 hours;

[0182] - second metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 50 pm;

[0183] - third heat treatment by annealing carried out in two steps, a first step with a temperature reaching 400-450°C lasting approximately 30 minutes and a second step with a temperature reaching 800- 900°C lasting between 60 and 120 minutes;

[0184] - an initial chemical treatment by acid etching (HNO3).

[0185] EXAMPLE 2

[0186] In a second embodiment according to this invention, the method comprises the following steps:

[0187] - melting in an oxy-acetylene torch at the flame temperature of 2,000°C and a duration of between 10 and 20 seconds;

[0188] - simultaneous doping with the first doping substance (platinum) and the second doping substance (Al or AI2O3);

[0189] - first metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 1 mm;

[0190] - first heat treatment by annealing at approx. 900°C for a time interval of approx. 2 hours;

[0191] - second metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 50 pm;

[0192] - second heat treatment by annealing carried out in two steps, a first step with a temperature reaching 400-450°C lasting approximately 30 minutes and a second step with a temperature reaching 800- 900°C lasting between 60 and 120 minutes;

[0193] - an initial chemical treatment by acid etching (HNO3).

[0194] EXAMPLE 3

[0195] In a third embodiment according to this invention, the method comprises the following steps:

[0196] - first melting in an oxy-acetylene torch at the flame temperature of 2,000°C and a duration of between 10 and 20 seconds;

[0197] - simultaneous doping with the first doping substance (platinum) and the second doping substance (Al or AI2O3); - second melting inside a melting (arc) furnace at a temperature of approximately 1 ,800°C (1 ,768.2°C), for a time interval of approximately 5 seconds;

[0198] - cooling by means of a conductive copper plate lasting approximately 5 seconds;

[0199] - first metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 1 mm;

[0200] - first heat treatment by annealing at approx. 900°C for a time interval of approx. 2 hours;

[0201] - second metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 50 pm;

[0202] - second heat treatment by annealing carried out in two steps, a first step with a temperature reaching 400-450°C lasting approximately 30 minutes and a second step with a temperature reaching 800- 900°C lasting between 60 and 120 minutes;

[0203] - an initial chemical treatment by acid etching (HNO3).

[0204] EXAMPLE 4

[0205] In a fourth embodiment according to this invention, the method comprises the following steps:

[0206] - first melting in an oxy-acetylene torch at the flame temperature of 2,000°C and a duration of between 10 and 20 seconds;

[0207] - simultaneous doping with the first doping substance (platinum) and the second doping substance (Al or AI2O3);

[0208] - second melting inside a melting (arc) furnace at a temperature of approximately 1 ,800°C (1768.2°C), for a time interval of approximately 5 seconds;

[0209] - cooling by means of a conductive copper plate lasting approximately 5 seconds;

[0210] - first metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 1 mm; - second metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 50 pm;

[0211] - first heat treatment by annealing carried out in two steps, a first step with a temperature reaching 400-450°C lasting approximately 30 minutes and a second step with a temperature reaching 800-900°C lasting between 60 and 120 minutes;

[0212] - an initial chemical treatment by acid etching (HNO3).

[0213] EXAMPLE 5

[0214] In a fifth embodiment according to this invention, the method comprises the following steps:

[0215] - first melting in an oxy-acetylene torch at the temperature of 2,000°C and a duration of between 10 and 20 seconds;

[0216] - simultaneous doping with the first doping substance (platinum);

[0217] - first metallurgical treatment by rolling the industrial product to a plate shape with a thickness ranging between 200 pm and 1 mm;

[0218] - second melting inside a melting (arc) furnace at a temperature of approximately 1 ,800°C (1768.2°C), for a time interval of approximately 5 seconds;

[0219] - cooling by means of a conductive copper plate lasting approximately 5 seconds;

[0220] - simultaneous doping with the second doping substance (Al or AI2O3);

[0221] - second metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 1 mm;

[0222] - first heat treatment by annealing at approx. 900°C for a time interval of approx. 2 hours;

[0223] - second metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 50 pm;

[0224] - second heat treatment by annealing carried out in two steps, a first step with a temperature reaching 400-450°C lasting approximately 30 minutes and a second step with a temperature reaching 800- 900°C lasting between 60 and 120 minutes; an initial chemical treatment by acid etching (HNO3).

[0225] EXAMPLE 6

[0226] In a sixth embodiment according to this invention, the method comprises the following steps:

[0227] - first melting inside a melting (arc) furnace at a temperature of approximately 1 ,800°C (1768.2°C), for a time interval of approximately 5 seconds;

[0228] - cooling by means of a conductive copper plate lasting approximately 5 seconds;

[0229] - simultaneous doping with the first doping substance (platinum) and the second doping substance (Al or AI2O3) and / or with the third doping substance (Si);

[0230] - first metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 1 mm;

[0231] - first heat treatment by annealing at approx. 900°C for a time interval of approx. 2 hours;

[0232] - second metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 50 pm;

[0233] - second heat treatment by annealing carried out in two steps, a first step with a temperature reaching 400-450°C lasting approximately 30 minutes and a second step with a temperature reaching 800- 900°C lasting between 60 and 120 minutes;

[0234] - an initial chemical treatment by acid etching (HNO3).

[0235] EXAMPLE 7

[0236] In a seventh embodiment according to this invention, the method comprises the following steps:

[0237] - first melting inside a melting (arc) furnace at a temperature of approximately 1 ,800°C (1768.2°C), for a time interval of approximately 5 seconds;

[0238] - cooling by means of a conductive copper plate lasting approximately 5 seconds;

[0239] - simultaneous doping with the first doping substance (platinum) and with the second doping substance (Al or AI2O3);

[0240] - first heat treatment by annealing at approx. 900°C for a time interval of approx. 2 hours;

[0241] - first metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 1 mm;

[0242] - second heat treatment by annealing at approx. 900°C for a time interval of approx. 2 hours;

[0243] - second metallurgical treatment by rolling the industrial product to a plate shape with a thickness of approximately 50 pm;

[0244] - third heat treatment by annealing carried out in two steps, a first step with a temperature reaching 400-450°C lasting approximately 30 minutes and a second step with a temperature reaching 800- 900°C lasting between 60 and 120 minutes;

[0245] - an initial chemical treatment by acid etching (HNO3).

[0246] An electrode produced with the characteristics of the invention, preferably by means of the process of the invention, makes it possible to maximise (or at least significantly increase) the repeatability of excess energy (or excess power) production in palladium deuteride, obtained using an electrochemical process.

[0247] It has been observed that the energy produced, when distributed over all the particles in the sample, is in fact orders of magnitude greater than that attributable to a chemical process. This evidence, and the fact that the excess energy occurs predominantly using deuterium, points strongly in the direction of a nuclear process.

[0248] In fact, with regard to the nuclear nature of the process, it should be noted that palladium is the material with the highest screening effect for nuclear reactions between light, low-energy nuclei in condensed matter.

[0249] It should also be noted that with the occurrence of these nuclear processes, it was possible to observe and detect significant radio frequency emissions, with spectral characteristics in the frequency range between MHz and GHz.

[0250] In addition, the structures identified “ex situ”, that is, outside the cell, have compositional states that can be traced back to those of P-N, MIS and MOS diodes.

[0251] The layered structure found on active electrodes was also reconstructed on palladium using thin film deposition techniques, and preliminary, electrical measurements conducted on these structures showed that they possessed the typical characteristic of a diode.

[0252] This actually confirms how the electrochemical effects generated on the surface of the sample produced according to the invention, at the electrode-electrolyte interphase, lead to the generation of a structure possessing typical diode characteristics.

[0253] The invention achieves the purposes proposed and entails significant advantages.

[0254] Advantageously, the use of a process with a sequence of dopings, rollings and annealings, starting with a plate-like industrial product of the correct composition and suitable for efficient deuterium loading during electrolysis, provides an electrode with optimised surface characteristics to favour the occurrence of excess power at low temperatures.

Claims

CLAIMS1. A process for making a metal plate (1 a) to be used as an electrode in an electrochemical cell for the production of energy, comprising the steps of:- preparing an industrial product (100) made using one of the following materials: palladium, nickel, vanadium, titanium, uranium, yttrium, niobium, or their alloys;- at least partial melting of the industrial product (100) at a temperature above 2500°C inside a melting furnace for less than 10 seconds;- first doping of the industrial product (100) during said melting by adding a first doping substance selected from the following: platinum, rhodium, silver, gold and iridium, chromium, manganese, iron, nickel, cobalt, copper, and zinc in a quantity ranging between 350 and 3500 ppm by weight;- second doping of the industrial product (100) during said melting by adding a second doping substance selected from the following: aluminium or aluminium oxide in a quantity ranging between 25 and 2500 ppm by weight and / or a third doping substance containing silicon;- rolling of said doped plate-shaped industrial product (101 ) with the first and / or second doping substance until achieving a first thickness ranging between 20 and 2000 pm;- first annealing of the doped plate-shaped industrial product (101 ) at a temperature ranging between 400 and 1500°C and following said rolling, preferably between 800 and 1000°C.

2. The process according to claim 1 , wherein said industrial product (100) is made of palladium with a degree of purity above 99%, preferably above than 99.5%, more preferably above 99.95%.

3. The process according to claim 1 or 2, wherein said melting comprises,in succession or alternatively:- a first melting done at a temperature above 2500°C;- a second melting, following to the first, carried out inside a melting furnace at a temperature ranging between 1500 and 3500°C and for less than 10 seconds.

4. The process according to claim 3, wherein said first doping is done during said first melting.

5. The process according to claim 3 or 4, wherein said second doping is done alternately:- during the first melting, by adding aluminium oxide in a quantity ranging between 350 and 3500 ppm by weight;- during the second melting, by adding aluminium in a quantity ranging between 350 and 2500 ppm by weight, preferably between 50 and 1200 ppm.

6. Process according to any one of the preceding claims, comprising a quick cooling step of the industrial product (100) carried out immediately downstream of said second melting; said second doping being performed between said melting step and said cooling step.

7. The process according to any one of the preceding claims, wherein said rolling comprises:- a first cold rolling of the doped industrial product (101 ) until achieving a first thickness ranging between 500 and 2000 pm;- a second cold rolling of the doped industrial product (101 ) until achieving a first thickness ranging between 30 and 100 pm; wherein said first annealing is done between said first and said second rolling.

8. The process according to claim 7, comprising a second annealing done following said second rolling at a temperature ranging between 800 and 1000°C for an interval of time ranging between 1 and 3 hours.

9. The process according to any one of the preceding claims, comprising a treatment of one surface layer of the doped plate-shaped industrial product (101 ) via chemical etching.

10. The process according to claim 9, wherein said treatment of a surface layer of the doped plate-shaped industrial product (101 ) via chemical etching comprises the following steps:- etching with a mixture containing nitric acid for an interval of time ranging between 5 seconds and 10 minutes;- etching with a mixture of nitric and hydrochloric acid, with hydrochloric acid from 10 ppm to 50%, as is or in a 50% solution with water for an interval of time ranging between 5 seconds and 10 minutes.11 . The process according to any one of the preceding claims, comprising a step of depositing a surface layer of chromium, preferably via sputtering.

12. An electrode to use for producing energy, comprising:- a metal plate (1 a) that has a first face (2) and a second exposed face (3) that are opposite each other and separated by a predetermined thickness and made from a material selected from the following: palladium, nickel, vanadium, titanium, uranium, yttrium, niobium or their alloys; said plate having a grain structure, with each grain having a larger diameter, a preset edge thickness and an area, wherein: said larger diameter ranges between 50 and 150 pm; a ratio between said larger diameter and said area is greater than or equal to 0.01 pm-1; characterised in that said plate (1 a) is doped with:- at least one first doping substance selected from the following: platinum, rhodium, silver, gold and iridium, chromium, manganese, iron, nickel, cobalt, copper, and zinc;- a second doping substance containing aluminium and / or a third doping substance containing silicon, wherein:- a concentration of the first doping substance is kept constant for the whole thickness of the metal plate (1a);- a concentration of said second doping substance, in a first surface area (4) and in a second surface area (5), near, respectively, said first face (2) and second face (3) and with a thickness less than 10% of the thickness of the plate (1 a), achieves a value of at least triple the concentration of aluminium present in a central area (6) of the plate ranging between said first (4) and second surface area (5).- the third doping substance can only be detected in the first (4) and in the second surface area (5), being absent in the central area (6).

13. The electrode according to claim 12, wherein said concentration of platinum has a maximum variability equal to ±15% of an average value defined as the average between a peak value and a minimum value of said concentration through the whole thickness of the plate (1 ).

14. The electrode according to claim 13, wherein said concentration of platinum ranges, at every point of the electrode, between 2500 and 4500 ppm by weight, preferably between 3500 and 4000 ppm by weight.

15. The electrode according to any one of the claims from 12 to 14, wherein said second doping substance is aluminium or aluminium oxide, wherein the concentration of aluminium inside the electrode has a peak value at a first intermediate plane (P1) of each surface area (4, 5), basically equidistant between the respective first (2) or second face (3)and an interface plane (7, 8) between the respective surface area (4, 5) and the central area (6).

16. The electrode according to claim 15, wherein said peak value of the concentration of aluminium ranges between 300 and 1200 ppm.

17. The electrode according to any one of the claims from 12 to 14, wherein said concentration of aluminium in the central area of the plate is always below 200 ppm, preferably below 150 ppm.

18. The electrode according to any one of the claims from 12 to 17, wherein said third doping substance is silicon and a concentration of silicon inside the electrode has a peak value at a second intermediate plane (P2) of each surface area.

19. The electrode according to claim 18, wherein said peak value of the concentration of silicon ranges between 100 and 300 ppm, preferably between 150 and 250 ppm.

20. The electrode according to any one of the claims from 12 to 19, comprising both said second and said third doping substance.

21. The electrode according to any one of the claims from 12 to 20, wherein said first (4) and second surface area (5) have a thickness ranging between 2 and 8 pm, preferably between 3 and 6 pm.

22. The electrode according to any one of the claims from 12 to 21 , characterised in that it is made using a process according to any of the claims from 1 to 10.

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