Generators Comprising Active Organic Materials, Generator Modules Comprising the Generators, and Methods for Making the Generators

Abstract

The present invention relates to power generating devices and modules that include active organic materials.

Description

[Technical Field]

[0001] The present invention relates to power generating devices that include active organic materials. [Background technology]

[0002] The use of thermoelectric and thermionic generators to convert thermal energy directly into electrical energy is well known.

[0003] Thermoelectric generators are devices based on the thermoelectric effect, or Seebeck effect, which involves the interaction of heat and electricity flow between solids. Examples of such devices are disclosed in European Patent No. 2521192 and European Patent Application No. 2277209. Broadly speaking, a thermoelectric generator consists of three main components: a thermoelectric material, a thermoelectric module, and a thermoelectric system that interfaces with a heat source.

[0004] Thermoelectric materials generate electricity directly from heat by converting a temperature difference into a voltage. In particular, these materials typically have both high electrical conductivity and low thermal conductivity. The low thermal conductivity ensures that when one side is heated to a high temperature, the other side remains cool. This helps generate large voltages during a temperature gradient.

[0005] A thermoelectric module is a circuit containing thermoelectric materials that generates electricity directly from heat. The module consists of two different thermoelectric materials, a negatively charged semiconductor and a positively charged semiconductor, joined at their ends. When a temperature gradient exists between the two materials, a direct current flows through the circuit. Such a gradient is typically provided by a thermoelectric system with heat exchangers used on either side of the module to provide heating and cooling, respectively.

[0006] Thermionic power generators, also known as thermionic power converters, convert heat directly into electricity. They typically contain two electrodes located within a containment vessel. One of these is heated to a temperature high enough to become the thermionic emitter or "hot plate." The other electrode receives the emitted electrons and is therefore called the collector. The collector operates at a significantly lower temperature. The space between the electrodes may be a vacuum or, alternatively, filled with a low-pressure vapor gas. Thermal energy may be provided by chemical, solar, or nuclear sources.

[0007] Thermoelectric and thermionic generators have many drawbacks, including low conversion efficiency and the need to provide a temperature gradient. Additionally, such generators require a relatively constant heat source.

[0008] SUMMARY OF THE INVENTION It is therefore a main object of the present invention to provide an electrical generating device capable of converting part of the thermal energy into electrical energy, making it possible to overcome the drawbacks of the prior art devices.

[0009] WO 2018 / 029139 already describes an active material that, surprisingly, can generate current when applied to one electrode and contained between at least two electrodes, depending on temperature, without initial charging. Specifically, the material described in WO 2018 / 029139 includes at least one oxygen-containing compound selected from the group consisting of MgO, ZnO, ZrOCl2, ZrO2, SiO2, Bi2O3, Al2O3, and TiO2; at least one thickener additive selected from the group consisting of agar, xanthan gum, methylcellulose, and gum arabic; and at least one plasticizer additive, wherein the particle size of the oxygen-containing compound has a specific average diameter. The performance of such an active material was worse at temperatures above 80°C, and temperatures above 90°C induced degradation of the active material, resulting in a decrease in device performance and a decrease in the stability of the final device.

[0010] WO 2019 / 122215 proposes a further active material capable of generating electrical energy and having high temperature stability, thus offering an alternative and improvement over the prior art. The further active material is an essentially dry active material comprising at least one oxygen-containing compound selected from the group consisting of MgO, ZnO, ZrOCl2, ZrO2, SiO2, Bi2O3, Fe3O4, Al2O3, TiO2, BeO, CaO, Ga2O3, In2O3, GeO2, SnO2, and PbO2, wherein the particle size of the oxygen-containing compound has an average diameter in the range of 10 nm to 40 μm, and the thickener additive selected from the group consisting of agar, xanthan gum, methylcellulose, and gum arabic is not present.

[0011] The inventors have found that the performance of this essentially dry active material deteriorates with use over time, resulting in a loss of device performance in terms of power recovery after extended use due to aging.

[0012] Therefore, a further object of the present invention is to provide a power generating device that can stably supply electric energy even under long-term use conditions without compromising performance in terms of recovery of generated power. Therefore, a further object of the present invention is to provide a power generating device that can supply electric energy at a constant, uniform temperature and / or with a temperature gradient between the two electrodes of the same power generating device, and even under conditions of long-term use of the device itself. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] European Patent No. 2521192 [Patent Document 2] European Patent Application No. 2277209 [Patent Document 3] International Publication No. 2018 / 029139 [Patent Document 4] International Publication No. 2019 / 122215 Summary of the Invention

[0014] The inventors have surprisingly found that new power generating devices comprising active organic materials are capable of delivering electrical energy at a constant, uniform temperature and / or with a temperature gradient between at least one electrode and at least one current collector of the same power generating device, even under long-term operating conditions, without compromising performance in terms of power recovery.

[0015] Accordingly, the present invention provides an electric power generating system (EPG), comprising: at least one electrode; at least one current collector; at least one active organic material interposed between at least one electrode and at least one current collector; at least one oxygen-containing compound layer; the at least one active organic material comprises at least one organic polymer obtained by heating a mixture comprising 5% to 70% by weight of polyvinyl alcohol and 30% to 95% by weight of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol, based on the total weight of the at least one organic polymer, at a temperature in the range of 60°C to 160°C for 1 to 3 hours; at least one oxygen-containing compound layer is in contact with said at least one active organic material; The at least one oxygen-containing compound layer is in contact with at least one current collector for an electric power generating device (EPG).

[0016] The EPG according to the present invention can indeed supply electrical energy at a constant, uniform temperature and / or with a temperature gradient between at least one electrode and at least one current collector of the same generator, even under conditions of long-term use of the same generator. The inventors have unexpectedly found that, thanks to the at least one active organic material described above, the recovery of generated power of the EPG is further increased, thus offering a further improvement compared to prior art EPGs.

[0017] The present invention also relates to a generator set module (PGM) with multiple EPGs that can be connected in series or parallel without compromising EPG characteristics (voltage and current).

[0018] The advantages of the power generating plant module (PGM) have been outlined above with respect to the EPG according to the present invention and will not be repeated here.

[0019] Further features and advantages of the present invention will become more apparent in light of the detailed description of preferred embodiments of the active material and power generating device taken in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0020] [Figure 1] 1 shows the structure of a generator (EPG1) comprising active organic materials according to the present invention. [Figure 2] 1 shows the structure of a further configuration of a power generating device (EPG2) comprising active organic materials according to the present invention. [Figure 3] 1 shows an example of an electrical circuit with a PGM having two EPGs according to the invention in parallel. [Figure 4] 1 shows an example of an electrical circuit with a PGM having two EPGs according to the invention in series. [Figure 5] 1 shows the response curve of an EPG constructed according to Example 3 (EPG1) determined during exposure testing according to Example 5. [Figure 6] 10 shows the response curve of a stack of EPGs in series assembled according to Example 4 (EPG2) determined during exposure testing according to Example 6. [Figure 7] 10 shows the response curve of a stack of EPGs in series assembled according to Example 4 (EPG2) determined during exposure testing according to Example 7. [Figure 8] 1 shows the response curve of an EPG constructed according to Example 4 (EPG2) determined during exposure testing according to Example 8. [Figure 9]10 shows the voltage and current response curves of an EPG assembled according to Example 2, as determined during exposure testing according to Example 9. [Figure 10] 1 shows the response of EPG2 at different temperatures tested in Example 10. [Figure 11] 1 shows an electric power generating device 2 (EPG2) of the present invention with electrical contacts for connection. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention provides an electric power generating system (EPG), comprising: at least one electrode; at least one current collector; at least one active organic material interposed between at least one electrode and at least one current collector; at least one oxygen-containing compound layer; The at least one active organic material comprises at least one organic polymer obtained by heating a mixture comprising 5% to 70% by weight of polyvinyl alcohol and 30% to 95% by weight of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol, based on the total weight of the at least one organic polymer, at a temperature in the range of 60°C to 160°C for 1 hour to 3 hours; at least one oxygen-containing compound layer is in contact with said at least one active organic material; The at least one oxygen-containing compound layer is in contact with at least one current collector for an electric power generating device (EPG).

[0022] In the present invention, when the following terms are used: "Contacting" means that an interface is formed between two materials having an actual contact area of ​​more than 90% of the geometric area, with a preferred value being 95% or greater; "At least one current collector" refers to an essential element of the EPG of the present invention that collects and modulates electrical charge; "primary current collector" means at least one current collector made of metallic and / or organic / inorganic materials that collect and modulate charge; A "secondary current collector" is intended to be at least one current collector made of metallic and / or organic materials that collect and modulate charge and interact electrically with the oxygen-containing compound layer.

[0023] Within the framework of this specification and the claims that follow, unless otherwise indicated, all numerical entities expressing quantities, parameters, percentages, and the like are to be understood in all instances to be preceded by the term "about." Also, all ranges of numerical entities include all possible combinations of maximum and minimum values, and all possible intermediate ranges, in addition to those specifically set forth herein below.

[0024] The EPG according to the present invention can indeed supply electrical energy at a constant, uniform temperature and / or with a temperature gradient between at least one electrode and at least one current collector of the same generator, even under conditions of long-term use of the same generator. The inventors have unexpectedly found that, thanks to the at least one active organic material described above, the recovery of generated power of the EPG is further increased, thus offering a further improvement compared to prior art EPGs.

[0025] The present invention, in one or more of the above aspects, may exhibit one or more of the characteristics disclosed below.

[0026] The EPG according to the present invention comprises at least one active organic material comprising at least one organic polymer obtained by heating a mixture comprising 5% to 70% by weight of polyvinyl alcohol and 30% to 95% by weight of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol, based on the total weight of the at least one active organic polymer, at a temperature in the range of 60°C to 160°C for 1 to 3 hours.

[0027] Preferably, the at least one activated organic polymer is obtained by heating the aforementioned mixture at a temperature ranging from 120°C to 150°C, more preferably at 140°C.

[0028] In a particularly advantageous embodiment, the invention may provide a second heating step of between 120°C and 150°C, more preferably 140°C.

[0029] Even more preferably, the second step may provide for the addition of a thickening agent, preferably glycerol.

[0030] Preferably, the at least one active organic polymer is obtained by heating the mixture for a period of time between 1 hour and 2.5 hours, more preferably, the at least one active organic polymer is obtained by heating the mixture for about 2 hours, even more preferably in air or in an inert atmosphere.

[0031] The mixture according to the invention comprises 5% to 70% by weight of polyvinyl alcohol and 30% to 95% by weight of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol, relative to the total weight of the at least one active organic polymer. Preferably, the mixture comprises 8% to 40% by weight of polyvinyl alcohol and 60% to 92% by weight of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol, relative to the total weight of the at least one active organic polymer.

[0032] In an advantageous and preferred embodiment, the polyvinyl alcohol has a viscosity of 1.19 to 1.31 g / cm at 20°C. 3 The density of polyvinyl alcohol can be measured using methods known to those skilled in the art for this purpose, for example by pycnometry.

[0033] Preferably, the polyvinyl alcohol has a degree of hydrolysis ranging from 86% to 89%. The degree of hydrolysis of the polyvinyl alcohol can be determined according to any one of the methods known to those skilled in the art for this purpose, for example, titration.

[0034] In a preferred embodiment of the present invention, the at least one active organic material comprises at least one thickener additive, preferably selected from the group consisting of agar, xanthan gum, methylcellulose, glycerol and gum arabic.

[0035] In a further preferred embodiment of the present invention, the at least one active organic material is free of thickener additives, more preferably a thickener additive selected from the group consisting of agar, xanthan gum, methylcellulose, glycerol and gum arabic is absent from the at least one active organic material of the EPG according to the present invention.

[0036] An EPG according to the present invention comprises at least one electrode and at least one current collector.

[0037] The at least one electrode and at least one current collector may be made of a metal, an alloy, and / or a carbon-based material such as graphite. If more than one electrode is present, the additional electrodes may be made of the same or different materials.

[0038] Preferably, the thickness of at least the electrodes, and independently of the at least one current collector, is in the range of 0.1 to 3000 μm, more preferably 50 to 1000 μm, even more preferably 300 to 600 μm.

[0039] In a preferred embodiment of the EPG according to the present invention, the at least one electrode and the at least one secondary current collector are made of Cu and Al, respectively, preferably in the form of a substantially parallel array or foil. In the case of a flexible EPG, both freestanding flexible materials and metallized polymers can be considered electrodes and current collectors. However, the shape of the at least one electrode or the at least one current collector is not binding.

[0040] The at least one electrode, and, independently, the at least one current collector, are preferably made of Cu or Al and may more preferably be cleaned and etched prior to use in the generator of the present invention.

[0041] An EPG according to the present invention includes at least one oxygen-containing compound layer.

[0042] Preferably, said at least one oxygen-containing compound layer may be said at least one passivation layer of at least one current collector, preferably a secondary current collector, or a layer of at least one oxygen-containing compound selected from the group consisting of MgO, ZnO, ZrOCl2, ZrO2, SiO2, Bi2O3, Fe3O4, Al2O3, TiO2, BeO, CaO, Ga2O3, In2O3, GeO2, SnO2 and PbO2.

[0043] In one embodiment, the at least one oxygen-containing compound layer is a passivation layer of the at least one current collector, but may also be a layer of at least one oxygen-containing compound deposited on the at least one current collector. According to a further embodiment, the at least one oxygen-containing compound layer is both a passivation layer on one side of the at least one current collector and a layer of at least one oxygen-containing compound deposited on the other side of the at least one current collector.

[0044] In an advantageous embodiment, the at least one oxygen-containing compound layer can be formed in situ after assembly of the EPG when the at least one current collector is a secondary current collector, in this embodiment, the secondary current collector is aluminum.

[0045] Preferably, said at least one oxygen-containing compound has an average particle diameter in the range of 5 nm to 40 μm, preferably in the range of 15 nm to 10 μm, more preferably in the range of 20 nm to 5 μm. In another advantageous and preferred embodiment of the present invention, the particles of the oxygen-based compound have an average diameter in the range of 10 to 200 nm, more preferably in the range of 15 to 100 nm, even more preferably in the range of 20 to 40 nm.

[0046] The oxygen-containing compound may be anhydrous or may contain a certain amount of water as coordinated water molecules resulting from the process for preparing it, and the inventors believe that such coordinated water in the oxygen-containing compound can improve the performance of the final device obtained therefrom. The oxygen-containing compound may contain coordinated water in the range of 0.5% to 7.5% by weight, preferably 0.5% to 3.5%, and more preferably 0.5% to 1.5% of the oxygen-containing compound.

[0047] The at least one oxygen-based compound may be placed as a powder on said at least one electrode or at least one current collector and pressed onto it using a mechanical press, thus obtaining at least one oxygen-containing compound layer. Alternative techniques already known in the art, such as sol-gel, inkjet printing and sputtering, can be used.

[0048] According to the present invention, at least one oxygen-containing compound layer is in contact with at least one active organic material as described above, which means that there is the formation of an interface between the two materials with an actual contact area of ​​more than 90% of the geometric area, with a preferred value being 95% or more.

[0049] According to the present invention, the at least one oxygen-containing compound layer is also in contact with at least one current collector.

[0050] According to the present invention, the at least one oxygen-containing compound layer may be a passivation layer of the at least one current collector described above. The at least one current collector having a passivation layer may be commercially available or may be prepared by passivating the current collector by thermal or electrolytic oxidation.

[0051] The active organic material of the EPG of the present invention is preferably deposited in contact with at least one oxygen-containing compound layer having a thickness of 100 nm to 5 mm, although the optimum thickness will vary depending on the application, e.g., doctor blade, spray, etc.

[0052] In a preferred embodiment, at least one electrode may be a secondary current collector in contact with at least the oxygen-containing compound layer.

[0053] In a preferred embodiment, the secondary current collector is made of the same material as at least one electrode. In a more preferred embodiment, the EPG includes a secondary current collector, preferably made of a material different from the material of at least one electrode.

[0054] Preferably, said secondary current collector is made of a material selected from the group consisting of metals, porous carbon, and conductive oxides, sulfides, alloys with approximately constant electrical resistivity, manganese oxide and its compounds, phosphates, and mixtures or composites thereof. According to the invention, an alloy with approximately constant electrical resistivity is, for example, constantan (55% copper and 45% nickel).

[0055] In a preferred embodiment, the EPG comprises a further current collector, which in a more preferred embodiment is the primary collector.

[0056] In an even more preferred embodiment, the EPG comprises a primary current collector, more preferably in contact with said secondary current collector, said secondary current collector featuring an oxygen-containing layer on one or both sides of the collector.

[0057] Preferably, said primary current collector is made of a material selected from the group consisting of pyrolytic graphite, carbon coke and / or carbon-based materials (e.g., graphene), boron, silicon, germanium, silver and chemically stable semiconductors in their intrinsic and extrinsic states (e.g., gallium arsenide), ceramic materials as carbides and nitrides, perovskites, spinel compounds, PET (polyethylene terephthalate), and mixtures or composites thereof.

[0058] Preferably, the electric power generating device (EPG) according to the present invention may comprise at least one porous layer. More preferably, said at least one active organic polymer may be adsorbed on said at least one porous layer.

[0059] Preferably, said at least one porous layer is made of cellulose, a cellulose composite material, a porous carbonaceous material, and a composite material with a carbon matrix.

[0060] More preferably, the cellulosic material is sodium carboxymethylcellulose.

[0061] More preferably, the porous carbonaceous material is powdered activated carbon.

[0062] In a preferred embodiment, said at least one porous layer comprises 85% water, 1% sodium carboxymethylcellulose and 14% powdered activated carbon.

[0063] Preferably, the electric power generating device (EPG) according to the present invention comprises at least one porous layer in contact with the at least one active organic material described above.

[0064] Preferably, the porous layer has a thickness of 100 to 600 m2 / g The surface area can be determined according to any one of the methods known to those skilled in the art for this purpose, for example according to capillary porosimetry or BET adsorption.

[0065] Thus, in a preferred embodiment as shown diagrammatically in FIG. 1, an EPG according to the invention (EPG1) comprises: a current collector (1), specifically a secondary current collector; an oxygen-containing compound layer (2) as a passivation layer in contact with the secondary current collector; an active organic material (3); and an electrode (4).

[0066] In a further preferred embodiment, as shown diagrammatically in FIG. 2, the EPG according to the invention comprises: a primary current collector (5); a current collector (1), specifically a secondary current collector; an oxygen-containing compound layer (2) as a passivation layer in contact with the secondary current collector; an active organic material (3); A porous layer (6); an electrode (4); a secondary current collector (1); and a primary current collector (5).

[0067] The present invention also relates to a generator set module (PGM) with multiple EPGs that can be connected in series or parallel without compromising EPG characteristics (voltage and current).

[0068] Thus, in a further aspect, the present invention relates to a power generator module (PGM) with multiple EPGs that can be connected in series or in parallel. In this regard, Figure 3 shows a circuit with a PGM with two EPGs connected in parallel, and Figure 4 shows a circuit with a PGM with two EPGs connected in series. Both the circuits of Figures 3 and 4 have a load resistor R L = 100 ohms. The voltage to the PGM is determined by, for example, connecting a potentiostat / galvanostat to a load resistor R Lcan be monitored by connecting in parallel with

[0069] Specifically and advantageously, the current measured by the power generating device (EPG) of the present invention increases by a factor ranging from 1.5 to 4 with increasing temperature from 20°C to 80°C.

[0070] The EPG of the present invention was characterized from an electrical standpoint. First, the open circuit voltage (OCV) was measured using a multimeter, and the EPG device showed a voltage of 0.6 V in a configuration including aluminum oxide and graphite as electrodes.

[0071] 3 and 4, a dedicated electrical circuit EC was selected to characterize the EPG from an electrical point of view, measuring the voltage across a 100 ohm resistor connected to the EPG and the current circulating through the resistor. The invention will now be illustrated by some non-limiting examples of active materials and EPGs of the invention. [Example]

[0072] Example 1 Preparation of active organic materials 24 grams of polyvinyl alcohol (Zeus) and 76 grams of ethylene glycol (Sigma Aldrich) were charged into a glass reactor and then mixed to obtain a mixture. The mixture was heated to 140°C with stirring for about 2 hours, specifically 1 hour and 55 minutes, to obtain a transparent, homogeneous melt of the active organic material. The active organic material was then poured to form a film and cooled to 25°C.

[0073] Example 2 Preparation of active organic materials adsorbed on porous layers An active organic material was prepared according to Example 1. The resulting active organic material was a transparent, homogeneous melt, which was poured into a porous cellulose layer and then cooled to 25°C.

[0074] Example 3 Preparation of the power generating device 1 (EPG1) of the present invention The EPG1 device was assembled starting from a graphite electrode (4) of 15 mm x 35 mm size and 1 mm thickness on top of which was deposited, via a doctor blade device, the active organic material (3) prepared according to Example 1) with a thickness of 5 mm.

[0075] Thereafter, a secondary current collector (1) having an aluminum passivation layer (at least one oxygen-containing compound layer (2)) was prepared. The latter was a secondary current collector (15 mm x 35 mm) having a passivation layer (2) on the current collector. Specifically, the passivation layer (2) was made of commercially available aluminum foil for capacitors (0.36 to 0.80 μF / cm). 2 ) on one side.

[0076] The final EPG1 device shown in Figure 1 a current collector (1) which is a secondary current collector having an oxygen-containing compound layer (2) (anodic passivation layer); The active organic material (3) of Example 1; and an electrode (4).

[0077] Example 4 Preparation of EPG2 of the present invention (EPG2) The EPG2 device was assembled starting from a primary current collector (5) made of pyrolytic graphite with dimensions of 15 mm x 50 mm and a thickness of 1 mm. On top, the EPG2 device was clad in contact with a secondary current collector (1) in the form of a graphite foil with dimensions of 15 mm x 35 mm and a thickness of 100 μm.

[0078] Then, an electrode (4) made of carbon powder with dimensions of 15 mm x 35 mm and a thickness of 100 μm and a porous layer (6) made of 85% water, 1% sodium carboxymethylcellulose, and 14% powdered activated graphite dispersed on its surface with dimensions of 15 mm x 35 mm and a thickness of 1 mm were deposited on top of the secondary current collector (1).

[0079] Subsequently, the active material (3) prepared according to Example 1 was deposited on the porous layer (6) to a thickness of 5 mm.

[0080] Then, a secondary current collector (1) made of aluminum and having a passivation layer (at least one oxygen-containing compound layer (2)) was prepared. The latter was a secondary current collector (15 mm × 35 mm) having a passivation layer on the current collector. Specifically, it was a commercially available aluminum foil for capacitors (0.36 to 0.80 μF / cm). 2 ) on one side.

[0081] Finally, a primary current collector (5) made of pyrolytic graphite and having dimensions of 15 mm x 50 mm and a thickness of 6 mm was deposited on top of the secondary current collector (1) to obtain the final EPG2 device.

[0082] EPG2 shown in Figure 2 a primary current collector (5) (15 mm × 50 mm) made of pyrolytic graphite (6 mm thick); a secondary current collector having an oxygen-containing compound layer (2) (anodic passivation layer); The active organic material (3) of Example 1 a porous layer (6) containing 85% water, 1% sodium carboxymethylcellulose, and 14% powdered activated carbon; Electrode (4) and a secondary current collector (1) (15 mm x 35 mm) in the form of a graphite foil (100 μm thick); It was equipped with a primary current collector (5) (15 mm x 50 mm) made of pyrolytic graphite (thickness 1 mm).

[0083] Example 5 Characterization of the EPG2 of the present invention (EPG2) The EPG 2 according to Example 4 was exposed to a constant temperature of 25°C, and the voltage across the two collectors connected in parallel with a 100 ohm load for 2 minutes and disconnected for 2 minutes was measured over multiple cycles. Figure 5 shows the response of the EPG. When connected, the EPG exhibited a voltage drop from 0.5-0.6 V to approximately 0.1 V, and when disconnected, a substantially complete recovery of the initial value. This behavior, which consists of reaching 0.1 V when connected and recovering the initial voltage when disconnected, can be exploited over many cycles of connecting and disconnecting the EPG from a load. This behavior demonstrates the EPG's ability to spontaneously recover charge during the disconnection phase.

[0084] Example 6 Characterization of PGM1 in three stacks in a series of five EPGs of the present invention Three stacks, each consisting of five EPGs 2 assembled according to Example 4, were connected in series, exposed to a constant temperature of 25°C, and the voltage across the two collectors under a 100 ohm load was measured. Figure 6 shows the response of PGM 1. When connected, the PGM exhibits a voltage drop from 1.6-1.5 V to approximately 0.2 V and a stable current of approximately 2 mA. This configuration demonstrates the feasibility of connecting EPGs in series.

[0085] Example 7 Characterization of PGM2 of the five parallel EPGs of the present invention Five EPGs 2, each constructed according to Example 4, were connected in parallel, exposed to a constant temperature of 25°C, and the voltage across the two collectors under a 100 ohm load was measured. Figure 7 shows the response of the PGMs 2. When connected, the PGMs 2 exhibit a voltage drop from 0.5-0.6 V to approximately 0.25 V and a stable current of approximately 2.7 mA. This configuration demonstrates the feasibility of connecting EPGs in parallel.

[0086] Example 8 Characterization of the EPG of the present invention (EPG2) An EPG constructed according to Example 4 was exposed to a constant temperature of 25°C and the voltage across the two collectors connected across a 100 ohm load was measured. The graph in Figure 8 shows the response of the EPG. Once connected, the EPG exhibits a voltage drop from 0.3-0.35 V to approximately 0.025 V and a steady current of approximately 0.3 mA.

[0087] Example 9 Characterization of the Flexible EPG2 (EPG2) of the Present Invention The EPG2 device is 660cm 2 The assembly started with a primary current collector (5) made of PET polyethylene terephthalate polymer foil with a silver conductive layer having dimensions of 1.5 mm and a thickness of 80 μm. On top, the EPG2 device was placed at 660 cm. 2 A secondary current collector (1) was deposited in the form of graphite with dimensions of 10 μm and a thickness of 10 μm.

[0088] Then, 660cm 2 and a thickness of 24 μm, and an electrode (4) made of carbon powder with a thickness of 660 cm 2 A porous layer (6) made of 85% water, 1% sodium carboxymethylcellulose, 14% powdered activated graphite dispersed on the surface having dimensions of 1.0 μm and a thickness of 24 μm was deposited on top of the secondary current collector (1).

[0089] Subsequently, the active material (3) prepared according to Example 1 was deposited to a thickness of 48 μm on the porous layer (6) between commercial capacitor papers.

[0090] Then, a secondary current collector (1) made of aluminum and having a passivation layer (at least one oxygen-containing compound layer (2)) was prepared. The latter (commercial capacitor aluminum foil) was used as the current collector (660 cm 2 ) and a secondary current collector having a passivation layer on it. Specifically, a commercially available aluminum foil for capacitors (0.36 to 0.80 μF / cm 2 ) on one side.

[0091] Finally, a primary current collector (5) made of pyrolytic graphite and having dimensions of 15 mm x 50 mm and a thickness of 6 mm was deposited on top of the secondary current collector (1) to obtain the final EPG2 device.

[0092] The EPG was exposed to a constant temperature of 25°C and the voltage across the two collectors connected to a 100 ohm load was measured. The graph in Figure 9 shows the response of EPG2. When connected, EPG2 exhibits a voltage drop from 0.60-0.65 V to approximately 0.375 V and a steady current of approximately 7 mA.

[0093] Example 10 Characterization of the flexible EPG2 of the present invention (EPG2) at T = 40°C and 50°C The EPG2 device of Example 9 was tested at different temperatures relative to room temperature. The graph in Figure 10 shows the response of EPG2. When connected, EPG2 exhibited a voltage drop from 0.60-0.65 V to approximately 0.375 V and a current of approximately 5 mA; as the temperature increased, the voltage and current values ​​increased proportionally to the established temperature.

[0094] Example 11 Preparation of Generator 2 (EPG2) of the Present Invention with External Electrical Contacts Figure 11 shows an electrical generator 2 (EPG2) of the present invention with electrical contacts for connection, said contacts being outside the active area of ​​the device.

Claims

1. at least one electrode; at least one current collector; at least one active organic material interposed between the at least one electrode and the at least one current collector; at least one oxygen-containing compound layer; the at least one active organic material comprises at least one organic polymer obtained by heating a mixture comprising 5% to 70% by weight of polyvinyl alcohol and 30% to 95% by weight of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol, based on the total weight of the at least one organic polymer, at a temperature in the range of 60°C to 160°C for 1 hour to 3 hours; the at least one oxygen-containing compound layer is in contact with the at least one active organic material; The at least one oxygen-containing compound layer is in contact with the at least one current collector.

2. 2. Electric power generator (EPG) according to claim 1, wherein the at least one organic polymer of the at least one active organic material is obtained by a mixture comprising 8% to 40% by weight of polyvinyl alcohol and 60% to 92% by weight of at least one glycol selected from the group consisting of ethylene glycol and propylene glycol, relative to the total weight of the at least one organic polymer.

3. 3. Electric power generating device (EPG) according to claim 1 or 2, wherein said at least one oxygen-containing compound layer is at least one passivation layer of said at least one current collector.

4. The at least one oxygen-containing compound layer is selected from the group consisting of MgO, ZnO, and ZrOCl. ２ , ZrO ２ , SiO ２ , Bi ２ O ３ , Fe ３ O ４ , Al ２ O ３ , TiO ２ , BeO, CaO, Ga ２ O ３ , In ２ O ３ , GeO ２ , SnO ２ and PbO ２ 3. The power generating device (EPG) according to claim 1 or 2, wherein the layer is at least one oxygen-containing compound selected from the group consisting of:

5. 5. The power generating device (EPG) of claim 4, wherein said at least one oxygen-containing compound has a mean particle diameter in the range of 5 nm to 40 μm.

6. 5. The power generating device (EPG) of claim 4, wherein said at least one oxygen-containing compound has a mean particle diameter in the range of 15 nm to 10 μm.

7. 5. The power generating device (EPG) of claim 4, wherein said at least one oxygen-containing compound has a mean particle diameter in the range of 20 nm to 5 μm.

8. 8. Electric power generating set (EPG) according to any one of claims 1 to 7, wherein the EPG comprises a further current collector which is a primary current collector.

9. 9. Electric power generating device (EPG) according to any one of claims 1 to 8, wherein the at least one current collector is a secondary collector made of a material selected from the group consisting of metals, porous carbon, and conductive oxides, sulfides, alloys with nearly constant electrical resistivity, manganese oxide and its compounds, phosphates, and mixtures or composites thereof.

10. 9. Electric power generating device (EPG) according to claim 8, wherein said primary current collector is made of a material selected from the group consisting of pyrolytic graphite, carbon coke and / or carbon based materials, chemically stable semiconductors of boron, silicon, germanium, silver and their intrinsic and extrinsic states, ceramic materials as carbides and nitrides, perovskites, spinel compounds and PET (polyethylene terephthalate) and mixtures or composites thereof.

11. 10. Electric power generating system (EPG) according to claim 9 when dependent on claim 8, wherein the primary current collector is in contact with the secondary collector.

12. 9. The electric power generating system (EPG) of claim 8, wherein the primary current collector is made of a PET polyethylene terephthalate polymer foil having a silver conductive layer.

13. 13. The power generating device (EPG) of claim 1, wherein the EPG comprises at least one porous layer, the porous layer being in contact with the at least one active organic material.

14. 14. The power generating device (EPG) according to claim 13, wherein said at least one porous layer is made of cellulose, a cellulose composite material, a porous carbonaceous material, and a composite material with a carbon matrix.

15. 15. The electric power generating system (EPG) of claim 14, wherein said at least one porous layer comprises 85% water, 1% sodium carboxymethyl cellulose, and 14% powdered activated carbon.

16. 16. Electric power generating device (EPG) according to any one of claims 13 to 15, wherein said at least one organic polymer is adsorbed onto said at least one porous layer.

17. 17. A generator module (PGM) comprising a plurality of generators (EPG) according to any one of claims 1 to 16, said generators being connected in parallel or in series.

18. 3. The method for making an electric power generating device (EPG) according to claim 1 or 2, wherein when the at least one current collector is a secondary current collector, the at least one oxygen-containing compound layer is formed in the assembled state after the EPG is assembled.

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