Improved method and apparatus for extracting electricity from water

Abstract

The present invention relates to a method (200) and apparatus for extracting electricity from a volume of water comprising the steps of: - providing (210) the volume of water in a first and a second portion, no dissolved electrolytes being present in water; - contacting (220) a respective first (70) and second (80) electrode in each first (60) and second (90) portion; - extracting (230) electricity from the volume of water by connecting a load (R) between the aforesaid electrodes (70,80); the method being characterized in that: - the respective first (70) and second (80) electrode are made of elect roconductive but chemically inert materials with respect to the generation of oxidoreductive phenomena on the surface thereof; each first and second portion is comprised in respective non-metallic first material (60) and second material (90) selected from hydrophilic materials; - the respective first (70) and second (80) electrode are different from each other and / or the respective first (60) and second (90) material have different hydrophilicity; thus preventing the production or adsorption of ions on the surface of the respective first (70) and second (80) electrodes.

Description

[0001] Improved method and apparatus for extracting electricity from water

[0002] To: Oxhy S.r.l.

[0003] Inventors: Roberto Germane, Francesco Paolo Tuccinardi,

[0004] Graziano Terenzi

[0005] The present invention relates to a method and apparatus for extracting electricity from water, having environmental radiation, mainly Infrared, as a source.

[0006] Background art

[0007] Energy demand is growing rapidly due to the everwidening spread of even more accessible electronic devices in several fields of the market, including mobile devices, wearables, personal computers, loT, telecommunications, household appliances, and industrial equipment. On the other hand, the increasing scarcity and costs associated with traditional energy sources, such as oil and gas, require a profound transformation of our modern energy supply systems [1], which in turn require a further development of renewable sources and energy recovery systems to make our societies more self- sufficient and resilient.

[0008] Energy harvesting is the method by which energy is obtained from external sources - ambient energy - and then captured and made available to electronic circuits, such as those used in appliances, computers, wearables and wireless sensor networks. Currently, energy recovery devices convert ambient energy into electric current, but are limited to the production of reduced amounts of energy.

[0009] There is almost general agreement among market analysts regarding the trends and dynamics of the Energy Harvesting market as an early-stage market.

[0010] According to Allied Market Research [4], the global Energy Harvesting systems market was valued at $511.6 million in 2020 and is expected to reach $1,057.7 million by 2030, growing at a compound annual growth rate (CAGR) of 7.5% from 2021 to 2030. In addition, Mordor Intelligence [4] raises the growth estimate for the 2023- 2028 period, as the global Energy Harvesting systems market is expected to register a CAGR of 9.8% in the prediction period.

[0011] With many countries committed to the use of renewable resources, the need to improve this segment has increased. There is, for example, the need to manage solutions in the global market for the control and prediction of energy consumption. According to Indian Brand Equity Foundations, India had a renewable energy capacity of 101.53 GW as of September 2021, representing 38% of the total installed energy capacity. By 2030, the country hopes to have about 450 gigawatts (GW) of renewable energy capacity installed, with solar accounting for about 280 GW (almost 60%).

[0012] In 2021, China connected a record 54.9 gigawatts of solar generation capacity to the grid, up 14% from 2020 and representing 31% of the country's total capacity additions. According to the National Energy Administration (NEA), China's total solar power capacity reached 306.56 GW in 2021. In the same year, there were 47.6 GW of new wind power installations, down 34% from the previous year's record of 71.7 GW. Offshore wind capacity reached a new record of 16.9 GW.

[0013] Factors such as the wide deployment of loT devices in automation, the proliferation of the urban population, the growing demand for safe, energy-efficient and durable systems, the growing trend towards green energy, the penetration of energy harvesting technology in the automation of buildings and homes and the favorable initiatives by governments, are expected to stimulate the growth of the market during the prediction period.

[0014] Consumer electronics will hold a significant market share in the field of Energy Harvesting [5]:

[0015] — Energy harvesting systems are increasingly used in consumer electronics, such as wearables, smartphones, remote controls, wireless appliances, implants in the body, etc. They allow consumer electronics to operate where conventional energy sources are not available. Such features not only extend use but also eliminate the geographical constraint whereby the devices must be close to a source of energy. These features are driving the use of energy harvesting systems in consumer electronics.

[0016] — Energy harvesting systems are used in remote controls, where the energy is obtained from the force exerted by the user pressing the button. Recently, ARM made a device with the ARM Cortex- M0+ low-consumption processor. - Technology vendors in the market are increasingly developing connected devices, and wearable devices are among the latest devices which are undergoing rigorous testing and innovation .

[0017] - The trend in this segment has been to increase the battery life of devices. Manufacturers are expanding the battery capacity of their devices, this being the reason why the demand for shorter charging times is driving the market growth in this field.

[0018] - Energy harvesting systems eliminate the need to replace batteries in devices such as smartphones and laptops, providing energy sources which generate energy from the device itself. In the near future, energy harvesting systems could collect energy from different sources and have a very low discharge rate, drastically improving the useful life of the devices.

[0019] Patent 10201290205151705 [6] describes a method and apparatus for extracting electricity from water.

[0020] With reference to Fig. 1 taken from such a prior art patent, such a method for extracting electricity from a volume of water 2 comprises the steps of:

[0021] - dividing the volume of water 2 by means of a membrane-filter 5 adapted to separate said volume into a first 3 and a second 4 sub-volume of water, said water being distilled water;

[0022] - immersing a respective electrode 7,8 in each of the first 3 and second 4 sub-volumes; - contacting one of said sub-volumes 3,4 of water with a hydrophilic surface 6 or immersing in one of said sub-volumes 3,4 insoluble nanoparticles adapted to modify the organizational structure of water;

[0023] - extracting electricity from the volume of water by connecting a load R between the aforesaid electrodes 7,8.

[0024] This method and the related apparatus shown in Figure 1 have the following weaknesses, with regard to the engineering possibilities:

[0025] 1. Free liquid water is used, which involves problems related to managing and preventing evaporation.

[0026] 2. NAFION® is used as a highly hydrophilic fluorinated polymer, which is a very expensive and unsustainable material (it contains Fluorine), which is also patented, as well as a registered trademark of Dupont. In particular, the production thereof requires the use of materials and methods which can be harmful to the environment. Furthermore, NAFION is not biodegradable and can cause environmental problems if disposed of improperly.

[0027] 3. The extraction of electric current tends to decay to reduced values within a few days.

[0028] 4. Use of Platinum electrodes (expensive, and not eco- sustainable) .

[0029] 5. A fairly expensive sub-micrometric filter is required.

[0030] 6. To obtain currents of interesting intensity, it is also important to use hydrogen peroxide (H2O2).

[0031] 7. The dimensions of the macroscopic system (tens of cm).

[0032] The document ROJALEENA DAS ET AL: "Electricity generation by splitting of water from hydroelectric cell: An alternative to solar cell and fuel cell", INTERNATIONAL JOURNAL OF ENERGY RESEARCH, WILEY, CHICHESTER, GB, vol. 44, no. 14, 27 July 2020 (2020-07- 27), pages 11111-11134 and the document SHAH JYOTI ET AL: "Water splitting on the mesoporous surface and oxygen vacancies of iron oxide generates electricity by hydroelectric cell", MATERIALS CHEMISTRY AND PHYSICS, ELSEVIER SA, SWITZERLAND, TAIWAN, REPUBLIC OF CHINA, vol. 258, 26 October 2020 concern a hydroelectric and not an "oxyhydroelectric" phenomenon as in the prior art mentioned above. Furthermore, such documents explicitly discuss specific electrochemical phenomena based on the circulation of ions inside the cell, with the following reactions to the electrodes:

[0033] Zn + 2OH- -> Zn (OH)2 + Eoxidation 0.76V (anode) 2H3O++ 2e- -> H2-) + 2H2O Ereduction 0.22V (cathode)

[0034] Such an operation with redox is precisely the basis of the disadvantages of the prior art, as the electrodes are subject to consumption.

[0035] A need remains for a method and apparatus for extracting electricity from water which is more efficient, less expensive, and eco-sustainable.

[0036] Purpose and object of the invention

[0037] It is the object of the present invention to provide a method and apparatus for extracting electricity from water which overcomes the drawbacks and solves the problems of the prior art.

[0038] The present invention relates to a method and apparatus according to the appended claims.

[0039] Detailed description of embodiments of the invention

[0040] List of drawings

[0041] The invention will now be described by way of a nonlimiting illustration, with particular reference to the figures in the accompanying drawings, in which:

[0042] - Figure 1 shows an apparatus for extracting electricity from water according to the prior art;

[0043] - Figure 2 shows a flow diagram of an embodiment of the method according to the invention;

[0044] - Figure 3 shows a diagram of an apparatus according to an embodiment of the invention;

[0045] - Figure 4 shows an example of an infrared voltage response, over time, of an example apparatus according to the present invention;

[0046] - Figure 5 shows the voltage response of a first device according to an embodiment of the invention on consecutive days (a) and (b);

[0047] - Figure 6 shows the voltage response of a second device according to an embodiment of the invention on consecutive days (a) and (b);

[0048] - Figure 7 shows the voltage response in (a) a first test device and in (b) a second test device according to an embodiment of the invention; - Figure 8 shows the voltage response in (a) a third test device and in (b) a fourth test device according to an embodiment of the invention;

[0049] - Figure 9 shows the voltage response of three devices according to the invention in parallel and a resistance of 220kΩ;

[0050] - Figure 10 shows the results of tests according to the invention on 5 devices in parallel and a resistance of 180kΩ on two consecutive days (from left to right);

[0051] - Figure 11 shows the results of tests according to the invention on 5 devices in series and a resistance of 180kΩ; and

[0052] - Figure 12 shows the results of tests according to the invention on 5 devices in series and a resistance of 220kΩ;

[0053] - Figure 13 shows the deconvolution of the FTIR spectra of PAAC (hydrogel Poly (acrylic acid)); the ordinates show the relative absorbance measured, the abscissae show the wavelength; the numbers indicated in the figure are the relative percentages of the 4 Gaussians in which the region of water in the PAAC was deconvoluted;

[0054] - Figure 14 shows the deconvolution of the FTIR spectra of distilled water; the ordinates show the relative absorbance measured, the abscissae show the wavelength; the numbers indicated in the figure are the relative percentages of the 4 Gaussians in which it was deconvoluted in the same region of the previous figure;

[0055] — Figure 15 shows the case of Figure 13 but at various time instants of a continuous mixing of the PAAC, where at 45 minutes the result of Fig. 13 is obtained;

[0056] - Figure 16 shows the voltage response of a device according to an embodiment of the invention along consecutive days in (A) and after about 45 days in (B).

[0057] It is here specified that elements of different embodiments can be combined to provide further embodiments, without restrictions, by respecting the technical concept of the invention, as those skilled in the art will effortlessly understand from the description .

[0058] The present description also makes reference to the prior art for the implementation thereof in relation to the detail features not described, such as elements of minor importance usually used in the prior art in solutions of the same type, for example.

[0059] When an element is introduced, it is always understood that there can be "at least one" or "one or more".

[0060] When a list of elements or features is given in this description, it is understood that the finding according to the invention "comprises" or alternatively "consists of" such elements.

[0061] When listing features in the same sentence or bullet list, one or more of the single features can be included in the invention without connection with the other features on the list. Two or more of the parts (elements, devices, systems) described above can be freely associated and considered as part kits according to the invention.

[0062] Embodiments

[0063] The present invention is an innovative Energy Harvesting system which utilizes infrared radiation to generate electricity based on a recently discovered quantum effect, called the Oxhydroelectric Effect [2] [3], to be positioned on the market to create value by helping to solve three of the most current crucial issues concerning energy recovery and energy supply, namely scarcity, availability and scalability.

[0064] In the present invention, contrary to the prior art, instead of using free liquid water, with the related problems of managing and preventing evaporation, materials are used incorporating - in various manners - water in the liquid state; this in itself solves a good part of the problems related to the evaporation and practical management of the liquid phase.

[0065] Such materials are hydrophilic, possibly with a different degree of hydrophilicity, i.e., the ability to attract and retain water, this ability also able to be negative. The ability to retain water can also be seen in relation to how water is structured therein (measurable by means of infrared spectroscopic techniques, according to an aspect of the invention made for the first time by the inventors.

[0066] Preferably according to the invention, the hydrophilic materials are non-metallic. The combination of electrodes and hydrophilic materials is such as to generate an asymmetry between two regions of the water volume. Furthermore, highly hydrophilic polymers can be used, in particular hydrogels, cheaper and more eco-sustainable materials, which replace the expensive and unsustainable NAFION®.

[0067] Thereby, a duration of the electric current extraction of several months is ensured (limited only by the mechanical properties of the polymers / hydrogels).

[0068] The electrodes can be inexpensive (graphite, passivated metal, conductive gel, electro-conductive material, etc.).

[0069] The sub-micrometric filter of the prior art is no longer necessary.

[0070] The apparatus of the invention, shown in Fig. 3, and the method of the invention, diagrammed in Fig. 2, also work without the addition of hydrogen peroxide (H2O2).

[0071] According to the invention, no electrolytes are present in the cell water. As the electrodes are inert, redox reactions and the generation or adsorption of ions on the electrode surface are not possible.

[0072] The electrodes in an oxyhydroelectric cell of the invention are essential for collecting and transporting the electrons generated by infrared (IR) radiation, for generating the electric field necessary for load separation, and for ensuring an efficient electrical connection to the external circuit, thus maximizing the energy conversion efficiency, but must not generate mobile ions in solution. Furthermore, they can contribute to the generation of physical asymmetry between the two regions of liquid water, but without any chemical role.

[0073] Therefore, the approach is to always use inert electrodes, i.e., which do not release metal ions so that they do not generate redox reactions. Then two equal electrodes and two hydrophilic materials can be used or a single hydrophilic material and two different electrodes .

[0074] Thereby, the dimensions of the system are centimeters, but can be millimeters and potentially submillimeters .

[0075] With reference to Figs. 2 and 3, the method 200 for extracting electricity from a volume of water according to the invention can comprise the steps of:

[0076] - providing 210 the volume of water in a first and a second portion, each first and second portion being comprised in a respective first 60 and second 90 different hydrophilic material selected from materials which retain water;

[0077] - contacting (or even immersing) in 220 in each first 60 and second 90 hydrophilic material a respective first 70 and second 80 electrode;

[0078] - extracting 230 electricity from the volume of water by connecting a load R between the aforesaid electrodes 70,80.

[0079] According to an aspect of the invention, the first 60 and second 90 hydrophilic materials can be a first and a second hydrogel, which are equal (and in this case the electrodes are different) or different (and in this case the materials of the electrodes can also be equal). In any case, the first and second materials are not metal materials, and therefore, for example, ferrites, metal oxides (in particular TTiO2, V2O5, Cr2O3, Mn3O4, Sc2O3, Co304, CuO, NiO, CeO2, Fe2O3, A12O3, Si02, ZnO, SnO2, MgO, Fe3O4, BaO), multiferroic materials and compounds (in particular BaTi03-CoFe204 and MgO.8LiO.2Fe2O4), metal sulfides are excluded in a non-limiting manner.

[0080] According to an aspect of the invention, the volume of water is without the addition of hydrogen peroxide (H2O2).

[0081] The apparatus 100 for extracting electricity from water according to an embodiment of the invention can therefore comprise:

[0082] - a container 110 partially or entirely filled with a volume of water;

[0083] - a first 60 and second 90 different hydrophilic material selected from materials which retain water, positioned in respective portions of said container 110;

[0084] - a first 70 and a second 80 electrode, respectively contacted (or even immersed) with said first 60 and said second (90) hydrophilic material;

[0085] - a load R connected between said first and second electrodes 70,80.

[0086] According to an aspect of the invention, the first 60 and second 90 hydrophilic material each extend in a respective closed volume inside said container 110. For example, such a closed volume can result from the use of special caps in the region where the electrodes are inserted.

[0087] According to an aspect of the invention, merely by way of non-limiting example, the electrodes can be made of one or more of the materials of the group: platinum, gold, graphite, metals or metal alloys passivated on the surface by virtue of the generation of a chemically inert oxide film, conductive polymers, etc.

[0088] According to an aspect of the invention, the first 70 and second 80 electrode are made of the same material but are different in the surface structure thereof. In particular, the surface structure can differ by degree of surface roughness Ra, "arithmetical mean roughness", and / or Sa "Arithmetic Mean Height - 3D" and / or Sq "Root Mean Square Height - 3D", typically measured by noncontact optical profilometry, or by AFM, or confocal microscopy .

[0089] For example, a surface treatment can be that of a platinum electrode on which what is known as platinum black is deposited, which is a fine powder of platinum with good catalytic properties. The resulting "platinized platinum" has a real surface which is much more elevated than the geometric surface of the electrode and, therefore, shows a greater action than that of polished platinum.

[0090] According to an aspect of the invention, said surface structure differs by degree of hydrophilicity, typically evaluated by the classic measurement of the static contact angle with drops of deionized water, by means of an optical tensiometer. Fig. 4 shows an example of an infrared response in an example of the invention: turning on the IR lamp records a passage from 0.85 microWatt extracted (IR lamp turned off) to 2.6 microWatt extracted (IR lamp turned on), i.e., the 300% increase in electrical power extracted (in the figure the voltage at the ends of a resistor is indicated, the value of which was however used to make the Watts calculation). The fairly stable value of the current extracted in the first phase of the graph should be noted, in which the system is exposed to the ambient thermal bath, about 13 hours, from time t= 00.00 h to time tl = 13.00 h (it should be noted that the graphed voltage (t=0.00) is measured (tl=13h) at the ends of a 47 kΩ resistor).

[0091] The graph in Fig. 4 shows the clear and immediate response of the system to the IR radiation added by a lamp in point A; in fact, the measured voltage increases from about 200 mV to 350 mV in a time of 3600 s (lh), that is, 75% increase in extracted electrical power.

[0092] When the lamp is switched off (point B), the voltage decreases with a certain time constant, due to the capacitive component of the system, but visibly lower than that characterizing the ascent, which shows that the generation of energy derives from the ambient background which still allows the system to generate as a baseline a current corresponding to the voltage of about 210 mV at the ends of a 47 kOhm resistor.

[0093] At point C, the lamp was turned on again to confirm the effect of the first turning on. The lamp is switched off again in point D. It is also important to note that at room temperature the electric power extracted is already equal to 0.85 microwatt (~ 1 microwatt), which corresponds to a Power density of the order of ~ IW / m3, since the cell in question has a volumetry of the order of cm3.

[0094] The hydrophilic film generates a coherent water region at the boundary between the surface thereof and water, thus causing a separation between "more coherent water" and "less coherent water" (see publications [2,3]); the presence of the O2 molecules in the electrolyte (ensured by the addition of H2O2) stimulates the excitation of the almost free electrons from the water CDs which should pass through an energy barrier of 0.44 eV, and thereby the O2 molecules become privileged receptors of the electrons which tunnel out of the CD (Coherence Domain), a gap of about one tenth of eV being sufficient. The diagram of the possible general mechanism in place for the extraction of electron current from water (mediated or not by O2 molecules) is as follows: (Ambient heat = photons of infrared radiation) + 2H2O (EZ water) + 02 ^ 02 + 2H2O ("bulk" water) + (Electronic excitation). The "reducer", i.e., that which can allow the development of redox reactions, is the same coherence domain of water. In the absence of O2the dynamics are the same, only the energy gap changes (about 0.44 eV) which in any case falls in the range of the infrared electromagnetic spectrum.

[0095] One or more elements of the apparatus of the invention can be 3D printed. It is important to underline that, with respect to the systems discussed above, and present in the publications cited, the following advances have been achieved:

[0096] — Possibility of using an inexpensive hydrophilic gel, which not only "replaces" the very expensive NAFION®, but lends itself to obtaining a mini-cell saturated with polymer and therefore without the presence of "free" liquid water.

[0097] - Electrical current generated for months (there are only "mechanical" limits of the polymer) which does not decay.

[0098] — Inexpensive electrodes (platinum is no longer necessary).

[0099] — A micrometer filter is no longer necessary.

[0100] - It also works without the presence of H2O2.

[0101] Over time, multiple experiments were conducted, which demonstrated the oxyhydroelectric effect and made it possible to understand the qualitative and quantitative operation thereof.

[0102] 5 Eppendorf polypropylene (does not release contaminants) tubes with a diameter of about 1 cm were used, cutting them to a length of 3.5 cm, thus obtaining an almost perfect cylinder, which was filled, after ideally dividing it into two halves, with two different non-commercial hydrophilic gels, designed ad hoc so as not to release any electrolytes in water, and to be made in-house at very low costs. Distilled water was then introduced in the tube to rehydrate the constituent polymers in an embodiment of the hydrophilic materials. The two ends of the tube were then closed with two Eppendorf caps, on which a small central hole was thermally made to pass the electrodes. The electrodes are not made of Platinum, but of a low-cost conductive material, covered with an oxide layer, so as to be practically inert with respect to new possible oxidation phenomena.

[0103] The devices were numbered and the measurement set-up was developed, consisting of a Keithley 2700 multimeter interfaced with a PC to record the voltage data at the ends of the resistor as a function of time, acquiring at a rate of 1 Hz, and a 150W Leuci IR lamp.

[0104] Over time, a very wide range of measurements were made, of which only a few relevant results are reported here.

[0105] The measurements were aimed at:

[0106] A. Verifying a reproducible behavior of the different devices.

[0107] B. Verifying a repeatable behavior of the different devices over time.

[0108] The "measurement protocol" was selected based on the behavior of the first device tested, and can be summarized as follows:

[0109] - Time equal to approx. 30 min to reach stabilization at room temperature.

[0110] - Switching on the IR lamp and device subjected to IR irradiation for approx, lh.

[0111] - Switching off the IR lamp and waiting for the achievement of new stability conditions in a time of approx. 1.5h. Device No. 1

[0112] Fig. 5 below shows the results of the measurements made on device No. 1 on 2 different days (Figs. 5(a) and 5 (b)). Current and electrical power values are shown in the following Table (Tab. I, the subscript "i" indicates the start time instant, the subscript "f" indicates that of the end of the phase at room temperature and the phase with added infrared irradiation, the subscript "f2" indicates that of the end of the phase at room temperature following the added irradiation phase; the subscript "amb" stands for ambient (room temperature), the subscript IR for "infrared irradiation"), and are calculated from the measured values of the voltage at the ends of the resistor in the points of interest. Tab. I

[0113] Fig. 5 shows the response of the system to the IR radiation added by means of a lamp for the duration of 1 h, practically until the saturation of the phenomenon; the measured voltage goes from about 60 mV to about 130 mV in the time of lh, with an increase of more than 100%, and when the lamp is turned off the voltage decreases with a certain constant of time, due to the capacitive component of the system, but visibly lower than that characterizing the ascent, which shows that the generation of energy derives from the ambient background which still allows the system to generate as a baseline a current corresponding to the voltage measured at the ends of the 47 kOhm resistor.

[0114] Fig. 16(A) shows a similar result with other materials on the scale of days in (A) and after about one month in (B). A rise in the extracted current is seen in the first phase following the first contact with the electrodes of the system. After a certain time (about 1 month) this system stabilizes and the extracted current has an almost constant trend. The visible changes can be attributed to changes in room temperature.

[0115] Device No. 2

[0116] Fig. 6 instead shows the results of the measurements carried out on device No. 2 on 2 different days (day 1 in Fig. 6(a) and day 2 in Fig. 6(b)) and in Tab. II the reference values for the device 2 (Fig. 6(b).

[0117] Tab. II

[0118] For the other devices prepared in this first step, the measurement trend is the same, both from the qualitative point of view and as regards the ranges of the current and electrical power values.

[0119] Similar behavior is also recorded over time (2 measurements performed on different days).

[0120] Preparation of the second set of test devices and verification of the behavior thereof

[0121] With the aim of verifying / recording any changes in the behavior of the individual devices as a function of the materials / preparation method of the sample to be tested, 4 devices were prepared starting from threaded fittings in D glass ("D glass" is a category of optical glass with a low dispersion (low "prism effect") 1.2x5 joined two by two so as to make a single cylinder of length always equal to 4.5 cm. The possibility of closing the ends with plastic caps was also utilized so as to avoid the evaporation of water with which the two types of non-commercial hydrophilic polymers were hydrated, with which the two inner halves were filled. A small hole was made in the center of the two caps to pass electrodes of the same material used previously.

[0122] The devices were again numbered and the same measurement set-up and a 47kΩ resistor were used. This time it was intended to verify only the first step of the previous "measurement protocol", i.e., the achievement of stable conditions at room temperature, without then "stressing" the devices with IR radiation.

[0123] The table below shows the results of the measurements carried out, on the same day, on the 4 glass devices (see Figs. 7 and 8), and the following Table (Tab. Ill) shows the current and electrical power values calculated starting from the measured values of the voltage at the ends of the resistor at the beginning (more precisely when the "descent" begins, indicated with subscript "i") and at the end of the measurement (indicated with subscript "f").

[0124] Tab. Ill

[0125] The devices were again numbered and the same measurement set-up and a 47kΩ resistor were used. This time it was intended to verify only the first step of the previous "measurement protocol", i.e., the achievement of stable conditions at room temperature, without then "stressing" the devices with IR radiation.

[0126] In all the graphs there is a rise time which in Figs. 7 (a) and 7(b) is very short with respect to the abscissa scale.

[0127] Configuration in parallel with the devices of the first test set; behavior verification

[0128] To verify the behavior of the test devices connected in parallel, the tubes obtained from the 1 cm diameter PP Eppendorf tubes prepared in the first phase were used. The measurement concerned the achievement of stable conditions at room temperature.

[0129] In this case, the choice of the load value was 180 kΩ and 220 kΩ; therefore, values suitably higher with respect to those used for the individual elements (47 kΩ), for the purpose of ensuring that too much energy was not extracted from the system too quickly, so as not to generate an "emptying" that would not allow the phenomenon to remain in equilibrium, but would tend to cause it to decay, as already discussed.

[0130] Below are the results (load impedance adaptation) of the measurements carried out in the following configurations .

[0131] No. 3 devices in parallel and a 220kΩ resistor

[0132] Fig. 9 and the table show the results obtained (the subscript "i" stands for the measurement at the maximum voltage point reached, without having used an infrared lamp).

[0133] No. 5 devices in parallel and a 180kΩ resistor in 2 consecutive days

[0134] Fig. 10 and the table show the results obtained (the subscript "i" stands for the measurement at the maximum voltage point reached, without having used an infrared lamp).

[0135] Configurations in series with the devices of the first test set; behavior verification

[0136] To verify the behavior of the test devices arranged in series, the tubes obtained from the 1 cm diameter PP Eppendorf tubes prepared in the first phase were used. The measurement concerned the achievement of stable conditions at room temperature. Below are the results of the measurements carried out in the following configurations .

[0137] No. 5 devices in series and a 180kΩ resistor

[0138] Fig. 11 and the table show the results obtained (the subscript "i" stands for the measurement at the maximum voltage point reached, without having used an infrared lamp). No. 5 devices in series and a 220kΩ resistor

[0139] Fig. 12 and the table show the results obtained (the subscript "i" stands for the measurement at the maximum voltage point reached, without having used an infrared lamp).

[0140] Therefore, the infrared stacks behave substantially like normal photovoltaic cells when connected in series or in parallel, but with apparently lower efficiency, probably due to the structural diversity between the individual experimental systems. If two batteries of nominal voltage VI and V2 and nominal current Al and A2 are connected

[0141] - in series, the voltage is summed (i.e., Vtotal = VI + V2), while the current remains constant;

[0142] - in parallel, the current is summed (i.e., Atotal = Al + A2), while the voltage remains constant.

[0143] In fact, in general, it occurs as with standard batteries, in which:

[0144] - Connection in series of different batteries:

[0145] • Voltage differences: If the batteries have different rated voltages, problems can occur when they are connected in series. The battery with the higher voltage will tend to discharge faster than the others, which could lead to overcharging the batteries with lower voltages and potentially damaging them or causing overheating.

[0146] • Capacity differences: batteries with different capacities can also create problems when connected in series. The battery with the lowest capacity will discharge faster, forcing the others to discharge to match the voltage. This could lead to an overall reduced useful life of the system and a decrease in performance.

[0147] - Connection in parallel of different batteries:

[0148] • Capacity differences: batteries connected in parallel with different capacities could cause improper current flow therebetween. Batteries with higher capacities could end up carrying the majority of the load, discharging more slowly than those with lower capacities. This could lead to misalignment of the batteries and faster degradation of batteries with lower capacity.

[0149] • Voltage differences: even if batteries connected in parallel with different voltages tend to balance, an improper current flow could still occur therebetween, resulting in discharging or overcharging some batteries. This can lead to overheating or even a short circuit. The cell thus made is highly sensitive to light in the infrared range, which could lead it to be used as a sensor system.

[0150] The cell of the invention can also be used as an infrared radiation sensor, in which a processing unit which detects infrared radiation based on the current passing in the load R is comprised. The sensitivity measured in some tests carried out by the inventors was < 10-5W / cm2.

[0151] The system of the invention is capable of producing significant amounts of energy by utilizing natural infrared radiation in almost all environmental conditions, both indoor and outdoor. The system can be specifically designed with the aim of integrating it with a variety of microelectronic devices.

[0152] The system is based on a modular architecture comprising the following modules:

[0153] - Oxyhydroelectric cell battery in parallel or in series with adequate microcircuits;

[0154] - Communication module between the cell circuitry and the external systems;

[0155] - Firmware / Software module to monitor and control energy production and distribution;

[0156] - Additional modules can be added to give the system the configuration of an advanced energy production system which adapts to different application domains.

[0157] The efficiency of the Oxyhydroelectric Cells and the ability to generate electricity reliably and consistently were evaluated. The experiments carried out thus far highlight a current extraction pattern which, as anticipated, varies with the variation of IR radiation, is long-lasting and highly efficient. Considering that in an environment at 25°C, the infrared energy density is approximately 454.9 Watts per square meter (W / m2), therefore, with easy calculations, the volume density of infrared energy per cubic centimeter (W / cm3) « 455 microW / cm3is obtained. Therefore, a system of the invention which currently extracts 1 microW / cm3currently has an efficiency of about 1 / 500 = 2 %oo, which means that miniaturization alone would allow a millimeter-sized oxyhydroelectric cell to have an efficiency of 30%. Further research on Hydrogels could also increase the amount of electrons extracted at the same volume.

[0158] There are thus elements to conclude that the current extraction and thus the duration of the Oxyhydroelectric Cells over time is extremely long-lived with the ability to maintain long-term performance. According to the QED model of water used, 1 cm3of water - i.e., lg of water - contains 6.7 * 1022molecules and therefore there are 3.4 * 1021almost free electrons, i.e., which can be extracted with an amount of energy equivalent to that of ambient IR radiation. This means that for every cm3of water at room temperature, we would have about 103Coulombs "available" only for the almost free electrons. To date, the oxyhydroelectric effect has extracted about 1 microAmpere, which is equivalent to 1 microCoulomb per second, but there is still a billion times more energy available which could theoretically be extracted. It should be noted that a lightning bolt has a total charge of only about 5 Coulombs. This means that a drop of water has an "almost free" electric charge equal to about 200 lightning bolts. Furthermore, to date, no decay phenomena have been observed as long as water in the cell does not evaporate.

[0159] Miniaturization is a key aspect for the development of specific applications and for increasing efficiency. This is equivalent to developing a design which allows the miniaturization of the cells to integrate them in the battery, while ensuring significant efficiency and energy production. To date, by virtue of Microscale Additive Manufacturing techniques, it is possible to create micrometer-sized cells, inject appropriate hydrogels therein and print the microcircuitry necessary for the conduction of the electric current in the battery circuit and then supply it to external devices, or in any case proceed with the direct printing (2D and 3D) of gel systems and electrodes in appropriate connection.

[0160] With respect to the conventional renewable technologies, the Oxyhydroelectric Effect offers several significant advantages. First of all, the extraction of current by means of the Oxyhydroelectric Effect can occur in any light condition, including the total absence of visible light, infrared being pervasive in conditions far from the absolute zero temperature, allowing a continuous and reliable use. This eliminates the limitations related to the availability of direct sunlight or other light energy sources, which are typical of conventional photovoltaic technologies. Furthermore, the Oxyhydroelectric Effect allows the extraction of current from low-temperature heat sources, including temperatures between -20° and 100°C (in fact, in hydrophilic gels, water can remain liquid even below -20°C due to the well-known phenomenon of cryoscopic lowering; furthermore, we also have ebullioscopic raising, and therefore water can remain liquid, allowing the phenomenon in question to take place, even above 100°C as long as suitable gels or materials are used). This means that it can utilize common ambient heat sources, such as air or water, without the need for high temperatures. This flexibility opens up new possibilities for energy efficiency, allowing the use of thermal energy which is otherwise wasted (thermal waste typical of production companies).

[0161] Another significant advantage of the Oxyhydroelectric Effect is the ability thereof to overcome the power limitations typical of current energy recovery technologies.

[0162] While the existing energy recovery devices produce limited amounts of energy, the Oxyhydroelectric Effect promises to produce significant amounts of electricity. This opens up new opportunities for the large-scale application of this technology, providing a more reliable and efficient source of renewable energy.

[0163] The device according to the invention achieves these advantages also by eliminating ion exchange inside the cell and thus eliminating the need for electrolytes. In fact, the oxyhydroelectric effect consists of the generation of voltage and electric current in pure liquid water, without any electrolyte, following exposure to electromagnetic radiation in the infrared range, after creating a physical (non-chemical) asymmetry in the liquid water, for example by virtue of a strongly hydrophilic polymer, such as Nation. Since the publication of the first seminal research, other independent research referring to this effect has been published in peer-reviewed and reputable scientific journals (with impact factors above the median in the respective fields). The system can be described as a photovoltaic cell operating in the infrared electromagnetic range, based on liquid water instead of a semiconductor. The model proposed by Roberto Germane and his collaborators, who first observed the effect, is based on the well-known concept of an exclusion zone. In 2006 Gerald Pollack published seminal work on the exclusion zone and these observations were then reported by several other groups, which all report observations of a coherent water region created at the border between the surface of a hydrophilic material and mass water. Inspired by QED, the model deduces liquid water to be a system consisting of two phases: a matrix of non-coherent water molecules which hosts many "Coherence Domains" (CD), about 0.1 um in size, found in the exclusion zone, but also in the mass volume. The two phases are characterized by different thermodynamic parameters and are in a state of stable non-equilibrium. The coherent phase is described by a quantum state, and in particular a state oscillating between a fundamental state, in which the electrons are firmly bound (ionization energy of 12.60 eV), and an excited state characterized by a configuration of almost free electrons. The energy of the excited state is 12.06 eV, which means that only a small amount of energy, equal to (12.60 - 12.06) eV = 0.54 eV (infrared range), is sufficient to extract an electron. Thus, at a fixed temperature and for a molecule density above a threshold, the transition of the noncoherent water molecules to the coherent state is spontaneous because it brings the system to a lower energy configuration. More precisely, the nearly free electrons must overcome an energy barrier of (0.54 -X) eV, where X ~ 0.1 eV is the difference in electric potential at the boundary of the CD with the non-coherent water. This small amount of energy, ~ 0.44 eV, necessary for electron extraction, makes the coherent water a tank of nearly free electrons that can be easily released by infrared stimulation, quantum tunneling, or small external perturbations. In the case of the two hydrophilic materials, for example, the two phases of water, with the different potentials thereof, behave like the two components of a photovoltaic cell based on semiconductors. Thus, in the cell described in the patent, one of the two sectors has hydrophilic material, which originates more coherence domains in that sector, with respect to the other sector.

[0164] Regarding the physical asymmetry mentioned, the study [7] uses ATR-FTIR spectroscopy in the range 2700-3700 cm-1. Aqueous solutions were prepared with various electrolytes (NaCl, MgCl2, KC1, etc.) at increasing concentrations. The O-H stretching band was analyzed, which is very sensitive to the structure of the hydrogen bond. The result is the constant presence of an isosbestic point at about 3200 cm-1in all the solutions, regardless of the type of electrolyte or concentration (within certain limits). This suggests the coexistence of two states of water: a structured (coherent) one and a disordered (non-coherent) one, as provided by the QED theory of water. The study confirms that water in the presence of electrolytes maintains a two-phase structure, and that the isosbestic point can be seen as an experimental signature of the quantum coherence of water, supporting the theory of Emilio Del Giudice and Giuliano Preparata. Moreover, this work [7] refers to the article [8] on some cells for producing energy from water "Another water based technology in which water droplets jumps from super hydrophobic copper oxide to the hydrophilic copper surface develops an electric output of 15 pw / cm2", which however describe a jumping phenomenon of charged droplets from one metal material to another without there being electrodes, and applying a thermal gradient between the two materials. Preferably according to the invention, no thermal gradient is applied in the cell of the invention, in particular between the two non-metallic hydrophilic materials.

[0165] The inventors found in the laboratory that such a two-phase structure is surprisingly present also in water without electrolytes, observing that the addition of salts does not destroy the coherent domains, but changes the quantitative balance thereof with respect to the disordered fraction. Therefore, the results of the study [7] also apply to water in the absence of salts, i.e., electrolytes. Absorption around 3200 cm-1is associated with the coherent phase, while that at 3400- 3600 cm-1with the free phase. The isosbestic point highlights the reversible transformation between these two states.

[0166] In particular, in the case of water in a hydrophilic gel, water can be in several states:

[0167] — Free water (bulk-like): little or not at all affected by the matrix.

[0168] — Bound water: associated with the polar groups of the gel network.

[0169] — Intermediate water (interface): neither completely free nor rigidly bound.

[0170] Therefore, these states profoundly modify the structure of the hydrogen bond, and therefore also the FTIR spectrum, in particular in the O-H band (stretching between 3000-3700 cm-1), as follows according to the deconvolution of the O-H band into several Gaussian / Lorentzian components:

[0171] — ~3200 cm-1structured water (strong H bonds, similar to ice or the coherent phase) .

[0172] — ~3400-3450 cm-1-> intermediate water.

[0173] — ~3600-3650 cm-1free water (almost without H- bond).

[0174] As an example, Figs. 13-15 show the deconvolution of the FTIR spectra of distilled water and PAAC (hydrogel Poly (acrylic acid)) obtained by the inventors in a specific case. The ordinates show the variation in intensity of the reflected wave on a sample with respect to the incident one and the abscissae show the wavelength in cm-1. The numbers indicated in the figure are the relative percentages of the 4 Gaussians in which the water region was deconvoluted. 4 (instead of 3 Gaussians as in [7]) were used because another OH binding component is present in the gel bound to the structure of the gel and not to water. It is seen that in the case of distilled water (in the region of the OH group associated with water) there is less structuring of the water molecules, while in the PAAC the shorter wavelength components decrease. Fig. 15 shows the result of the PAAC at various time points of a continuous mixing, where at 45 minutes the result of Fig. 13 is obtained.

[0175] The polymer or peptide matrix (in general hydrophilic material) according to the invention favors the formation of coherent domains of water (e.g., confinement, polarity, orientation), or it can break them, favoring disorganization, and thus generating asymmetry. Asymmetry can also be generated by different phenomena occurring on the surface of different inert electrodes, as shown above.

[0176] In this regard, it is possible to use as a hydrogel, or integrated into a hydrogel as a hydrophilic material, xerosydryle, a solid and stable form of water aggregates, which has unique properties of semi-conductivity and interaction with infrared radiation, see [9] and Italian patent No. 1020220000204772 "Method and apparatus for the capture and storage of CO2 carbon in the Xerosydryle structure" for the definition of xerosydryle. Such an xerosydryle is already a structured form of water and therefore lends itself well to use as or in the hydrogels according to the invention. In fact, the inventors have observed that xerosydryle can be produced as a hydrogel.

[0177] Overall, the Oxyhydroelectric Effect is a promising solution for extracting current, offering key advantages with respect to the existing renewable technologies. The ability thereof to convert low-quality thermal energy into high-quality electricity, continuously and in any light condition, opens up new prospects for a sustainable and efficient energy supply.

[0178] References

[0179] [1] International Energy Agency (2022), "Renewables 2022: Analysis and forecast to 2027", Technical Report

[0180] [2] R. Germane, V. Tontodonato, C. Hison, D. Cirillo, F.P. Tuccinardi (2012), "Oxhydroelectric Effect: Electricity from Water by Twin Electrodes", Key Engineering Materials, 495, 100-103

[0181] [3] R. Germane, E. Del Giudice, A. De Ninno, V. Elia, C. Hison, E. Napoli, V. Tontodonato, F. P. Tuccinardi, G. Vitiello (2013), "Oxhydroelectric Effect in bi-distilled water", Key Engineering Materials, 543, 455-459

[0182] [4] Allied Market Research (2021), "Energy Harvesting System Market by Technology (Light Energy Harvesting, Vibration Energy Harvesting, Radio Frequency Energy Harvesting, and Thermal Energy Harvesting), Component (Energy Harvesting Transducers, Power Management Integrated Circuits (PMIC), and Storage System), and Application (Building & Home Automation, Consumer Electronics, Industrial, Transportation, and Others): Global Opportunity Analysis and Industry Forecast, 2021- 2030", Market Research Report

[0183] [5] Mordor Intelligence (2022), "Global Energy Harvesting Systems Market - Growth, Trends, Covid-19 Impact, And Forecasts (2023 - 2028)", Market Research Report

[0184] [6] Italian patent No. 1411927 (11 November 2014) - Procedimento ed apparato per I'estrazione di energia elettrica dall'acqua [Method and apparatus for extracting electricity from water] - Inventors: Roberto Germane, Vittorio Elia; Applicant: OXHY Sri

[0185] [7] A. De Ninno, M. De Francesco, ATR-FTIR study of the isosbestic point in water solution of electrolytes, Chemical Physics 513 (2018) 266-272

[0186] [8] Miljkovic N, Preston DJ, Enright R, Wang EN. Jumpingdroplet electrostatic energy harvesting. Appl. Phys. Lett. 2014

[0187] [9] V. Elia, E. Napoli, R. Germane, D. Naviglio, M. Ciaravolo, G. Dal Poggetto, D. Caputo, R. Oliva, T. A. Yinnon, New physicochemical properties of liquid water resulting from recurrent contact with hydrophilic polymers. Characteristics of the resulting supramolecular aggregates: the Xerosydryle, WATER, 12, 72-85 (2022) DOI: 10.14294 / WATER.2021.2

[0188] Preferred embodiments have been described above and variations of the present invention have been suggested, but it should be understood that those skilled in the art may make modifications and changes without departing from the related scope of protection, as defined by the appended claims.

Claims

CLAIMS1. A method (200) for extracting electricity from a volume of water comprising the steps of:- providing (210) the volume of water in a first and a second portion, no dissolved electrolytes being present in water;- contacting (220) a respective first (70) and second (80) electrode in each first (60) and second (90) portion;- extracting (230) electricity from the volume of water by connecting a load (R) between the aforesaid electrodes (70,80); the method being characterized in that:— the respective first (70) and second (80) electrode are made of electroconductive but chemically inert materials with respect to the generation of oxidoreductive phenomena on the surface thereof;— each first and second portion is comprised in respective non-metallic first material (60) and second material (90) selected from hydrophilic materials;— the respective first (70) and second (80) electrode are different from each other and / or the respective first (60) and second (90) material have different hydrophilicity; thus preventing the production or adsorption of ions on the surface of the respective first (70) and second (80) electrode.

2. The method (200) according to claim 1, wherein the respective first (70) and second (80) electrode are made of the same material but are different in the surface structure thereof.

3. The method (200) according to claim 2, wherein said surface structure differs by degree of surface roughness Ra, "arithmetical mean roughness", and / or Sa "Arithmetic Mean Height - 3D" and / or Sq "Root Mean Square Height - 3D", wherein preferably said surface structure differs by degree of hydrophilicity.

4. The method according to one of claims 1 to 3, wherein, at least on the surface, said respective first (70) and second (80) electrode are made of a material selected from the group comprising or consisting of: platinum, graphite, metal, passivated metal alloy.

5. The method according to one of claims 1 to 5, wherein said first (60) and second (90) hydrophilic material are different first and second hydrogels.

6. The method according to one of claims 1 to 5, wherein said first (60) and second (90) hydrophilic material are a first and a second hydrogel which are equal.

7. The method according to one of claims 1 to 6, wherein said first hydrogel and / or said second hydrogel contain or are made of xerosydryle.

8. The method according to one of claims 1 to 7, wherein said volume of water is without the addition of hydrogen peroxide.

9. The method according to one of claims 1 to 8, wherein no thermal gradient is applied between the firstand second material and / or between the first and second electrode.

10. An apparatus (100) for extracting electricity from water comprising:- a container (110) filled with a volume of water in a first and a second container portion, no dissolved electrolytes being present in water;- a first (70) and a second (80) electrode, respectively placed in contact with water in said first (60) and said second (90) portion;- an electrical load (R) connected between said first and second electrode (70,80); the apparatus being characterized in that:— the respective first (70) and second (80) electrode are made of electroconductive but chemically inert materials with respect to the generation of oxidoreductive phenomena on the surface thereof— each first and second portion is comprised in respective non-metallic first material (60) and second material (90) selected from hydrophilic materials;— the respective first (70) and second (80) electrode are different from each other and / or the respective first (60) and second (90) material have different hydrophilicity; thus preventing the production or adsorption of ions on the surface of the respective first (70) and second (80) electrodes.

11. The apparatus according to claim 10, wherein the respective first (70) and second (80) electrode are madeof the same material but are different in the surface structure thereof, preferably said surface structure differs by degree of roughness or by degree of hydrophilicity .

12. The apparatus according to one of claims 10 or11, wherein, on the surface, said respective first (70) and second (80) electrode are made of a material selected from the group comprising or consisting of: platinum, graphite, metal, passivated metal alloy.

13. The apparatus according to one of claims 10 to12, wherein said first (60) and second (90) hydrophilic material are different first and second hydrogels or said first (60) and second (90) hydrophilic material are a first and a second hydrogel which are equal.

14. The apparatus according to one of claims 10 to13, wherein said volume of water is without addition of hydrogen peroxide.

15. An infrared radiation sensor, comprising the apparatus according to one of claims 11 to 14, wherein a processing unit detecting infrared radiation based on the current passing through the load (R) is comprised.

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