WO2021228897A1 - Flexible system for generating electrical energy, apparatus for discharging electrical energy, method for producing the flexible system and uses thereof - Google Patents

Abstract

The present invention relates to a flexible system, that is, a system which can bend without negatively influencing functionality, for generating electrical energy, an apparatus for discharging electrical energy comprising a plurality of flexible systems, a method for production of the flexible system and uses thereof.

Description

Flexible system for generating electrical energy, device for delivering electrical energy, method for producing the flexible system and

Uses thereof

The present invention relates to a flexible, i.e. bendable system for generating electrical energy, i.e. a system which can be bent without impairing its function, a device for delivering electrical energy comprising a plurality of the flexible systems, a method for producing the flexible system and uses thereof.

For many applications, such as hearing aids, sensors, data loggers or small radio modules, inexpensive primary energy storage devices with very high energy densities and / or high specific energy are required. So far, primary batteries or accumulators ("accumulators") have mostly been used, but they can only provide limited specific amounts of energy and / or are costly and / or toxic and / or have limited storage are capable (e.g. alkaline manganese batteries with approx. 150 Wh / kg, 350 Wh / L, zinc-air batteries with approx. 400 Wh / kg, 1200 Wh / K and lithium thionyl chloride batteries with approx. 600 Wh / kg, 1100 Wh / L).

In addition, fuel cells are known which are coupled to a chemical disposable storage device for generating hydrogen by hydrolysis of a chemical substance (see WO 2014/198948 A1). Metal hydrides offer the advantage of extremely high material-specific energy densities and specific energies, particularly in the case of hydrolysis in fuel cell applications. For example, magnesium hydride has the material-specific energy content of 2900 Wh / L or 2300 Wh / kg (including loss of efficiency) in the following chemical reaction when the resulting hydrogen is converted into electricity in a fuel cell:

MgH + 2 H ₂ 0 _{→ 2H 2} + Mg (OH) ₂

The problem here, especially for mobile and small applications, is that the water required for the reaction and thus to be transported in the system considerably reduces the effective system energy density and system-specific energy of hydrolysis-based power generators.

The patent literature provides the following approaches to solving the problem: Fuel cells are coupled to hydrolysis-based hydrogen gas generators that extract the (ambient air) moisture from the fuel cell or air by means of a selectively water-permeable membrane and transport the hydrogen produced into the fuel cell by means of an electromechanical conveyor device (see WO 2006/091227 A1). The disadvantage here, however, are mechanically moving parts in the conveyor, which lead to a higher system weight, require additional space, cause additional costs and are prone to defects and wear.

US 2003/0228252 A1 describes a metal hydride encased by a water-permeable membrane as a hydrogen generator, for example for fuel cell applications. The disadvantage here, however, is that a hydrogen generator is required as a further component in addition to the fuel cell. This leads under Among other things, it leads to high manufacturing costs and makes system integration difficult, especially for very small applications.

From US 10,522,864 B1 devices are known that can be operated ben with fuel cells. These devices can be operated for a longer period of time if the fuel cells are adapted in such a way that they extract the reactants required to generate electricity from the environment Reactant enriched atmosphere kept at a sufficient level.

DE 10 2006 041 503 relates to a fuel cell system, a fuel cell system and a method for producing a fuel cell system.

In particular, the flexibility of the systems known from the prior art is unsatisfactory, so that they cannot be used in applications in which a certain flexibility is required, or are damaged or even destroyed with appropriate use and / or processing .

Based on this, it was the object of the present invention to provide a device for generating electrical energy, which no longer has the disadvantages known in the prior art.

The object is achieved by a flexible system for generating electrical energy with the features of claim 1, a device for outputting electrical energy with the features of claim 29, a method for producing a system according to the invention with the Merkma len of claim 33 and the use of a system according to the invention having the features of claim 37. The dependent claims show advantageous developments of the invention.

The invention thus relates to a flexible system for generating electrical energy, comprising a) an electrically conductive anode permeable to gases; b) an electrically conductive first gas diffusion layer arranged on the anode; c) a proton exchange membrane which is permeable for protons and for water and largely impermeable for hydrogen and which is arranged on the first gas diffusion layer; d) a second electrically conductive gas diffusion layer arranged on the proton exchange membrane; e) a for water and / or water vapor and oxygen permeable cathode, which is arranged on the second electrically conductive gas diffusion layer; and f) a removable barrier that is at least impermeable to water and / or water vapor and is arranged on the cathode, the anode having at least one space compartment that contains a plastically deformable or flowable, preferably pasty or powdery substance mixture that is suitable for this purpose To release hydrogen through contact with water, and / or the plastically deformable or flowable, preferably pasty or powdery substance mixture is kept in at least one separate space compartment on the side facing away from the proton exchange membrane on the side facing away from the proton exchange membrane, wherein the anode applied to one another, The first gas diffusion layer, proton exchange membrane, second gas diffusion layer and cathode are designed so that they can be reversibly and / or permanently bent in at least one spatial direction in a non-destructive manner and without impairing their function.

Because the overall assembly of the system according to the invention is designed to be flexible, ie it can be bent in a non-destructive manner and without impairing the function, the above-mentioned object can be achieved. The The system according to the invention can thus be used in many ways, especially in application areas in which flexibility of a system to be used is required.

In the system according to the invention, the hydrogen required for operation on the anode side is produced by a chemical reaction of at least one substance of the plastically deformable or flowable, preferably pasty or powdery substance mixture with the water and / or with the moisture of the fluid on the cathode side during operation of the system generated. The fluid on the cathode side can in particular be moist ambient air, which always contains a certain water vapor content; However, other oxygen-containing gas mixtures that also contain gaseous and / or condensed, atomized and / or otherwise finely divided water are also possible.

The term substance includes not only pure chemical substances, but also complex chemical substances of variable composition to which a clear CAS registration number has been or can be assigned.

The terms normal conditions, room temperature and normal pressure are each derived from this information, but refer - unless explicitly stated otherwise - to an atmosphere of dry air (0% relative humidity).

Unless otherwise stated, humid ambient air is understood to mean air with a relative humidity in the range between 5 and 100% with a standard reference atmosphere of 1000 hPa and 20 ° C (based on ISO 8778: 2005).

The remaining subsystem from the middle of the proton exchange membrane and / or its immediate surroundings in which the oxidation of hydrogen takes place is understood as the hydrogen side (synonymous with the anode side).

The remaining subsystem from the middle of the proton exchange membrane and / or its immediate surroundings in which the reduction of oxygen takes place is understood as the oxygen side (synonymous with the cathode side). The anode (synonymous with anode space) is the entire gas space and / or space that is connected to the first gas diffusion layer without any further valves or other shut-off devices and that contains the plastically deformable or flowable, preferably pasty or powdery substance mixture, the hydrogen side of the system which can be designed as a hydrogen flow field, for example, and contains or comprises at least one layer that is electrically conductively connected to the first gas diffusion layer and the catalyst coating of the first gas diffusion layer and / or on the proton exchange membrane on the hydrogen side.

The cathode or cathode space is the space with open structures on the oxygen side of the system that are freely accessible for oxygen-containing fluids, which contains or comprises at least one layer that is electrically conductive with the second gas diffusion layer and the catalyst coating on and / or on the second gas diffusion layer the proton exchange membrane on the oxygen side is connected.

The contacting of the at least one hydrogen-releasing substance in the anode compartment with water releases hydrogen, which can be used to operate the fuel cell. For example, the water required for this can come from the cathode compartment of the system. Furthermore, water is produced during the operation of the system, which can be used to come into contact with the hydrogen-releasing substance located in the anode compartment and thus to release hydrogen (again). The water content of the fluid on the cathode side required for the hydrogen release reaction can thus be reduced or, in other words, the water produced during operation of the fuel cell is recuperated for the chemical reaction to release hydrogen.

Moisture from the cathode compartment can diffuse through the proton exchange membrane into the anode compartment, which can be greatly accelerated by a hygroscopic and / or deliquescent component in the anode compartment. The water transported in this way into the anode compartment then generates the hydrogen necessary for the operation of the fuel cell directly by reaction with the least one substance of the substance mixture which releases hydrogen on contact with water. The term hygroscopic refers to substances which, when stored in humid ambient air, attract humidity, accumulate water and preferably gradually dilute, dissolve and / or clump. The increase in mass of these substances due to absorbed water is preferably more than 1% by weight when the substances are stored in moist ambient air as defined above and a relative humidity of 65% within the first hour.

To start and / or to maintain the generation of electrical energy, the at least one moisture-impermeable or only slightly moisture-permeable barrier can be removed, damaged or made permanently or temporarily otherwise more permeable to moisture, for example by a switching process, which in particular is applied by applying an electrical voltage the barrier can be triggered. The barrier can be part of the device, encasing it, e.g. closing the cathode side of the system. After this barrier (for example a membrane or foil) has been removed, damaged, pierced or otherwise made permeable to moisture, moisture can reach its proton exchange membrane via the cathode space of the system.

The removable barrier, which is at least impermeable to water and water vapor, can in particular be implemented as a reversibly or irreversibly detachable film. This can also be done with an adhesive coating, for example, in order to enable reuse.

Before electricity is generated, the anode compartment can be filled with a certain supply of substance which releases hydrogen on contact with water. In particular, no further substance which releases hydrogen on contact with water is fed to the anode compartment, in particular during operation of the fuel cell contained therein.

The functional principle of the system is therefore somewhat reminiscent of that of a primary battery, in which the amount of energy is also determined by the amount of substance. is given and what enables a simpler and more cost-effective production for the system according to the invention due to the possible dispensing with mechanically movable parts for conveying substances.

A preferred embodiment provides that the bending radius of the anode, first gas diffusion layer, proton exchange membrane, second gas diffusion layer and cathode, which can be achieved without destroying or impairing the function of the fuel cell, is less than 100 mm, preferably less than 50 mm, particularly in at least one spatial direction is preferably less than 10 mm.

According to a further preferred embodiment, the total thickness of the anode, first gas diffusion layer, proton exchange membrane, second gas diffusion layer and cathode is less than 10 mm, preferably less than 5 mm, more preferably from 0.1 to 5 mm, particularly preferably from 0.5 to 2 mm .

In particular, it can be provided that, independently of one another, the anode and cathode have a thickness of 10 μm to 2000 μm, the two gas diffusion layers a thickness of 10 μm to 1000 μm, preferably a thickness of 100 μm to 500 μm, the proton exchange membrane a Thickness of 10 μm to 1000 μm, preferably 10 μm to 50 μm, and the barrier impermeable to water / water vapor has a thickness of 10 μm to 1000 μm, preferably 10 μm to 100 μm.

It is also advantageous that the cathode is designed as a plastic film provided with a large number of openings.

Another advantageous embodiment provides that the at least water and water vapor impermeable, removable barrier at least one material selected from the group consisting of polyethylene, polypropylene, cycloolefin copolymers, polyethylene naphthalate, polyvinylidene chloride, polyvinyl chloride, ethylene-vinyl alcohol copolymer, polyacrylonitrile Contains or consists of polyamide, polyimide, polyvinyl alcohol, polyethylene terephthalate, aluminum, silicon oxide, aluminum oxide and liquid crystalline polymers. The system according to the invention is designed in particular planar or designed in a rotationally symmetrical, preferably cylindrical design, the anode being on the inside of the rotating body and the cathode on the outside thereof.

In the event that the substance mixture is kept in a separate space compartment adjoining the anode on the side facing away from the proton exchange membrane, the anode, first gas diffusion layer, proton exchange membrane, second gas diffusion layer and cathode attached to each other are preferably reversibly detachable / connectable from the space compartment connected to the room compartment.

The reversible composite can preferably be produced by means of Velcro fasteners, clips, bolts, press studs and / or adhesive connections.

In particular, in the system according to the invention, the anode can have at least one space compartment that contains the plastically deformable or flowable, preferably pasty or powdery substance mixture, on the side of the anode facing away from the first gas diffusion layer, a mechanical carrier can be applied, which at least for oxygen and / or Water impermeable, in particular a carrier in the form of a film, particularly preferably in the form of a film metallized on one side, or the plastically deformable or flowable, preferably pasty or powdery substance mixture in a separate space compartment adjoining the anode on the side facing away from the proton exchange membrane be kept in stock, the plastically deformable or flowable, preferably pas tous or powdery substance mixture in an at least for oxygen and / or water impermeable carrier and / or housing be stocked, which at least partially with that of the first gas diffuser ion layer are in contact with the side facing away from the anode, or the plastically deformable or flowable, preferably pasty or powdery substance mixture is in direct contact with the side of the anode facing away from the first gas diffusion layer. Another preferred embodiment provides that the mechanical carrier and / or the housing has a plurality of openings on the side of the anode facing away from the first gas diffusion layer.

It is also advantageous if the mechanical carrier and / or housing is / are cylinder-shaped, the substance mixture being arranged inside the cylinder and the anode, first gas diffusion layer, proton exchange membrane, second gas diffusion layer and cathode being formed on the surface of the cylinder. The last-mentioned embodiment, in which the system is designed in the form of a cylinder, can have the external dimensions of a commercially available battery.

This cylindrical embodiment can in particular be produced by rolling up and / or by winding up a planar system.

Current collectors are preferably arranged at the front ends of the cylinder, one current collector being connected to the anode and the opposing current collector to the cathode in an electrically conductive manner.

It is also preferred that the mechanical carrier and / or the housing is / are formed from a plastic.

In addition, it is advantageous if at least one element to increase the migration speed and / or to reduce the migration paths of one or more fluids (e.g. hydrogen or water) is / are attached within the carrier and / or housing. Furthermore, it is advantageous if this at least one element is designed as a wick, fabric, capillaries, lattice structure and / or an open-line foam structure.

According to a further advantageous embodiment of the present invention, the anode has a hole structure or lattice structure and / or is designed as a woven or nonwoven fabric, with the substance mixture in the holes in the event that the anode has at least one space compartment that contains the substance mixture , is contained in the recesses of the grid and / or within the fabric or nonwoven fabric. Furthermore, it is advantageous if the perforated structure or lattice structure is formed from perforated or lattice-structured polymer foils, metallized polymer foils, metal foils and / or the fabric from graphite fabric foils.

It is also preferred that the plastically deformable or flowable substance mixture i) contains at least one substance for providing hydrogen, selected from the group consisting of substances that are suitable for the chemical reduction of H2O to H2, preferably substances selected from Group consisting of alkali metals, metal hydrides, alkali metal hydridoboranes, alkaline earth metal hydroboranes, alkali metal silicides and mixtures thereof, particularly preferably substances selected from the group consisting of NaH, LiH, LiAIH ₄ , NaAIH ₄ , MgH, CaH, NaBH ₄ , LiBH ₄ , NaSi LiSi, Mg _X RE _fi -x _j H _y with 0 <x <l; 0 <y <3, MgxTMβ-x _j H _y with 0 <x <l; 0 <y <3, (Mg-RE-TM) H _y with 0 <y <3 and mixtures and / or combinations thereof, where RE represents the lanthanides La to Lu of the periodic table and TM represents the transition metals of the periodic table re; and / or ii) less than 10 mm, preferably less than 1 mm, particularly preferably less than 0.1 mm, from the proton exchange membrane and / or from the first gas diffusion layer. The distance described above can also be 0, in which case the substance mixture is in direct contact with the first gas diffusion layer. The distances can be adjusted by varying the thicknesses of the gas diffusion layer and, if necessary, the mechanical carrier.

Another preferred embodiment of the system according to the invention provides that the plastically deformable or flowable substance mixture contains at least one hygroscopic and / or deliquescent component which is different from the substance for providing hydrogen.

In the aforementioned embodiment, it is particularly advantageous if the at least one hygroscopic and / or deliquescent component i) contains or consists of at least one substance which, after incubation with air for one hour at a relative humidity of at least 90% at standard pressure and temperature, binds enough water that its weight gain is at least 0.1 % By weight, preferably at least 1% by weight, particularly preferably at least 10% by weight, standard pressure being understood to mean a pressure of 1013 hPa and standard temperature being understood to mean a temperature of 25 ° C .; and / or ii) a deliquescent humidity of less than 90% relative humidity, preferably less than 75% relative humidity, particularly preferably less than 60% relative humidity at standard pressure and temperature, with a pressure of 1013 under standard pressure hPa and the standard temperature is understood to mean a temperature of 25 ° C; and / or iii) in the at least one space compartment in an amount, based on the total amount of components or substances, 1 to 50% by weight, preferably 10-40% by weight, particularly preferably 15-30% by weight amounts to; and / or iv) an inorganic material selected from the group consisting of zeolite, magnesium silicate, calcium chloride, magnesium chloride, magnesium sulfate, potassium chloride, potassium nitrate, sodium nitrate, magnesium nitrate, calcium nitrate, iron (III) chloride, ammonium nitrate, ammonium chloride, ammonium sulfate, silica gel and contains or consists of mixtures thereof; and / or v) an organic material selected from the group consisting of acetonitrile, urea, dimethyl sulfoxide, ethylene glycol, glycerol, glycerol triacetate, polyethylene glycol and mixtures thereof.

The system according to the invention can preferably be connected on the cathode side with a source of oxygen and water, preferably with i) a gaseous atmosphere, preferably air; and / or ii) a surface of a living or dead person and / or a living or dead animal, preferably a skin surface of a person and / or animal, optionally with the outlet of a respiratory tract of a person and / or animal; and / or iii) a surface of a living or dead plant. System according to one of the preceding claims, characterized in that the proton exchange membrane of the fuel cell i) a material, in particular a copolymer selected from the

5 Group consisting of poly-perfluorosulfonic acid (PFSA), polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), polyperfluoroimidic acid (PFIA), in particular 2- [l- [difluoro [(trifluoroethenyl) oxy] methyl] -1,2,2,2-tetrafluoroethoxy] -1,1,2,2-tetrafluoroethanesulfonic acid contains or consists of it;

10 and / or ii) has a coating with a catalyst, the catalyst being selected from the group consisting of catalysts which catalyze an oxidation of hydrogen with oxygen, preferably a catalyst made from a material selected from

15 Group consisting of Pt, Pt-Co, Pt-Fe, Pt-Ru, Pt-Ni, Pt-Rh, Pt-C.

According to a further preferred embodiment it is provided that the substance mixture contained contains at least one organic substance which

20 is suitable for mediating the reaction between the substance for providing hydrogen with water, the organic substance preferably i) being liquid at a temperature of 25 ° C and a pressure of 1013 hPa; and or

25 ii) is at least partially miscible with water at a temperature of 25 ° C and a pressure of 1013 hPa; and / or iii) is selected from the group of substances which contain at least one carboxylic acid ester group; and / or iv) with the substance for providing hydrogen and / or with

BO of the hygroscopic substance is present as a mixture, preferably present as a homogeneous mixture, the mixture having a semi-solid, spreadable and / or pasty consistency, in particular at a temperature of 25 ° C. and a pressure of 1013 hPa.

The system according to the invention preferably comprises one or more electronic components based on flexible circuit board technology. It is also preferred that no opening to the environment of the system is attached to the anode and / or the carrier and the anode and / or the carrier have no connections for fluids, in particular no feed lines for hydrogen that is stored outside the system, having.

The aforementioned embodiment applies to both variants of the present invention, i. H. both for the variant according to which the anode has at least one space compartment which contains a plastically deformable or flowable, preferably pasty or powdery substance mixture which is suitable for releasing hydrogen through contact with water, as well as the variant according to which the substance mixture in at least one separate space compartment adjoining the anode on the side facing away from the proton exchange membrane is kept.

A system is also in accordance with the invention if it is designed and suitable, in particular, for delivering an electrical power of less than 100 W, preferably 100 pW to 10 W, particularly preferably 1 mW to 100 mW.

In particular, the system according to the invention does not contain any moving mechanical components, in particular no moving components in a hydrogen flow path, especially no pump, no delivery unit, no impeller, no propeller, no impeller, no paddle wheel and no turbine. This significantly reduces the mechanical complexity of the system according to the invention, so that maintenance of the system is superfluous.

An active delivery device for the generated hydrogen or another water-transporting membrane next to the fuel cell is therefore not required, the device for generating electrical energy can be manufactured as a unit, so a hydrogen generator separated from the fuel cell is also not necessary. The most important advantage is the possibility of inexpensive production of a device for generating electrical energy, which can have a multiple of the energy density and specific energy of conventional primary energy stores, but also of accumulators. The system of the present invention can in particular be configured as a fuel cell.

In addition, the present invention relates to a device for delivering electrical energy, comprising a plurality of electrically interconnected systems.

In the device according to the invention, it is advantageous if it is electrically conductively connected to flexible electronic components such as sensors or antennas or flexible printed circuits.

In addition, it is preferred in the device that the fuel cell and substance mixture and, if applicable, electronic components can be reversibly released by means of mechanically releasable connections and the connections are preferably made by means of Velcro fasteners, clamp connectors, screws, spring contacts, magnetic connectors, snap fasteners and / or adhesive connections .

Another preferred embodiment of the device provides that it is part of a device for monitoring medical parameters (e.g. body temperature, blood oxygen saturation, heartbeat) of a person or animal.

The present invention also relates to a method for producing a system according to the invention as described above, in which the plastically deformable or flowable substance mixture (001) is processed to provide hydrogen by printing, spraying, dipping, dispensing, injection molding and / or film casting.

A preferred embodiment of the method provides that the printing takes place by means of screen and / or stencil printing and / or roll-to-roll processes and / or pad printing processes.

For example, the plastically deformable or flowable, preferably paste or powdery substance mixture (001) can also be used to provide Hydrogen is mixed with binder, applied to a substrate and dried ge.

A method is also advantageous if the foils contained in the device are laminated by applying a pressure of more than 100 Pa relative and / or a temperature of more than 50 ° C. and / or using an activatable adhesive.

Furthermore, the present invention relates to the use of a system according to the invention or a device according to the invention as an energy source in an i) data recording device, preferably a device for electronic monitoring of the condition of wounds in a person, an animal and / or a plant, the Device preferably records min least a temperature and humidity; and / or ii) sensor, preferably a sensor for wireless transmission of data, preferably a sensor for radio transmission of data or a sensor for determining a measured variable, eg a temperature sensor, pH sensor or pressure sensor, and / or iii) medical Device, preferably in a hearing aid and / or a wound dressing; and / or iv) device for playing music files and / or video files, preferably a portable device for playing music files and / or video files; and / or v) remote control device, preferably a remote control device for a television set; and / or vi) Device that is attached to the body of the user and / or is integrated into his clothing, preferably a device for analyzing physical and / or medical and / or sporting activities, particularly preferably a wristwatch with a microprocessor (smart watch) , a device for recording physical activity (activity tracker), glasses with additional electronic functions or a sleep analyzer; and or vii) intelligent label, characterized in that it contains at least one electronic component, preferably a microprocessor and particularly preferably also a display unit and / or unit for the wireless transmission of data; and / or viii) headset, headphones or earphones.

In the case of the above-described use, it is advantageous if the at least one opening of the cathode of the device is connected to i) a person and that a water-containing fluid gets into the at least one opening of the device through sweating and / or breathing and / or wound secretion of a person; and / or ii) an animal is connected and that a water-containing fluid reaches the at least one opening of the device through sweating and / or breathing and / or wound secretion of an animal; and / or a plant is connected so that a water-containing fluid reaches the at least one opening of the device by transpiration of the plant.

The present invention is explained in more detail with reference to the following figures, without restricting the invention to the specific embodiments shown.

Here show:

Figure 1 shows a first embodiment of a system according to the present invention,

Figure 2 A second embodiment of a system according to the present invention in the form of a hose,

FIG. 5 shows a third embodiment of a system according to the present invention, in particular for medical applications; Figure 1 illustrates the basic structure of the system according to the invention for generating electrical energy. The system has a mechanical carrier 002 on which an electrically conductive anode with a grid structure 101 is applied. A substance mixture for hydrogen release 001 is introduced into the grid openings (see enlarged detail). A first, electrically conductive gas diffusion layer 102 is arranged over the anode 101. Above this is a proton exchange membrane 10S, above it a second, electrically conductive gas diffusion layer 104 and finally a polymer film (cathode 105) metallized on one side and provided with openings. All of the aforementioned components are implemented as foils that are laminated to form an overall system. The reference symbol 100 denotes the components 101 to 105 combined to form a fuel cell arrangement.

These foils have, for example, thicknesses of 10-500 μm and are e.g.

Metal foils made of copper / aluminum / gold / stainless steels (but also metal mesh) or polymer foils metallized with the metals / alloys mentioned (e.g. for the components for current derivation - or carriers of the (paste-based) hydrogen storage material (components 101 and / or 104)

Polymer foils (e.g. for the carrier 002 of electronics or the metal foils and the proton exchange membrane 103) Graphite fabric foils (e.g. for the gas diffusion layers 102 and 104).

The foils can be structured, for example, by means of common working methods, such as laser structuring, by means of cutting tools, by etching and / or punching.

The substance mixture for hydrogen release 001 (in particular a paste containing MgH2) can e.g. by means of layer deposition, preferably by means of

Screen and stencil printing, pad printing, roll-to-roll process (R2R)

Dispensing by means of: aerosol jet, dispensing jet, microdispenser injection molding are applied and / or introduced.

The individual components can, for example, by means of

Lamination of all foils with pressure and temperature lamination using an adhesive (thermal / photo-activated or 2-component) can be joined to the overall system.

The system shown in Figure 1 is thus a flat structure and represents a thin (total thickness e.g. 0.5-5mm) flexible (bending radii:> 5 mm) energy system. It can be applied to surfaces with different curvatures (see embodiments). The system can be started by removing a start (possibly stop) film 003 (preferably as a moisture barrier) applied to the cathode 105. The overall system thus represents an integrated polymer electrolyte membrane fuel cell based on thin foils. The hydrogen storage device is integrated and, if necessary, designed to be exchangeable. The hydrogen is released on the basis of a hydrolysis reaction - in the case of paste containing MgH2: MgH2 + H2O - 2 H2 + Mg (OH) 2. Due to the flexibility, the integration of electronics based on flexible printed circuit board technology is possible, so that the system comprising printed circuit boards can also retain its flexibility.

FIG. 2 shows an integrated energy system which is constructed analogously to the basic principle presented in FIG. 1. In Figure 2, shown on the left is a longitudinal section through the system, shown on the right is a cross section that illustrates the cylinder-shaped structure. The same reference numerals as shown in FIG. 1 apply. The individual components are rolled up to form a cylinder or hose with a minimum bending radius of 3 mm. The dimensions of the system can also be matched to standard batteries. Also shown in FIG. 2 is the removable barrier 003 which is impermeable to water / water vapor (shown as partially removed). Particular advantages of the system shown in Figure 2 is the relatively large cavity inside the rolled up energy system, which can be used as a fuel storage space for the substance mixture 001 to provide large amounts of energy. As shown on the left in FIG. 2, the film 003 has been partially removed and the system has thus started. In the system shown in Figure 2, the integration of valves is also possible, please include. With the aid of these valves, for example a pressure relief valve 200, the hydrogen pressure inside the system can be controlled, for example. Refilling with a substance mixture to release hydrogen is also possible.

FIG. 5 shows a sensor system based on flexible foils which is suitable for monitoring various environmental parameters, in particular for medical applications. The same reference numerals apply as shown in FIG. The system can be arranged on a surface 300 of any shape, for example human body parts. A shape-flexible carrier 002 (for example a polymer film) that can be arranged on the surface 300 ensures the separation of surface 300 and substance mixture 001 and can additionally accommodate active / passive electronic components and / or function as a flexible printed circuit board. The components can, for example, be integrated circuits 301, antennas 302 and sensor-specific components 303, for example for monitoring a body function, and are supplied with power by the fuel cell 100. The electrical rewiring (also multilayered) can, for example, be based on flexible printed circuit board technology (copper-clad polyimide foils). It is also possible to equip electronics for voltage conversion, signal conditioning and transmission. In the case of a rigid design, the components (301, 302, 303) can be selected to be small enough that the overall system remains flexible or, alternatively, can be flexibly integrated into the film. The rest of the system is structured analogously to the basic principle shown in FIG. The substance mixture for hydrogen release can be exchanged as a film composite; an energy system filled with a new hydrogen-generating substance mixture can be glued onto an electronic rewiring carrier. It is also possible to separate the electronics and the energy system so that individual components can be replaced.

FIG. 4 shows the configuration of a system according to the invention in which the individual components are interchangeably arranged on top of one another. All or individual components of the system can be exchanged (electronics / carrier or housing with substance mixture / fuel cell) so that only the necessary component is possible. In Figure 4 on the left is a system according to the invention, in which the fuel cell 100 (and the removable barrier for water / water vapor 003 arranged on it) by means of a releasable mechanical connection 400 (for example a Velcro or a detachable adhesive connection) on the substance mixture for Water-free set 001 is attached. An alternative embodiment is shown on the right in FIG. 4, in which the individual components of the system are reversibly connected to one another by means of a mechanical connection, for example a button or bolt connection. The fuel cell 100 and / or the substance mixture for hydrogen release 001 after complete consumption can thus be removed or removed and replaced by a new component.

All of the systems according to the invention presented above are particularly suitable for mobile applications in general, in particular for a

Power requirement of <1 watt. Exemplary devices are, for example, smart mobility devices, wareables, sport monitoring devices, IOT (internet of things) devices, medical monitoring devices, such as for monitoring body functions, wound healing monitoring, as well as medical emergency and warning systems and wireless sensor systems for monitoring physical Parameters (e.g. temperature, pressure, pH sensors)

Claims

Claims 1. A flexible system for generating electrical energy, comprising a) a gas-permeable, electrically conductive anode (101); b) an electrically conductive first gas diffusion layer (102) arranged on the anode (101); c) a proton exchange membrane (103) which is permeable for protons and for water and largely impermeable for hydrogen, which proton exchange membrane (103) is arranged on the first gas diffusion layer (102); d) a second electrically conductive gas diffusion layer (104) arranged on the proton exchange membrane (103); e) a for water and / or water vapor and oxygen perme able cathode (105) which is arranged on the second electrically conductive gas diffusion layer (104); and f) a barrier (003) which is at least impermeable to water and / or water vapor and which is removable and which is arranged on the cathode (105), the anode (101) having at least one space compartment which is a plastically deformable or flowable, preferably pasty or powdery substance mixture (001), which is suitable for releasing hydrogen through contact with water, and / or the plastically deformable or flowable, preferably pasty or powdery substance mixture (001) in at least one, separate, to the anode (101) is held in front of the adjacent space compartment on the side facing away from the proton exchange membrane (103), The anode (101), first gas diffusion layer (102), proton exchange membrane (103), second gas diffusion layer (104) and cathode (105) applied to one another are designed so that they can be reversed in at least one spatial direction in a non-destructive manner and without impairing their function and / or let it bend permanently. 2. System according to the preceding claim, characterized in that the bending radius of the stacked anode (101), first gas diffusion layer (102), proton exchange membrane (103), second gas diffusion layer (104), which can be achieved without destroying or impairing the function of the fuel cell (100) ) and cathode (105) in at least one spatial direction is less than 100 mm, preferably less than 50 mm, particularly preferably less than 10 mm. 3. System according to one of the preceding claims, characterized in that the total thickness of the anode (101), first gas diffusion layer (102), proton exchange membrane (103), second gas diffusion layer (104) and cathode (105) is less than 10 mm, preferably less than 5 mm, more preferably from 0.1 to 5 mm, particularly preferably from 0.5 to 2 mm. 4. System according to any one of the preceding claims, characterized in that, independently of one another, the anode (101) and cathode (105) have a thickness of 10 μm to 2000 μm, the two gas diffusion layers (102 and 104) have a thickness of 10 μm to 1000 pm, preferably a thickness of 100 pm to 500 pm, the proton exchange membrane (103) a thickness of 10 pm to 1000 pm, preferably of 10 pm to 50 pm and the barrier (003) impermeable to water / water vapor has a thickness of 10 pm to 1000 pm, preferably from 10 pm to 100 pm. 5. System according to any one of the preceding claims, characterized in that the cathode (105) is designed as a plastic film provided with a plurality of openings. 6. System according to one of the preceding claims, characterized in that the at least impermeable to water and water vapor, detachable barrier (003) is designed as a reversibly or irreversibly detachable polymer film. 7. System according to the preceding claim, characterized in that the at least for water and water vapor impermeable, detachable barrier (003) at least one material selected from the group consisting of polyethylene, polypropylene, cycloolefin copolymers, polyethylene naphthalate, polyvinylidene chloride, polyvinyl chloride , Ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyamide, polyimide, polyvinyl alcohol, polyethylene terephthalate, aluminum, silicon oxide, aluminum oxide and liquid crystalline polymers. 8. System according to one of the preceding claims, characterized in that it is designed in a planar manner or has a rotationally symmetrical, preferably cylindrical design, the anode (101) being on the inside of the rotary body and the cathode (105) on its outside. 9. System according to one of the preceding claims, characterized in that in the event that the plastically deformable or flowable, preferably pasty or powdery substance mixture (001) in a separate, to the anode (101) on which the proton exchange membrane ( 103), the adjacent room compartment facing away from each other is held, the superposed anode (101), first gas diffusion layer (102), proton exchange membrane (103), second gas diffusion layer (104) and cathode (105) from the room compartment are reversibly detachable / connectable to the room compartment. 10. System according to the preceding claim, characterized in that the reversible composite is produced by means of Velcro, clips, bolts, snaps and / or adhesive connection. 11. System according to one of the preceding claims, characterized in that in the case that the anode (101) has at least one space compartment that contains the plastically deformable or flowable, preferably pasty or powdery substance mixture (001) on which the first Gasdiffusi onsschicht (102) facing away from the anode (101), a mechanical carrier (002) is applied which is impermeable to oxygen and / or water, in particular a carrier in the form of a film, particularly preferably in the form of a film metallized on one side, or the plastically deformable or flowable, preferably pasty or powdery substance mixture (001) is kept in a separate space compartment adjoining the anode (101) on the side facing away from the proton exchange membrane (103), the substance mixture (001) in a space compartment at least for oxygen and / or water impermeable carrier (002) and / or housing is stored, which at least partially the side of the anode (101) facing away from the first gas diffusion layer (102) is in contact, or the substance mixture (001) is in direct contact with the side of the anode (101) facing away from the first gas diffusion layer (102). 12. System according to the preceding claim, characterized in that the mechanical carrier (002) and / or the housing has a large number of openings on the side of the anode (101) facing away from the first gas diffusion layer (102). 13. System according to one of the two preceding claims, characterized in that the mechanical carrier (002) and / or housing is / are cylindrical, the plastically deformable or flowable, preferably pasty or powdery mixture (001) arranged inside the cylinder and anode (101), first gas diffusion layer (102), proton exchange membrane (103), second gas diffusion layer (104) and cathode (105) are formed on the surface of the cylinder. 14. System according to the preceding claim, characterized in that current collectors are arranged at the front ends of the cylinder, one current collector being connected to the anode (101) and the opposite current collector to the cathode (105) in an electrically conductive manner. 15. System according to one of claims 11 to 14, characterized in that the mechanical carrier (002) and / or the housing is formed from a plastic. 16. System according to one of claims 11 to 15, characterized in that at least one element for increasing the migration speed and / or for reducing the migration paths of one or more fluids (e.g. hydrogen or water) is attached within the carrier (002) and / or housing is, for example, a wick, Ge tissue, capillaries, a lattice structure and / or an open-line foam structure. 17. System according to one of the preceding claims, characterized in that the anode (101) has a hole structure or lattice structure and / or is designed as a woven or non-woven fabric, wherein in the case that the anode (101) has at least one space compartment, which contains the plastically deformable or flowable, preferably pas tous or powdery substance mixture (001), the substance mixture (001) is contained in the holes, in the recesses of the grid and / or within the fabric or nonwoven fabric. 18. System according to the preceding claim, characterized in that the perforated structure or lattice structure is formed from perforated or lattice-structured polymer films, metallized polymer films, metal foils and / or the fabric from graphite fabric foils. 19. System according to one of the preceding claims, characterized in that the plastically deformable or flowable substance mixture (001), i) contains at least one substance for providing hydrogen, selected from the group consisting of substances that are used for chemical reduction of H2O are suitable for H2, preferably substances selected from the group consisting of alkali metals, metal hydrides, alkali metal hydridoboranes, alkaline earth metal hydride boranes, alkali metal silicides and mixtures thereof, particularly preferably substances selected from the group consisting of NaH, LiH, LiAIH ₄ , NaAIH ₄ , MgH, CaH, NaBH ₄ , LiBH ₄ , NaSi, LiSi, Mg _X RE _fi -x _j H _y with 0 <x <l; 0 <y <3, MgxTTW _fi -x _j H _y with 0 <x <1; 0 <y <3, (Mg-RE-TM) H _y with 0 <y <3 and mixtures and / or combinations thereof, where RE represents the lanthanides La to Lu of the periodic table and TM represents the transition metals of the periodic table; and / or ii) less than 10 mm, preferably less than 1 mm, particularly preferably less than 0.1 mm, from the proton exchange membrane (103) and / or from the first gas diffusion layer (102). 20. System according to one of the preceding claims, characterized in that the plastically deformable or flowable substance mixture (001) contains at least one hygroscopic and / or deliquescent component which differs from the substance for providing hydrogen. 21. System according to the preceding claim, characterized in that the at least one hygroscopic and / or deliquescent component i) contains or consists of at least one substance which is suitable for after a one hour incubation with air at a relative humidity of at least 90% Standard print and temperature to bind so much water that their weight gain is at least 0.1% by weight, preferably at least 1% by weight, particularly preferably at least 10% by weight, with a pressure of 1013 hPa and standard temperature under standard pressure a temperature of 25 ° C is understood; and / or ii) a deliquescent humidity of less than 90% relative humidity, preferably less than 75% relative humidity, particularly preferably less than 60% relative humidity at standard pressure and temperature, with a pressure of 1013 under standard pressure hPa and the standard temperature is understood to mean a temperature of 25 ° C; and / or iii) in the at least one space compartment in an amount, based on the total amount of components or substances, 1 to 50% by weight, preferably 10-40% by weight, particularly preferably 15-30% by weight amounts to; and / or iv) an inorganic material selected from the group consisting of zeolite, magnesium silicate, calcium chloride, magnesium chloride, magnesium sulfate, potassium chloride, potassium nitrate, sodium nitrate, magnesium nitrate, calcium nitrate, iron (III) chloride, ammonium nitrate, ammonium chloride, ammonium sulfate, silica gel and Mixtures contains or consists of these; and / or v) an organic material selected from the group consisting of acetonitrile, urea, dimethyl sulfoxide, ethylene glycol, glycerin, glycerol triacetate, polyethylene glycol and mixtures thereof. 22. System according to one of the preceding claims, characterized in that the system can be connected on the cathode side with a source for oxygen and water, preferably with i) a gaseous atmosphere, preferably air; and / or ii) a surface of a living or dead person and / or a living or dead animal, preferably a skin surface of a person and / or animal, optionally with the outlet of a respiratory tract of a person and / or animal; and or iii) a surface of a living or dead plant. 23. System according to one of the preceding claims, characterized in that the proton exchange membrane (103) of the fuel cell (100) i) a material, in particular a copolymer selected from the group consisting of poly-perfluorosulfonic acid (PFSA), polytetrafluoroethylene (PTFE ), Polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), polyperfluoroimidic acid (PFIA), in particular 2- [l- [difluoro [(trifluoroethenyl) oxy] methyl] -l, 2,2,2-tetrafluoroethoxy] - contains or consists of 1,1,2,2-tetrafluoroethanesulphonic acid; and / or ii) has a coating with a catalyst, the catalyst being selected from the group consisting of catalysts which catalyze the oxidation of hydrogen with oxygen, preferably a catalyst made from a material selected from the group consisting of Pt, Pt-Co, Pt-Fe, Pt-Ru, Pt-Ni, Pt-Rh, Pt-C. 24. System according to one of the preceding claims, characterized in that the plastically deformable or flowable, preferably pasty or powdery substance mixture (001) contains at least one organic substance which is suitable for the reaction between the substance to provide hydrogen with To convey water, wherein the organic substance is preferably i) liquid at a temperature of 25 ° C and a pressure of 1013 hPa; and / or ii) is at least partially miscible with water at a temperature of 25 ° C and a pressure of 1013 hPa; and / or iii) is selected from the group of substances which contain at least one carboxylic acid ester group; and / or iv) is present as a mixture with the substance for providing hydrogen and / or with the hygroscopic substance, preferably as homogeneous mixture is present, the mixture having a semi-solid, spreadable and / or pasty consistency, in particular at a temperature of 25 ° C and a pressure of 1013 hPa. 25. System according to one of the preceding claims, characterized in that it comprises electronic components based on flexible circuit board technology. 26. System according to one of the preceding claims, characterized in that no opening to the environment of the system is made on the anode (101) and / or on the carrier (002) and the anode (101) and / or the carrier (002) has no connections for fluids, in particular no connections for hydrogen. 27. System according to one of the preceding claims, characterized by an electrical power of less than 100 W, preferably 100 pW to 10 W, particularly preferably 1 mW to 100 mW. 28. System according to one of the preceding claims, characterized in that it contains no moving mechanical components, in particular no moving components in a flow path of the hydrogen, especially no pump, no För dereinheit, no impeller, no propeller, no impeller, no Look wheel and not a turbine. 29. A device for delivering electrical energy, comprising a plurality of electrically interconnected systems according to one of the preceding claims. 30. The device according to the preceding claim, characterized in that it is electrically conductively connected to flexible electronic components, for example sensors or antennas or flexible printed circuits. 31. Device according to one of the preceding claims, characterized in that the fuel cell (100) and plastically deformable or flowable, preferably pasty or powdery substance mixture (001) and possibly electronic components by means of mechanically releasable connections (400) are reversibly released and the connections are preferably made by means of Velcro fasteners, clamp connectors, screws, spring contacts, magnetic connectors, snap fasteners and / or adhesive connections. 32. Device according to one of claims 29 to 31, characterized in that it is part of a device for monitoring medical parameters (e.g. body temperature, blood oxygen saturation, heartbeat) of a person or animal. 33. A method for producing a system according to one of claims 1 to 28, in which the plastically deformable or flowable, preferably pasty or powdery substance mixture (001) for providing hydrogen by printing, spraying, dipping and / or dispensing sen and / or injection molding and / or film casting is processed. 34. The method according to the preceding claim, characterized in that the printing takes place by means of screen and / or stencil printing and / or roll-to-roll processes and / or pad printing processes. 35. Method according to one of the two preceding claims, characterized in that the films produced by means of film casting are laminated by applying a pressure of more than 100 Pa relative and / or a temperature of more than 50 ° C and / or using an activatable adhesive will. 36. The method according to any one of claims 33 to 35, characterized in that the plastically deformable or flowable, preferably pasty or powdery substance mixture (001) is mixed with a binder to provide hydrogen, applied to a substrate and dried. 37. Use of a system according to one of claims 1 to 28 or a device according to one of claims 29 to 32 as an energy source in an i) data recording device, preferably a device for electronic monitoring of the condition of wounds in a person, an animal and / or a plant, the device preferably recording at least one temperature and the humidity; and / or ii) sensor, preferably a sensor for wireless transmission of data, preferably a sensor for radio transmission of data or a sensor for determining a measured variable, eg a temperature sensor, pH sensor or pressure sensor, and / or iii) medical Device, preferably in a hearing aid and / or a wound dressing; and / or iv) device for playing music files and / or video files, preferably a portable device for playing music files and / or video files; and / or v) remote control device, preferably a remote control device for a television set; and / or vi) Device that is attached to the body of the user and / or integrated into his clothing, preferably a device for analyzing physical and / or medical and / or sporting activities, particularly preferably a wristwatch with a microprocessor (Smart watch), a device for recording physical activity (activity tracker), glasses with additional electronic functions or a sleep analysis device; and / or vii) intelligent label, characterized in that it contains at least one electronic component, preferably a microprocessor and particularly preferably also a display unit and / or unit for the wireless transmission of data; and / or viii) headset, headphones or earphones. 38. Use according to claim 37, characterized in that the at least one opening of the cathode (105) of the device is connected to i) a person and that a water-containing fluid by sweating and / or breathing and / or wound secretion of a person into the at least one Opening of the device arrives; and / or ii) an animal is connected and that a water-containing fluid reaches the at least one opening of the device through sweating and / or breathing and / or wound secretion of an animal; and / or iii) a plant is connected so that a water-containing fluid reaches the at least one opening of the device by transpiration of the plant.